Soybean-Based Polyol as a Substitute of Fossil-Based Polyol on the Synthesis of Thermoplastic Polyurethanes: The Effect of Its Content on Morphological and Physicochemical Properties.

Thermoplastic polyurethanes (TPUs) are remarkably versatile polymers due to the wide range of raw materials available for their synthesis, resulting in physicochemical characteristics that can be tailored according to the specific requirements of their final applications. In this study, a renewable bio-based polyol obtained from soybean oil is used for the synthesis of TPU via reactive extrusion, and the influence of the bio-based polyol on the multi-phase structure and properties of the TPU is studied. As raw materials, 4,4'-diphenylmethane (MDI), 1,4-butanediol, a fossil-based polyester polyol, and a bio-based polyol are used. The fossil-based to soybean-based polyol ratios studied are 100/0, 99/1, 95/5, 90/10, 80/20, and 50/50% by weight, respectively. The TPUs were characterized by size exclusion chromatography (SEC), gel content analysis, Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS), dynamic mechanical analysis (DMA), and contact angle measurements. The results reveal that incorporating the renewable polyol enhances the compatibility between the rigid and flexible segments of the TPU. However, due to its high functionality, the addition of soybean-based polyol can promote cross-linking. This phenomenon reduces the density of hydrogen bonds within the material, also reducing polarity and restricting macromolecular mobility, as corroborated by higher glass transition temperature (Tg) values. Remarkably, the addition of small amounts of the bio-based polyol (up to 5 wt.% of the total polyol content) results in high-molecular-weight TPUs with lower polarity, combined with suitable processability and mechanical properties, thus broadening the range of applications and improving their sustainability.

Graphene oxide increases PMMA's resistance to fatigue and strength degradation.

OBJECTIVES: to characterize the effects of graphene oxide (GO) on polymethyl methacrylate's (PMMA) reliability and lifetime. The hypothesis tested was that GO would increase both Weibull parameters and decreased strength degradation over time. METHODS: PMMA disks containing GO (0.01, 0.05, 0.1, or 0.5 wt%) were subjected to a biaxial flexural test to determine the Weibull parameters (m: modulus of Weibull; σ0: characteristic strength; n = 30 at 1 MPa/s) and slow crack growth (SCG) parameters (n: subcritical crack growth susceptibility coefficient, σf0: scaling parameter; n = 10 at 10-2, 10-1, 101, 100 and 102 MPa/s). Strength-probability-time (SPT) diagrams were plotted by merging SCG and Weibull parameters. RESULTS: There was no significant difference in the m value of all materials. However, 0.5 GO presented the lowest σ0, whereas all other groups were similar. The lowest n value obtained for all GO-modified PMMA groups (27.4 for 0.05 GO) was higher than the Control (15.6). The strength degradation predicted after 15 years for Control was 12%, followed by 0.01 GO (7%), 0.05 GO (9%), 0.1 GO (5%), and 0.5 GO (1%). SIGNIFICANCE: The hypothesis was partially accepted as GO increased PMMA's fatigue resistance and lifetime but did not significantly improve its Weibull parameters. GO added to PMMA did not significantly affect the initial strength and reliability but significantly increased PMMA's predicted lifetime. All the GO-containing groups presented higher resistance to fracture at all times analyzed compared with the Control, with the best overall results observed for 0.1 GO.

Castor Oil-Based Polyurethane/S2 Glass/Aramid Hybrid Composites Manufactured by Vacuum Infusion.

This study evaluates the hybridization effect of S2-glass/aramid on polyurethane (PU) composites produced by vacuum infusion. Different laminates were produced with similar thickness (around 2.5 mm), using, as reinforcement, only aramid fabrics (five layers, named as K5) or only S2-glass fabrics (eight layers, named as G8). Furthermore, hybridization was obtained by manufacturing symmetrical hybrid inter-ply laminates, with four S2-glass layers and two of aramid, (G2K)S and (KG2)S. The mechanical response of the laminates was evaluated in tensile, interlaminar shear strength, dynamical mechanical analysis and quasi-static indentation tests, and related to their morphological characteristics. The main results show that the pure glass composites presented less voids, but a higher density as well as higher tensile stiffness and strength. The aramid laminates showed a high capability for absorbing impact energy (ca. 30% higher than the pure glass laminates), and the hybrid laminates had intermediate properties. More importantly, this work shows the possibility of using a polyurethane matrix for vacuum infusion processing, effective even for aramid/S2-glass hybrid composites with thermoset polyurethane resin. This study is therefore promising for impact absorption in applications such as protective armor. The studied hybrid laminate may display a suitable set of properties and greater energy absorption capability and penetration resistance for impact applications.

Mechanochemical Treatment in High-Shear Thermokinetic Mixer as an Alternative for Tire Recycling.

This publication highlights the use of a high-speed thermokinetic mixer as an alternative to recycling ground tire rubber (GTR) using mechanochemical treatment. The GTR initially had a gelled fraction of 80% and presented a reduction of up to 50% of gel fraction in the most intensive condition (5145 rpm, n2). The processing condition at the lowest speed (2564 rpm, n1) resulted in greater selectivity in chain scission (K~1). However, in the most intense processing condition (10 min to n2), more significant degradation was observed via random scission, reduction in the glass transition temperature, Tg (11 °C), increase in the soluble polymeric fraction, and a more significant reduction in the density of bonds occurs. The artificial neural network could describe and correlate the thermal degradation profile with the processing conditions and the physicochemical characteristics of the GTR. The n2 velocity resulted in the formation of particles with a smoother and more continuous surface, which is related to the increase in the amount of soluble phase. The approach presented here represents an alternative to the mechanochemical treatment since it can reduce the crosslink density with selectivity and in short times (1-3 min).

Tuning Thermal, Morphological, and Physicochemical Properties of Thermoplastic Polyurethanes (TPUs) by the 1,4-Butanediol (BDO)/Dipropylene Glycol (DPG) Ratio.

Thermoplastic polyurethanes (TPUs) are versatile polymers presenting a broad range of properties as a result of their countless combination of raw materials­in essence, isocyanates, polyols, and chain extenders. This study highlights the effect of two different chain extenders and their combination on the structure−property relationships of TPUs synthesized by reactive extrusion. The TPUs were obtained from 4,4-diphenylmethane diisocyanate (MDI), polyester diols, and the chain extenders 1,4-butanediol (BDO) and dipropylene glycol (DPG). The BDO/DPG ratios studied were 100/0, 75/25, 50/50, 25/75, and 0/100 wt.%. The TPUs were characterized by size exclusion chromatography (SEC), Fourier-transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS), UV−vis spectroscopy, and physical-mechanical properties. The results indicate that DPG promotes compatibility between rigid (HS) and flexible (SS) segments of TPUs. Consequently, increasing DPG content (>75 wt.%) reduced the organization of the rigid segments and the degree of phase separation, increasing the polydispersity of the interdomain distance and the transparency in the UV−visible spectrum of the TPUs. Furthermore, increasing DPG content also reduced the amount of hydrogen bonds present in the rigid phase, reducing or extinguishing its glass transition temperature (TgHS) and melting temperature (Tm), and increasing the glass transition temperature of the flexible phase (TgSS). Therefore, increasing DPG content leads to a deterioration in mechanical properties and hydrolysis resistance.

Physicochemical characterization, released profile, and antinociceptive activity of diphenhydraminium ibuprofenate supported on mesoporous silica.

The thermal, physical, and morphological properties of diphenhydraminium ibuprofenate ([DIP][IBU]) adsorbed onto mesoporous silica (SiO2-60 Šand SiO2-90 Å) from solution were determined. The thermal, physical, and morphological properties of [DIP][IBU] supported on silica were determined. The adsorption of [DIP][IBU] on the pores and surface of silica was proven by N2 adsorption/desorption isotherms. Additionally, release profiles were determined for all systems, and the antinociceptive activity of neat [DIP][IBU] and [DIP][IBU] supported on silica were determined. The interaction of [DIP][IBU] and silica was dependent on pore size, with the formation of a [DIP][IBU] monolayer on SiO2-60 and a multilayer on SiO2-90. The release profile was sustained and slow and dependent on the pore size of the silica, in which the smaller the pore size, the faster the release. The nociceptive evaluation showed that [DIP][IBU] presents a greater (99.21 ±â€¯0.85%) antinociceptive effect than the ibuprofen (46 ±â€¯4.3%). Additionally, [DIP][IBU] on SiO2-60 (90 ±â€¯5.8%) had a greater antinociceptive effect than on SiO2-90 (73 ±â€¯13.2%), which indicates that in vivo tests are in accordance with the in vitro experiments.

Tunable Structure and Properties of Segmented Thermoplastic Polyurethanes as a Function of Flexible Segment.

Segmented thermoplastic polyurethanes (PUs) were synthetized using macrodiols with different functional groups (carbonate, ester, and /or ether) as a segment with a molar mass of 1000 and 2000 g/mol, and 4,4'-diphenylmethane diisocyanate (MDI) and 1,4-butanediol as a rigid segment. The polyurethanes obtained reveal a wide variation of microphase separation degree that is correlated with mechanical properties and retention of tensile properties under degradation by heat, oil, weather, and water. Different techniques such as differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), Fourier transform infrared (FTIR), and synchrotron small-angle X-ray scattering (SAXS) were used to determine rigid-flexible segments' phase behaviour. Retention of tensile properties determines the stability of the samples under different external factors. This work reveals that pure polycarbonate-based macrodiols induce the highest degree of phase miscibility, better tensile properties, hardness shore A, and retention of tensile properties under external agents.

Soybean-modified polyamide-6 mats as a long-term cutaneous wound covering.

Engineered skin coverings have been adopted clinically to support extensive and deep wounds that result in fewer healthy skin remaining and therefore take longer to heal. Nonetheless, these biomaterials demand intensive labor and an expensive final cost. In comparison to conventional bandages, which do not meet all the requirements of wound care, electrospun fiber mats could potentially provide an excellent environment for healing. In this work, we developed two nanostructured scaffolds based on polyamide-6 (PA-6) to be tested as a wound covering in a rat model of full-thickness incisional wound healing. The central idea was to create a bioconstruct that is simple to implement and biologically safe, with a high survival rate, which provides physical support and biological recognition for new functional tissues. An unmodified PA-6 and a soybean-modified PA-6 were employed as nanofibrillar matrices in this study. The biomaterials showed a dimensional homology to natural extracellular matrix components and neither in vitro toxicity nor in vivo side effects. Both polymeric scaffolds were resistant to the sterilization process and could promote the attachment of 3T3 fibroblast cells, besides successfully incorporating the growth factor PDGF-BB, which had its bioactivity extended for up to 12 h under simulated conditions. The modification of PA-6 chains with a fatty acid derivative increased the scaffold's surface free energy, favoring cell proliferation, collagen formation, and ECM secretion. These results confirm the potential of these materials as a topical dermal covering for skin regeneration.

Polyurethane as a strategy for annulus fibrosus repair and regeneration: a systematic review.

AIM: Disc herniation is a spine disease that leads to suffering and disability. Discectomy is a Janus-faced approach that relieves pain symptoms but leave the intervertebral discs predisposed to herniation. This systematic review discussed the mechanical and biological requirements for a polyurethane-based biomaterial to be used in annular repair. METHODS: Search strategy was performed in PubMed, Web of Science and Scopus databases to define the main mechanical properties, biological findings and follow-up aspects of these biomaterials. The range was limited to articles published from January 2000 to December 2017 in English language. RESULTS: The search identified 82 articles. From these, a total of 18 articles underwent a full-text analysis, and 16 studies were included in the review. CONCLUSION: The polyurethane presents suitable properties to be used as an engineered solution to re-establish the microenvironment and biomechanical features of the intervertebral disc.

Correlation between rheological properties and capillary fixation for modelling creams

The Brazilian male beauty market occupies the second place in world consumption of cosmetics. Among the numerous products consumed by such audience is the capillary fixation mask, which is mainly composed by fixatives. These additives act on stabilizing the cosmetic emulsion, protecting the hair against moisture and also increasing the intensity of hair fixation. In this work, three formulations for modelling creams were prepared by different concentrations of the fixatives StylezeTM W20 and PVP K90 and their properties characterized by physicochemical, rheological and sensory analysis. The capillary masks produced were stable oil-in-water (O/W) emulsions with uniform droplets of 2.05-2.82 µm sizes and pseudoplastic thixotropic behavior (0.19 < n < 0.26). It was possible to correlate the increased concentration of PVP K90 to a greater thixotropy and an improved yarn fixation, despite the worsening in the spreadability of the formulations. These results suggest properly conducted rheological measurements can contribute to the prediction of the emulsion's sensory properties, which can save time and funds on the development of new cosmetics

Anti-Inflammatory Activity of Babassu Oil and Development of a Microemulsion System for Topical Delivery.

Babassu oil extraction is the main income source in nut breakers communities in northeast of Brazil. Among these communities, babassu oil is used for cooking but also medically to treat skin wounds and inflammation, and vulvovaginitis. This study aimed to evaluate the anti-inflammatory activity of babassu oil and develop a microemulsion system with babassu oil for topical delivery. Topical anti-inflammatory activity was evaluated in mice ear edema using PMA, arachidonic acid, ethyl phenylpropiolate, phenol, and capsaicin as phlogistic agents. A microemulsion system was successfully developed using a Span® 80/Kolliphor® EL ratio of 6 : 4 as the surfactant system (S), propylene glycol and water (3 : 1) as the aqueous phase (A), and babassu oil as the oil phase (O), and analyzed through conductivity, SAXS, DSC, TEM, and rheological assays. Babassu oil and lauric acid showed anti-inflammatory activity in mice ear edema, through inhibition of eicosanoid pathway and bioactive amines. The developed formulation (39% A, 12.2% O, and 48.8% S) was classified as a bicontinuous to o/w transition microemulsion that showed a Newtonian profile. The topical anti-inflammatory activity of microemulsified babassu oil was markedly increased. A new delivery system of babassu microemulsion droplet clusters was designed to enhance the therapeutic efficacy of vegetable oil.

Morphological and structural characterization of PHBV/organoclay nanocomposites by small angle X-ray scattering.

In this work, the morphological and structural behaviors of poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) nanocomposites were investigated using small angle X-ray scattering (SAXS), wide angle X-ray diffraction (WAXD) and transmission electron microscopy (TEM). The nanocomposites with 1, 3 and 5 wt.% of organically modified montmorillonite Cloisite® 30B (OMMT) were prepared by melt processing in a twin screw extruder using two different processing conditions (low and high shear intensity). The lamellar long period of the polymer was lower for the nanocomposites, with high polydispersity values. However, the crystalline thickness increased with the clay content and was independent of the processing conditions. This behavior resulted in a high linear crystallinity of the nanocomposites with 3 and 5 wt.% OMMT. The disruption factor (ß) was in agreement with the WAXD and TEM findings, indicating a good dispersion of the nanoparticles in the PHBV matrix with 3 wt.% of OMMT during the high shear intensity of melt processing.

Antimicrobial membrane cellulose acetate containing ionic liquid and metal nanoparticles.

Stable metallic Au(0), Ag(0) and Pt(0) nanoparticle-containing membrane films (20 microm thickness) were obtained by combining irregularly shaped nanoparticles of monomodal size distributions (11 +/- 1.5 nm Au(0), 8.9 +/- 2.1 nm Ag(0) and 2.8 +/- 0.4 nm Pt(0)) in the ionic liquid (IL) 1-n-butyl-3-methylimidazolium bis(trifluoromethane sulfonyl)imide (BMI x (NTf)2) with a syrup of cellulose acetate (CA) in acetone. The presence of small and stable Au(0), Ag(0) or Pt(0) nanoparticles induced an augmentation in the CA/IL film surface areas. The addition of the IL to the membrane resulted in an increase of its elasticity and a decrease in its tenacity and toughness, whereas its stress at break was not influenced. High antimicrobial activity was observed in membranes containing Au(0), Ag(0) and Pt(0) metal concentrations as low as 1 mg of metal per 5 g of CA. The CA/IL/nanoparticle combination enhanced the activity and durability of the metal nanoparticles and provided greater antimicrobial activity against E. coli and S. aureus bacteria.