Manufacturing and compatibilization of binary blends of polyethylene and poly(bulylene succinate) by injection molding

[EN] In this study was analyzed the effect of three different compatibilizers polyethylene-graft-maleic anhydride (PE-g-MA), unmodified halloysite nanotubes (HNTs), and HNTs treated by silanization with (3-glycidyloxypropyl) trimethoxysilane (GLYMO) (silanized HNTs) in blends of bio-based high-density polyethylene (bioPE) and poly(butylene succinate) (PBS) with a weight ratio of (70/30). Each compatibilizer was added in a proportion of (3 phr regarding PBS). Standard samples were obtained by extrusion and subsequent injection molding. The analyzes of the samples were performed by mechanical tests, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), field emission scanning electron microscopy (FESEM), and wettability (θw). Results suggest that the addition of modified HNTs (silanized HNTs) allowed to obtain better properties than samples compatibilized with unmodified HNTs and PE-g-MA, due to it contributes with the improvement in mechanical properties regarding bioPE/PBS blend, for instance, the tensile modulus and elongation at break increase about 8% and 13%, respectively. In addition, it was determined through FESEM images and that silanized HNTs particles were better dispersed over the matrix, which in fact contribute to the enhance in mechanical properties. TGA showed that silanized HNTs delay the degradation temperature regarding the uncompatibilized blend. While DMTA indicated the reduction in the mobility of the chains in samples with unmodified and modified HNTs. Therefore, it was successfully obtained compatibilized bioPE/PBS blends, which constitutes an interesting option to develop new sustainable polymers.Rojas-Lema, S.; Ivorra-Martinez, J.; Gomez-Caturla, J.; Balart, R.; Garcia-Garcia, D. (2021). Manufacturing and compatibilization of binary blends of polyethylene and poly(bulylene succinate) by injection molding. Journal of Applied Research in Technology & Engineering. 2(2):71-81. https://doi.org/10.4995/jarte.2021.15727OJS718122Abd El-Rahman, K.M., Ali, S.F.A., Khalil, A., & Kandil, S. (2020). Influence of poly (butylene succinate) and calcium carbonate nanoparticles on the biodegradability of high density-polyethylene nanocomposites. Journal of Polymer Research, 27(8), 1-21. https://doi.org/10.1007/s10965-020-02217-yAbdolrasouli, M.H., Nazockdast, H., Sadeghi, G.M.M., & Kaschta, J. (2015). Morphology development, melt linear viscoelastic properties and crystallinity of polylactide/polyethylene/organoclay blend nanocomposites. Journal of Applied Polymer Science, 132(3). https://doi.org/10.1002/app.41300Aldas, M., Pavon, C., Ferri, J.M., Arrieta, M.P., & López-Martínez, J. (2021). 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Composites Part A: Applied Science and Manufacturing, 40(5), 669-674. https://doi. org/10.1016/j.compositesa.2009.03.002Liu, L., Yu, J., Cheng, L., Yang, X. (2009). Biodegradability of poly(butylene succinate) (PBS) composite reinforced with jute fibre. Polymer Degradation and Stability, 94(1), 90-94. https://doi.org/10.1016/j.polymdegradstab.2008.10.013Lochab, B., Varma, I., & Bijwea, J. (2012). Sustainable polymers derived from naturally occurring materials. Advances in Materials Physics and Chemistry, 2(4), 221-225. https://doi.org/10.4236/ampc.2012.24B056Montava-Jorda, S., Chacon, V., Lascano, D., Sanchez-Nacher, L., & Montanes, N. (2019). Manufacturing and characterization of functionalized aliphatic polyester from poly (lactic acid) with halloysite nanotubes. Polymers, 11(8), 1314. https://doi.org/10.3390/polym11081314Nuñez, K., Rosales, C., Perera, R., Villarreal, N., Pastor, J. (2012). Poly(lactic acid)/low-density polyethylene blends and its nanocomposites based on sepiolite. 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Assessment of the mechanical and thermal properties of injection-molded poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)/hydroxyapatite nanoparticles parts for use in bone tissue engineering

In the present study, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) [P(3HB-co-3HHx)] was reinforced with hydroxyapatite nanoparticles (nHA) to produce novel nanocomposites for potential uses in bone reconstruction. Contents of nHA in the 2.5–20 wt % range were incorporated into P(3HB-co-3HHx) by melt compounding and the resulting pellets were shaped into parts by injection molding. The addition of nHA improved the mechanical strength and the thermomechanical resistance of the microbial copolyester parts. In particular, the addition of 20 wt % of nHA increased the tensile (Et) and flexural (Ef) moduli by approximately 64% and 61%, respectively. At the highest contents, however, the nanoparticles tended to agglomerate, and the ductility, toughness, and thermal stability of the parts also declined. The P(3HB-co-3HHx) parts filled with nHA contents of up to 10 wt % matched more closely the mechanical properties of the native bone in terms of strength and ductility when compared with metal alloys and other biopolymers used in bone tissue engineering. This fact, in combination with their biocompatibility, enables the development of nanocomposite parts to be applied as low-stress implantable devices that can promote bone reconstruction and be reabsorbed into the human body.L.Q.-C. wants to thank GVA for his FPI grant (ACIF/2016/182) and the Spanish Ministry of Education, Culture, and Sports (MECD) for his FPU grant (FPU15/03812). S.T.-G. acknowledges MICI for his Juan de la Cierva–Incorporación contract (IJCI-2016-29675). J.I.-M. wants to thank Universitat Politècnica de València for his FPI grant (PAID-2019- SP20190011). Microscopy services of the Universitat Politècnica de València (UPV) are acknowledged for their help in collecting and analyzing the FESEM images. Authors also thank Ercros S.A. for kindly supplying ErcrosBio® PH110.This research work was funded by the Spanish Ministry of Science and Innovation (MICI) project numbers RTI2018-097249-B-C21 and MAT2017-84909-C2-2-R and the POLISABIO program with grant number 2019-A02

The effects of processing parameters on mechanical properties of 3D-printed polyhydroxyalkanoates parts

[EN] The crystallisation process of polyhydroxyalkanoates (PHA) polymers plays a key role on final properties of manufactured parts due to most PHA are highly sensitive to physical aging which leads to embrittlement. The secondary crystallisation associated with the aging process can be partially controlled by the cooling process during manufacturing or, even, by heat treatments such as annealing. A critical parameter in additive manufacturing is the difficulty to achieve good adhesion of the material to the printing bed. The bed temperature plays a key role on PHBH crystallisation, which leads to shrinkage having a negative effect on polymer-to-bed adhesion. In this work, a study of the effect of different processing parameters such as the printing temperature, the bed temperature, the cooling conditions, as well as raster direction on the final properties of PHBH 3D-printed parts is carried out.This research is a part of the grant PID2020-116496RB-C22 funded by MCIN/AEI/10.13039/501100011033. Authors also thank Generalitat Valenciana-GVA for funding this research through the grant numbers AICO/2021/025 and CIGE/2021/ 094. Wants to thank the Ministerio de Ciencia e Innovación and Universities for his FPU grant (FPU19/01759). Wants to thank Generalitat Valenciana-GVA, for his FPI grant (ACIF/2021/ 185) and grant FPU20/01732 funded by MCIN/AEI/10.13039/ 501100011033 and by ESF Investing in your future. Funding for open access charge: Universitat Politècnica de València.Ivorra-Martinez, J.; Peydro, MA.; Gómez-Caturla, J.; Sanchez-Nacher, L.; Boronat, T.; Balart, R. (2023). The effects of processing parameters on mechanical properties of 3D-printed polyhydroxyalkanoates parts. Virtual and Physical Prototyping (Online). 18(1). https://doi.org/10.1080/17452759.2022.216473418

Development and Characterization of Weft-Knitted Fabrics of Naturally Occurring Polymer Fibers for Sustainable and Functional Textiles

[EN] This study focuses on the potential uses in textiles of fibers of soy protein (SP) and chitin, which are naturally occurring polymers that can be obtained from agricultural and food processing by-products and wastes. The as-received natural fibers were first subjected to a three-step manufacturing process to develop yarns that were, thereafter, converted into fabrics by weft knitting. Different characterizations in terms of physical properties and comfort parameters were carried out on the natural fibers and compared to waste derived fibers of coir and also conventional cotton and cotton-based fibers, which are widely used in the textile industry. The evaluation of the geometry and mechanical properties revealed that both SP and chitin fibers showed similar fineness and tenacity values than cotton, whereas coir did not achieve the expected properties to develop fabrics. In relation to the moisture content, it was found that the SP fibers outperformed the other natural fibers, which could successfully avoid variations in the mechanical performance of their fabrics as well as impair the growth of microorganisms. In addition, the antimicrobial activity of the natural fibers was assessed against different bacteria and fungi that are typically found on the skin. The obtained results indicated that the fibers of chitin and also SP, being the latter functionalized with biocides during the fiber-formation process, showed a high antimicrobial activity. In particular, reductions of up to 100% and 60% were attained for the bacteria and fungi strains, respectively. Finally, textile comfort was evaluated on the weft-knitted fabrics of the chitin and SP fibers by means of thermal and tactile tests. The comfort analysis indicated that the thermal resistance of both fabrics was similar to that of cotton, whereas their air permeability was higher, particularly for chitin due to its higher fineness, which makes these natural fibers very promising for summer clothes. Both the SP and chitin fabrics also presented relatively similar values of fullness and softness than the pure cotton fabric in terms of body feeling and richness. However, the cotton/polyester fabric was the only one that achieved a good range for uses in winter-autumn cloths. Therefore, the results of this work demonstrate that non-conventional chitin and SP fibers can be considered as potential candidates to replace cotton fibers in fabrics for the textile industry due to their high comfort and improved sustainability. Furthermore, these natural fibers can also serve to develop novel functional textiles with antimicrobial properties.This research work was funded by the Spanish Ministry of Science and Innovation (MICI) project number MAT2017-84909-C2-2-R.Ferrándiz, M.; Fages, E.; Rojas-Lema, SP.; Ivorra-Martinez, J.; Gomez-Caturla, J.; Torres-Giner, S. (2021). Development and Characterization of Weft-Knitted Fabrics of Naturally Occurring Polymer Fibers for Sustainable and Functional Textiles. Polymers. 13(4):1-17. https://doi.org/10.3390/polym13040665S11713

Upgrading argan shell wastes in wood plastic composites with biobased polyethylene matrix and different compatibilizers

The present study reports on the development of wood plastic composites (WPC) based on micronized argan shell (MAS) as a filler and high-density polyethylene obtained from sugarcane (Bio-HDPE), following the principles proposed by the circular economy in which the aim is to achieve zero waste by the introduction of residues of argan as a filler. The blends were prepared by extrusion and injection molding processes. In order to improve compatibility between the argan particles and the green polyolefin, different compatibilizers and additional filler were used, namely polyethylene grafted maleic anhydride (PE-g-MA 3 wt.-%), maleinized linseed oil (MLO 7.5 phr), halloysite nanotubes (HNTs 7.5 phr), and a combination of MLO and HNTs (3.75 phr each). The mechanical, morphological, thermal, thermomechanical, colorimetric, and wettability properties of each blend were analyzed. The results show that MAS acts as a reinforcing filler, increasing the stiffness of the Bio-HDPE, and that HNTs further increases this reinforcing effect. MLO and PE-g-MA, altogether with HNTs, improve the compatibility between MAS and Bio-HDPE, particularly due to bonds formed between oxygen-based groups present in each compound. Thermal stability was also improved provided by the addition of MAS and HNTs. All in all, reddish-like brown wood plastic composites with improved stiffness, good thermal stability, enhanced compatibility, and good wettability properties were obtained.Fil: Jorda Reolid, Maria. Asociación de Investigación de la Industria del Juguete; ArgentinaFil: Gomez Caturla, Jaume. Universidad Politécnica de Valencia; EspañaFil: Ivorra Martinez, Juan. Universidad Politécnica de Valencia; EspañaFil: Stefani, Pablo Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Rojas Lema, Sandra. Asociación de Investigación de la Industria del Juguete; ArgentinaFil: Quiles Carrillo, Luis. Asociación de Investigación de la Industria del Juguete; Argentin

Development and evaluation of novel nanofibers based on mango kernel starch obtained by electrospinning

[EN] This work reports on the development of fibers based on natural mango kernel starch (MKS) with diameters in the nanoscalse by means of the electrospinning technique. MKS was extracted from mango kernels and two synthetic polymers, namely polyvinyl alcohol (PVA) and polyvinylpyrrolidone (PVP), were blended with MKS in order to improve its spinnability, obtaining MKS/PVA and MKS/PVP fibers with a 10 wt% of total polymer concentration. Several electrospinning conditions (voltage and flux) were tested in solutions of MKS concentrations ranging from 0 to 5 wt% for both group of fibers. The morphology of all the fibers was evaluated by field emission scanning electron microscopy (FESEM) and their topography was analysed by means of atomic force microscopy (AFM). MKS/PVA nanofibers were obtained with a diameter range from 0.146 to 0.315 ¿m, with a ¿smooth fiber concentration threshold¿ of 3 wt%, while MKS/PVP, fibers with diameters from 0.080 to 0.339 ¿m were produced, but 5 wt% MKS concentration fibers were beaded fibers, as a result of an excess in starch concentration. Finally, the roughness of the optimal fibers showed quite a similar trend to that of fiber diameter, presenting roughnessess between 80 and 343 nm.This research is a part of the grant PID2020-116496RB-C22 funded by MCIN/AEI/10.13039/501100011033. Authors also thank Generalitat Valenciana-GVA, grant number AICO/2021/025 for supporting this work. J. Gomez-Caturla wants to thank Generalitat Valenciana-GVA, for his FPI grant (ACIF/2021/185) and grant FPU20/01732 funded by MCIN/AEI/10.13039/501100011033 and by ESF Investing in your future. J. Ivorra-Martinez wants to thank FPU19/01759 grant funded by MCIN/AEI/10.13039/501100011033 and by ESF Investing in your future. Microscopy Services at UPV are also acknowledged by their help in collecting and analyzing images.Gómez-Caturla, J.; Ivorra-Martinez, J.; Lascano-Aimacaña, DS.; Balart, R.; Garcia-Garcia, D.; Dominici, F.; Puglia, D.... (2022). Development and evaluation of novel nanofibers based on mango kernel starch obtained by electrospinning. Polymer Testing. 106:1-12. https://doi.org/10.1016/j.polymertesting.2021.10746211210

Development of Injection-Molded Polylactide Pieces with High Toughness by the Addition of Lactic Acid Oligomer and Characterization of Their Shape Memory Behavior

[EN] This work reports the effect of the addition of an oligomer of lactic acid (OLA), in the 5-20 wt% range, on the processing and properties of polylactide (PLA) pieces prepared by injection molding. The obtained results suggested that the here-tested OLA mainly performs as an impact modifier for PLA, showing a percentage increase in the impact strength of approximately 171% for the injection-molded pieces containing 15 wt% OLA. A slight plasticization was observed by the decrease of the glass transition temperature (T-g) of PLA of up to 12.5 degrees C. The OLA addition also promoted a reduction of the cold crystallization temperature (T-cc) of more than 10 degrees C due to an increased motion of the biopolymer chains and the potential nucleating effect of the short oligomer chains. Moreover, the shape memory behavior of the PLA samples was characterized by flexural tests with different deformation angles, that is, 15 degrees, 30 degrees, 60 degrees, and 90 degrees. The obtained results confirmed the extraordinary effect of OLA on the shape memory recovery (R-r) of PLA, which increased linearly as the OLA loading increased. In particular, the OLA-containing PLA samples were able to successfully recover over 95% of their original shape for low deformation angles, while they still reached nearly 70% of recovery for the highest angles. Therefore, the present OLA can be successfully used as a novel additive to improve the toughness and shape memory behavior of compostable packaging articles based on PLA in the new frame of the Circular Economy.This research work was funded by the Spanish Ministry of Science, Innovation, and Universities (MICIU) project numbers RTI2018-097249-B-C21 and MAT2017-84909-C2-2-R. L.Q.-C. wants to thank Generalitat Valenciana (GVA) for his FPI grant (ACIF/2016/182) and the Spanish Ministry of Education, Culture, and Sports (MECD) for his FPU grant (FPU15/03812). D.L. thanks Universitat Politècnica de València (UPV) for the grant received through the PAID-01-18 program. S.T.-G. is recipient of a Juan de la Cierva contract (IJCI-2016-29675) from MICIU. S.R.-L. is recipient of a Santiago Grisolía contract (GRISOLIAP/2019/132) from GVA. J.I.-M. wants to thank UPV for an FPI grant PAID-01-19 (SP2019001). Microscopy services of UPV are acknowledged for their help in collecting and analyzing the microscopy images. Authors also thank Condensia Química S.A. for kindly supplying Glyoplast OLA 2.Lascano-Aimacaña, DS.; Moraga, G.; Ivorra-Martínez, J.; Rojas-Lema, SP.; Torres-Giner, S.; Balart, R.; Boronat, T.... (2019). Development of Injection-Molded Polylactide Pieces with High Toughness by the Addition of Lactic Acid Oligomer and Characterization of Their Shape Memory Behavior. Polymers. 11(12):1-19. https://doi.org/10.3390/polym11122099S1191112Dijkstra, P. J., Du, H., & Feijen, J. (2011). 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The nutrigenetic influence of the interaction between dietary vitamin E and TXN and COMT gene polymorphisms on waist circumference: a case control study

Journal Article; Research Support, Non-U.S. Gov't;BACKGROUND Abdominal obesity (AO) is a common modifiable risk factor for certain non-communicable diseases associated with enhanced oxidative stress (OS). The objective of this work was to investigate whether the interaction between antioxidant vitamin intake and OS-related polymorphisms modulates gene-associated anthropometry in a Spanish population. METHODS A total of 246 subjects with AO, and 492 age and gender matched non-AO subjects were included in the study. Anthropometric, biochemical, and OS parameters, and antioxidant dietary intake data were assessed using validated procedures. DNA from white blood cells was isolated and the genotype of seven polymorphisms from genes involved in OS (pro-oxidant and antioxidant) were analyzed using the SNPlex system. The effects of the c.-793T > C polymorphism on promoter activity and thus thioredoxin (TXN) activity were examined using reporter assays. RESULTS The AO group had higher 8-Oxo-2'-deoxyguanosine levels and took in less vitamin A and vitamin E compared to the non-AO group. Logistic regression analysis revealed that the rs2301241 polymorphism in TXN and rs740603 in catechol-O-methyltransferase (COMT) were associated with waist circumference (WC) and AO. Moreover, these polymorphisms were more strongly associated with variations in WC in subjects with low vitamin E intakes. A promoter assay revealed that the T to C conversion at c.-793 (rs2301241) induced a more than two fold increase in reporter gene expression. CONCLUSIONS WC is associated both with dietary vitamin E intake and genetic variants of TXN and COMT suggesting that existence of a complex nutrigenetic pathway that involves regulation of AO.This work was co-funded with European Funds for Regional Development (FEDER), the Spanish Science and Technology Ministry [SAF2005-02883]; the health research fund from the Carlos III Health Institute [PI070497], CIBER Fisiopatología Obesidad y Nutrición (CIBERobn) [CB06/03], and CIBER de Diabetes y Enfermedades Metabólicas Relacionadas (CIBERDEM). CIBEROB and CIBERDEM are initiatives by the Carlos III Health Institute in Madrid and the Spanish Health Ministry. Funding also came from GRUPOS 03/101, PROMETEO/2009/029 and 2005/027, AMP07/075, and ACOMP/2009/201 from the Valencian Government and European Network of Excellence InGenious HyperCare (EPSS-037093) from the European Commission.Ye

Abacavir increases purinergic P2X7 receptor activation by ATP: does a pro-inflammatory synergism underlie its cardiovascular toxicity?

16 p.-9 fig.-1 tab.The cardiovascular toxicity of Abacavir is related to its purinergic structure. Purinergic P2X7-receptors (P2X7R), characterized by activation by high concentrations of ATP and with high plasticity, seem implicated. We appraise the nature of the interplay between Abacavir and P2X7R in generating vascular inflammation. The effects of Abacavir on leukocyte-endothelium interactions were compared with those of its metabolite carbovir triphosphate (CBV-TP) or ATP in the presence of apyrase (ATP-ase) or A804598 (P2X7R-antagonist). CBV-TP and ATP levels were evaluated by HPLC, while binding of Abacavir, CBV-TP and ATP to P2X7R was assessed by radioligand and docking studies. Hypersensitivity studies explored a potential allosteric action of Abacavir. Clinical concentrations of Abacavir (20 µmol/L) induced leukocyte-endothelial cell interactions by specifically activating P2X7R, but the drug did not show affinity for the P2X7R ATP-binding site (site 1). CBV-TP levels were undetectable in Abacavir-treated cells, while those of ATP were unaltered. The effects of Abacavir were Apyrase-dependent, implying dependence on endogenous ATP. Exogenous ATP induced a profile of proinflammatory actions similar to Abacavir, but was not entirely P2X7R-dependent. Docking calculations suggested ATP-binding to sites 1 and 2, and Abacavir-binding only to allosteric site 2. A combination of concentrations of Abacavir (1 µmol/L) and ATP (0.1 µmol/L) that had no effect when administered separately induced leukocyte-endothelium interactions mediated by P2X7R and involving Connexin43 channels. Therefore, Abacavir acts as a positive allosteric modulator of P2X7R, turning low concentrations of endogenous ATP themselves incapable of stimulating P2X7R into a functional proinflammatory agonist of the receptor.This work was supported by Ministerio de Economía y Competitividad and the European Regional Development fund of the European Union (FEDER) (SAF2015–67678-R, RTI2018-094436-B-I00 and CTQ2017-88353-R), Ministerio de Sanidad y Consumo (CB06/04/0071, CIBERehd) and Generalitat Valenciana (PROMETEOII/2014/035 and PROMETEO 2018/141), along with an unrestricted grant from GILEAD S.L. VCD and ASL were funded by VALI + D program from Generalitat Valenciana (grants number ACIF/2015/316 and ACIF/2016/119, respectively) and PGM by FPU program from Ministerio de Educación, Cultura y Deporte (grant number FPU16/06064) and MABR by FPU program from Ministerio de Ciencia, Innovación y Universidades (grant number FPU17/04249).Peer reviewe

The nutrigenetic influence of the interaction between dietary vitamin E and TXN and COMT gene polymorphisms on waist circumference: a case control study

Background: Abdominal obesity (AO) is a common modifiable risk factor for certain non-communicable diseases associated with enhanced oxidative stress (OS). The objective of this work was to investigate whether the interaction between antioxidant vitamin intake and OS-related polymorphisms modulates gene-associated anthropometry in a Spanish population. Methods: A total of 246 subjects with AO, and 492 age and gender matched non-AO subjects were included in the study. Anthropometric, biochemical, and OS parameters, and antioxidant dietary intake data were assessed using validated procedures. DNA from white blood cells was isolated and the genotype of seven polymorphisms from genes involved in OS (pro-oxidant and antioxidant) were analyzed using the SNPlex system. The effects of the c.-793T > C polymorphism on promoter activity and thus thioredoxin (TXN) activity were examined using reporter assays. Results: The AO group had higher 8-Oxo-2′-deoxyguanosine levels and took in less vitamin A and vitamin E compared to the non-AO group. Logistic regression analysis revealed that the rs2301241 polymorphism in TXN and rs740603 in catechol-O-methyltransferase (COMT) were associated with waist circumference (WC) and AO. Moreover, these polymorphisms were more strongly associated with variations in WC in subjects with low vitamin E intakes. A promoter assay revealed that the T to C conversion at c.-793 (rs2301241) induced a more than two fold increase in reporter gene expression. Conclusions: WC is associated both with dietary vitamin E intake and genetic variants of TXN and COMT suggesting that existence of a complex nutrigenetic pathway that involves regulation of AO