Properties of bio-based gum Arabic/clay aerogels

Lightweight bio-based aerogels from sustainable gum Arabic (GA) and sodium montmorillonite (Na+-MMT) clay were prepared by means of a simple freeze-drying process. GA/clay aerogels showed high porosity (87.9%–94.9%) of mainly open type and the mechanical properties were improved by the clay. When 40% of clay was added to pure GA, the specific modulus and the absorbed energy of resultant aerogels increased by 1.6 and 4.2 times respectively. On the other hand, the exponent value for modulus in the power-law model for cellular materials increased from 1.95 to 3.28 due to the more anisotropic structures induced by the presence of the clay. In terms of thermal stability and flame retardancy, clay content played a dominant role. With 50% of clay loading, the initial decomposition temperature increased by nearly 16 °C and the peak of heat release rate was 3-fold reduced.Peer ReviewedPostprint (author's final draft

A Review of the recent advances in cyclic butylene terephthalate technology and its composites

Cyclic butylene terephthalate (CBT®) oligomers are a relatively new class of material and are capable of polymerizing in an entropically driven ring-opening polymerization into high-molecular-weight polymerized CBT (pCBT) in very short times, i.e., within minutes. The most important feature of CBT is its very low, water-like melt viscosity prior to polymerization which gives rise to an excellent impregnation of fibrous reinforcements in contrast to conventional, high viscous thermoplastic resins. This opens up new possibilities in the thermoplastic composite production since thermoplastic-based composites show some advantages over thermoset-based ones. Specifically, they have a higher toughness and impact strength and they can be welded, postformed, and recycled due to their thermoplastic nature. CBT has the potential to substitute thermoset matrices in fiber-reinforced composites and may solve some of the today´s recycling issues associated with thermoset-based composites. Moreover, the low melt viscosity of CBT enhances the dispersion of nano- or conductive particles and can yield superior nano- and conductive composites. This article reviews the recent advances in processing–structure–property relationship, physical and chemical modification of pCBT, as well as the preparation of fiber-reinforced pCBT composites, pCBT nanocomposites, and conductive pCBT composites.Peer ReviewedPostprint (author's final draft

PVA/ alginate/ tannic acid crosslinked aerogels with low flammability and high mechanical resistance

Aerogels are ultra-light, highly porous materials derived from gels in which the solvent has been replaced by gas. Aerogels based on renewable and biodegradable materials are gained attention as environmentally friendly alternatives to conventional foam [1]. This study focuses on the mechanical, thermal, and combustion behavior of a polyvinyl alcohol (PVA), sodium alginate (SA) and tannic acid (TA) aerogel obtained by freeze-drying and ion crosslinking (Ca2+ and B - ). Aerogels containing 5g of PVA, 3g of TA, and 2g of SA exhibit the highest compressive resistance, which was increased by 30% after crosslinking (87.4 MPa/gcm -3 ). In comparison to pure PVA, the addition of TA and SA to the blends decreased its thermal degradation rate. The crosslinking further contributed to an 81% of reduction of the degradation rate (0.16 %/ºC) making samples high thermally stable. Regarding flammability samples burnt after being exposed to radiation due to the presence of the highly combustible PVA. However, the heat release rate (HRR) and fire growth (FIGRA) parameters decreased by 67% and 50% respectively when TA and SA was added to pure PVA aerogel. After crosslinking, an additional decrement of 35% in HRR and 54% in FIGRA respectively was obtained (76 kW/m2 and 1.96 kW/m2 s), which corresponds to a very low flame intensity. These results are down below of previous values reported by Wu et al.[2], who worked on PVA/SA crosslinking aerogels filled with inorganic montmorillonite. Hence, the cross-linked aerogels presented here can be considered a very promising sustainable alternative to conventional fossil-derived foams

Effect of the viscosity ratio on the PLA/PA10.10 bioblends morphology and mechanical properties

PLA bio-blends with a predominantly biosourced PA10.10 in the composition range 10-50wt.% were prepared by melt blending in order to overcome the advanced brittleness of PLA. Due to the inherent immiscibility of the blends, 30 wt.% of PA was needed to achieve a brittle-to-ductile transition and a co-continuous morphology was predicted at 58 wt.% of PA. The initial enhancement of the PLA rheological behaviour through the environmentally friendly reactive extrusion process yielded a finer and more homogeneous microstructure and hence enhanced the mechanical properties of the bio-blends at much lower PA contents. The brittle-to-ductile transition could be achieved with only 10 wt.% and co-continuity was observed already at 44 wt.% of PA. Results indicate the significant potential of modifying PLA flow behaviour as a promising green manufacturing method toward expanding PLA-based bio-blends applications.Peer ReviewedPostprint (published version

Properties of freeze-dried gelatin/clay aerogel composites crosslinked with tannic acid

Polymer-based aerogels are tough, low-density, and thermally insulating materials currently receiving increasing attention. In this work, robust all-natural aerogel composites have been obtained by incorporating nanoscale montmorillonite and tannic acid into a gelatin matrix via freeze-drying. The prepared aerogels exhibited low densities, good compressive properties, and low thermal conductivities. The significant improvement in the thermomechanical properties results from the strong bonding between gelatin and tannic acid. Under fire, the systems exhibited excellent flame retardancy with reduced thermal degradation rate and cone calorimeter burning parameters. A straightforward surface treatment with polydimethylsiloxane gave the aerogels exceptional and durable superhydrophobicity. These multifunctional composite aerogels are considered promising eco-friendly alternatives to synthetic polymer-based foams.Peer ReviewedPostprint (published version

PLA/PA bio-blends: induced morphology by extrusion

The effect of processing conditions on the final morphology of Poly(Lactic Acid) (PLA) with bio-based Polyamide 10.10 (PA) 70/30 blends is analyzed in this paper. Two types of PLA were used: Commercial (neat PLA) and a rheologically modified PLA (PLAREx), with higher melt elasticity produced by reactive extrusion. To evaluate the ability of in situ micro-fibrillation (µf) of PA phase during blend compounding by twin-screw extrusion, two processing parameters were varied: (i) Screw speed rotation (rpm); and (ii) take-up velocity, to induce a hot stretching with different Draw Ratios (DR). The potential ability of PA-µf in both bio-blends was evaluated by the viscosity (p) and elasticity (k’) ratios determined from the rheological tests of pristine polymers. When PLAREx was used, the requirements for PA-µf was fulfilled in the shear rate range observed at the extrusion die. Scanning electron microscopy (SEM) observations revealed that, unlike neat PLA, PLAREx promoted PA-µf without hot stretching and the aspect ratio increased as DR increased. For neat PLA-based blends, PA-µf was promoted during the hot stretching stage. DMTA analysis revealed that the use of PLAREx PLAREx resulted in a better mechanical performance in the rubbery region (T > Tg PLA-phase) due to the PA-µf morphology obtained.Peer ReviewedPostprint (published version

Ice-template crosslinked PVA aerogels modified with tannic acid and sodium alginate

With the commitment to reducing environmental impact, bio-based and biodegradable aerogels may be one approach when looking for greener solutions with similar attributes to current foam-like materials. This study aimed to enhance the mechanical, thermal, and flame-retardant behavior of poly(vinyl alcohol) (PVA) aerogels by adding sodium alginate (SA) and tannic acid (TA). Aerogels were obtained by freeze-drying and post-ion crosslinking through calcium chloride (CaCl2) and boric acid (H3BO3) solutions. The incorporation of TA and SA enhanced the PVA aerogel’s mechanical properties, as shown by their high compressive specific moduli, reaching up to a six-fold increase after crosslinking and drying. The PVA/TA/SA aerogels presented a thermal conductivity of 0.043 to 0.046 W/m·K, while crosslinked ones showed higher values (0.049 to 0.060 W/m·K). Under TGA pyrolytic conditions, char layer formation reduced the thermal degradation rate of samples. After crosslinking, a seven-fold decrease in the thermal degradation rate was observed, confirming the high thermal stability of the formed foams. Regarding flammability, aerogels were tested through cone calorimetry. PVA/TA/SA aerogels showed a significant drop in the main parameters, such as the heat release rate (HRR) and the fire growth (FIGRA). The ion crosslinking resulted in a further reduction, confirming the improvement in the fire resistance of the modified compositionsPeer ReviewedPostprint (published version

Isocyanate toughened pCBT: reactive blending and tensile properties

Electronic version of an article published as "Express polymer letters" vol. 7, nº. 2, February 2013, p. 172-185. Cyclic butylene terephthalate oligomers (CBT) were reacted in a ring-opening polymerization with three types of isocyanates: a bifunctional aromatic type, a bifunctional aliphatic type and a polymeric aromatic isocyanate. All reactions took place in a batch mixer. The use of 0.5 to 1 wt% isocyanate led to a dramatic increase in elongation at break of polymerized cyclic butylene terephthalate (pCBT), from 8 to above 100%. The stiffness and strength of the modified pCBT, however, were found to slightly decrease. Proton nuclear magnetic resonance (NMR) analysis shows that the formation of thermally stable amide groups is the dominant chain extension reaction mechanism. Gel content measurements suggest a linear structure for samples containing bifunctional isocyanates while pCBT modified with polyfunctional isocyanate exhibited some gel formation at higher isocyanate content. Melting and crystallization temperatures as well as degree of crystallinity were found to decrease with increasing isocyanate content. No phase separation was detected by scanning electron microscopy (SEM) analysis. Moreover, a high degree of polymerization is deduced due to the absence of CBT oligomer crystals.Peer ReviewedPostprint (published version

Nanocomposites of in-situ polymerized cyclic butylene terephthalate and polyhedral oligomeric silsesquioaxanes

Nanocomposites were prepared by in-situ polymerization of CBT®, a cyclic form of poly(butylene terephthalate) (PBT) and polyhedral oligomeric silsesquioxane (POSS®) with 2.5, 5 and 10 wt% POSS content. Three different types of POSS were used; two with reactive functional groups, Trisilanolphenyl POSS (TPOSS) and Glycidyl POSS (G-POSS) and one POSS type having non-reactive functionality, Isooctyl POSS (I-POSS). SEM analysis showed that I-POSS was finely dispersed at a nanoscale level within the CBT, whereas T-POSS and GPOSS formed agglomerates microscaled rather than nanoscaled. T-POSS hinders the polymerization reaction of the CBT, resulting in a poor consolidation of the composite. However, Glycidyl POSS was found to crosslink the CBT during polymerization, making it possible to alter the final material properties. All nanocomposites with 10 wt% POSS content showed a hindered cold crystallization and subsequently showed no melting peak of the formed polymer in a DSC scan.Peer ReviewedPostprint (author’s final draft

Preparation and optimization of a titanium-based feedstock for Fused Deposition Modeling

In this work the preparation and optimization of a titanium-based metal injection moulding (MIM) feedstock for Fused Deposition Modeling (FDM) is presented. The composition of the plastic binder system, consisting of a backbone polymer, a water-soluble polymer and a lubricant was optimized and MIM feedstocks with titanium contents ranging from 50 to 68 vol.% were prepared in a laboratory-scale internal mixer. During the feedstock preparation the torque of the mixing screws of the internal mixer was recorded, which allowed to determine an optimum Ti content of 59–61 vol.%. The morphology, thermal and rheological properties of the prepared MIM feedstocks were characterized using various techniques such as optical microscopy, SEM, FTIR, DSC, TGA, MFI and oscillatory rheometry. This study contributes to the emerging research on additive manufacturing of MIM feedstocks with the aim of producing pure titanium components with complicated shapes and high density from novel MIM feedstock as the starting material