Structure-properties relationships in thermoplastic polyurethane elastomer nanocomposites: Interactions between polymer phases and nanofillers

Polyurethane thermoplastic elastomer (TPU) nanocomposites were prepared by the incorporation of 1 wt% of high-structured carbon black (HSCB), carbon nanofibers (CNF), nanosilica (NS) and nanoclays (NC), following a proper high-shear blending procedure. The TPU nanofilled mechanical properties and morphology was assessed. The nanofillers interact mainly with the TPU hard segments (HS) domains, determining their glass transition temperature, and increasing their melting temperature and enthalpy. A significant improvement upon the modulus, sustained stress levels and deformation capabilities is evidenced. The relationships between the morphology and the nanofilled TPU properties are established, evidencing the role of HS domains on the mechanical response, regardless the nanofiller type.

High-temperature polymer based magnetoelectric nanocomposites

The use of polymer based magnetoelectric materials for sensing and actuation applications has been the subject of increasing scientific and technological interest. One of the drawbacks to be overcome in this field is to increase the temperature range of application above 100 ºC. In this way, a nanocomposite material composed by a mixture of two aromatic diamines, 1,3-Bis-2-cyano-3-(3 aminophenoxy)phenoxybenzene (diamine 2CN) and 1,3-Bis(3-aminophenoxy)benzene (diamine 0CN) and CoFe2O4 (CFO) nanoparticles was designed, fabricated and successfully tested for high temperature magnetoelectric applications. Results revealed that CFO nanoparticles are well distributed within the 0CN2CN polymer matrix and that the addition of CFO nanoparticles does not significantly alter the polyimides structure. The magnetization response of the composite is determined by the CFO nanoparticle content. The piezoelectric response of the 0CN2CN polymer matrix (≈11 pC.N-1) and the maximum α33 value (0.8mV.cm-1.Oe-1) are stable over time and decrease only when the composite is subjected to temperatures above 130 ºC. Strategies to further improve the ME response are also discussed.

Energy harvesting performance of BaTiO3/poly(vinylidene fluoride-trifluoroethylene) spin coated nanocomposites

The energy harvesting efficiency of poly(vinylidene fluoride-trifluoroethylene) spin coated films and its nanocomposites with piezoelectric BaTiO3 have been investigated as a function of ceramic filler size and content. It is found that the best energy harvesting performance of ~0.28 W is obtained for the nanocomposite samples with 20% filler content of 10 nm size particles and for 5% filler content for the 100 and 500 nm size fillers. For the larger filler average sizes, the power decreases for filler contents above 5% due to increase of the mechanical stiffness of the samples. Due to the similar dielectric characteristics of the samples, the performance is mainly governed by the mechanical response. The obtained power values, easy processing and the low cost and robustness of the polymer, allow the implementation of the material for micro and nanogenerator applications.

Effect of polymeric matrix on morphology and photoelectric properties of polymer-quantum dots nanocomposites

Recently, CdTe semiconductor quantum dots (QDs) have attracted great interest due to their unique properties [1]. Their dispersion into polymeric matrices would be very for several optoelectronics applications. Despite its importance, there has been relatively little work done on charge transport in the QD polymeric films [2], which is mainly affected by their structural and morphological properties. In the present work, polymer-quantum dot nanocomposites films based on optically transparent polymers in the visible spectral range and CdTe QDs with controlled particle size and emission wavelength, were prepared via solvent casting. Photoluminescent (PL) measurements indicate different emission intensity of the nanocomposites. A blue shift of the emission peak compared to that of QDs in solution occurred, which is attributed to the QDs environment changes. The morphological and structural properties of the CdTe nanocomposites were evaluated. Since better QDs dispersion was achieved, PMMA seemed to be the most promising matrix. Electrical properties measurements indicate an ohmic behavior.

Mechanical characterization of bio-epoxy ecocomposites reinforced with fibrous structures based on natural fibers

This work intends to evaluate the mechanical properties of eco-composites reinforced with natural fiber fabrics in different fibrous arrangements, with a thermoset matrix of natural origin. When integrated by hand lay-up process, the composites obtained present excellent mechanical characteristics combined with environment friendly features, being able to be used in various industrial sectors.

Cost efficiency and resistance to chemical attack of a fly ash geopolymeric mortar versus epoxy resin and acrylic paint coatings

This article presents results of an experimental investigation on the resistance to chemical attack (with sulphuric, hydrochloric and nitric acid) of several materials: OPC concrete, high-performance concrete, epoxy resin, acrylic painting and a fly ash-based geopolymeric mortar). Three types of acids with three high concentrations (10, 20 and 30%) were used to simulate long-term degradation. A cost analysis was also performed. The results show that the epoxy resin has the best resistance to chemical attack independently of the acid type and the acid concentration. However, the cost analysis shows that the epoxy resin-based solution is the least cost-efficient solution being 70% above the cost efficiency of the fly ash-based geopolymeric mortar.

Nanocomposites: the contribution of multiscale modelling to improve the dispersion levels

Tese de Doutoramento em Ciência e Engenharia de Polímeros e Compósitos

Patterned CNT-PDMS nanocomposites for flexible pressure sensors

This paper reports the fabrication process and characterization of a flexible pressure sensor based on polydimethylsiloxane (PDMS) and multi-walled carbon nanotubes (CNT-PDMS). The proposed approach relies on patterned CNT-PDMS nanocomposite strain gauges fabricated with SU-8 microstructures (with the micropatterns) in a low‑cost and simple fabrication process. This nanocomposite polymer is mounted over a PDMS membrane, which, in turn, lies on top of a PDMS diaphragm like structure. This configuration enables the PDMS membrane to bend when pressure is applied, thereby affecting the nanocomposite strain gauges, effectively changing their electrical resistance. Carbon nanotubes have several advantages such as excellent mechanical properties, high electrical conductivity and thermal stability. Furthermore, the measurement range of the proposed sensor can be adapted according to the application by varying the CNTs content and geometry of microstructure. In addition, the sensor’s biocompatibility, low cost and simple fabrication makes it very appealing for biomechanical strain sensing. The sensor’s sensitivity was about 0.073%ΔR/mmHg.

Synthesis and characterization of kraft lignin-based epoxy resins

Epoxidization is an interesting way to develop a new application of lignin and therefore to improve its application potential. In this work, kraft lignin-based epoxy resins were obtained by the epoxidization reaction, using the kraft lignin recovered directly from pulping liquor and modified by a methylolation reaction. The methylolated lignins were obtained by the reaction of original kraft lignin with formaldehyde and glyoxal, which is a less volatile and less toxic aldehyde. 1H-NMR spectroscopy showed that methylolated kraft lignin has more hydroxymethyl groups than glyoxalated kraft lignin. For the epoxidization reaction we studied the influence of the lignin:NaOH (w/w) ratio, temperature, and time of the reaction on the properties of the prepared epoxidized lignins. The structures of lignin-based epoxy resins were followed by epoxy index test and FTIR spectroscopy. Optimal conditions were obtained for lignin-based epoxy resin produced at lignin/NaOH = 1/3 at 70 ºC for 3h. Thermogravimetry analysis (TGA) revealed that the epoxidization enhances the thermal stability of lignins and may allow a wider temperature range for applications with lignin epoxy-PF blends

Characterization of alkaline lignins for use in penol-formaldehyde and epoxy resins

Besides polyurethanes and polyesters, phenolic and epoxy resins are the most prominent applications for technical lignins in thermosetting materials. To evaluate the potential application of lignin raw materials in phenol formaldehyde and epoxy resins, three types of alkaline lignins were characterized in terms of their structures and thermal properties. The lignin samples analyzed were kraft lignin (LIG-1), soda–rice straw lignin (LIG-2), and soda-wheat straw lignin (LIG-3). FTIR and 1H-NMR methods were used to determine their structure. Gel permeation chromatography (GPC) was used to determine the molecular weight distribution (MWD). Differential scanning calorimetry (DSC) was used to measure the glass transition temperature (Tg), and thermogravimetric analysis (TGA) to determine the thermal stability of lignin samples. Results showed that kraft lignin (LIG-1) has moderate hydroxyl-group content, is rich in G-type units, and has good thermal stability. These properties make it more suitable for direct use in phenol formaldehyde resins, and it is therefore a good raw material for this purpose. The alkaline soda-rice straw lignin (LIG-2) with a high hydroxyl-group content and excellent thermal stability is most suited to preparing lignin-based epoxy resin

Síntesi i propietats de vidres metàl•lics massissos i materials nanocomposites basats en Fe per aplicacions com a materials magnètics tous

Estudi realitzat a partir d’una estada a l’ Institut für Komplexe Materialien, Leibniz-Institut für Festkörper- und Werkstoffforschung Dresden, entre 2010 i 2011. S'ha explorat l'efecte de les condicions i influència dels elements d'aleació en la capacitat de formació de vidre, l'estructura i les propietats tèrmiques i magnètiques de vidres metàl•lics massissos i materials nanocristal•lins en base Fe. La producció d'aquests materials en forma de cintes de unes 20 micres de gruix ha estat àmpliament estudiada i s'ha vist que presenten unes propietats excel•lents com a materials magnètics tous. El propòsit general d'aquest projecte era l'obtenció de composicions òptimes amb alta capacitat de formar vidre i amb excel•lents propietats magnètiques com a materials magnètics tous combinat amb bones propietats mecàniques. El projecte prenia com a punt de partida l'aliatge [FeCoBSi]96Nb4 ja que és el que presenta millor capacitat de formar vidre i presenta una alta imantació de saturació i baix camp coercitiu. S'ha fet un estudi dels factors fonamentals que intervenen en la formació de l'estat vitri. La composició abans esmentada ha estat variada amb l'addició d'altres elements per estudiar com afecten aquests nous elements a les propietats, la formació de vidre i l'estructura dels aliatges resultants amb l'objectiu de millorar-ne les propietats magnètiques i la capacitat de formació de vidre. Entre altres s'ha usat el Zr, Mo, Y i el Gd per millorar la formació de vidre; i el Co i el Ni per millorar les propietats magnètiques a alta temperatura. S'han estudiat les relacions entre la capacitat de formació de vidre i la seva estabilitat tèrmica, la resistència a la cristal•lització i la estructura de l'aliatge resultant després del procés de solidificació. Per aquest estudi s'han determinat els mecanismes que controlen la transformació i la seva cinètica així com les fases que es formen durant el tractament tèrmic permetent la formulació de models predictius.

Level of accumulation of epoxy fatty acid in Arabidopsis thaliana expressing a linoleic acid delta12-epoxygenase is influenced by the availability of the substrate linoleic acid.

Arabidopsis thaliana (L.) Heynh. expressing the Crepis palaestina (L.) linoleic acid delta12-epoxygenase in its developing seeds typically accumulates low levels of vernolic acid (12,13-epoxy-octadec-cis-9-enoic acid) in comparison to levels found in seeds of the native C. palaestina. In order to determine some of the factors limiting the accumulation of this unusual fatty acid, we have examined the effects of increasing the availability of linoleic acid (9cis, 12cis-octadecadienoic acid), the substrate of the delta12-epoxygenase, on the quantity of epoxy fatty acids accumulating in transgenic A. thaliana. The addition of linoleic acid to liquid cultures of transgenic plants expressing the delta12-epoxygenase under the control of the cauliflower mosaic virus 35S promoter increased the amount of vernolic acid in vegetative tissues by 2.8-fold. In contrast, the addition to these cultures of linoelaidic acid (9trans, 12trans-octadecadienoic acid), which is not a substrate of the delta12-epoxygenase, resulted in a slight decrease in vernolic acid accumulation. Expression of the delta12-epoxygenase under the control of the napin promoter in the A. thaliana triple mutant fad3/fad7-1/fad9, which is deficient in the synthesis of tri-unsaturated fatty acids and has a 60% higher level of linoleic acid than the wild type, was found to increase the average vernolic acid content of the seeds by 55% compared to the expression of the delta12-epoxygenase in a wild-type background. Together, these results reveal that the availability of linoleic acid is an important factor affecting the synthesis of epoxy fatty acid in transgenic plants.

Synthetic applications of chiral unsaturated epoxy alcohols prepared by sharpless asymmetric epoxidation

An overview of the synthesis and applications of chiral 2,3-epoxy alcohols containing unsaturated chains is presented. One of the fundamental synthetic routes to these compounds is Sharpless asymmetric epoxidation, which is reliable, highly chemoselective and enables easy prediction of the product enantioselectivity. Thus, unsaturated epoxy alcohols are readily obtained by selective oxidation of the allylic double bond in the presence of other carbon-carbon double or triple bonds. The wide availability of epoxy alcohols with unsaturated chains, the versatility of the epoxy alcohol functionality (e.g. regio- and stereo-selective ring opening; oxidation; and reduction), and the arsenal of established alkene chemistries, make unsaturated epoxy alcohols powerful starting materials for the synthesis of complex targets such as biologically active molecules. The popularization of ring-closing metathesis has further increased their value, making them excellent precursors to cyclic compounds.

Performance Evaluation Of Iowa Bridge Decks Constructed With Epoxy-Coated Reinforcing Bars, RB06-011, 2011

Epoxy coatings have been used on the embedded reinforcing bars of bridge decks since the mid-1970s to mitigate deterioration caused by chloride-induced corrosion. The use of chloride-based deicers became common in the early 1960s and caused corrosion of conventional uncoated bars in bridge decks within 5 to 10 years of commencement of deicer applications. In response to this rapid deterioration, the National Bureau of Standards researched coatings to protect the reinforcement (National Bureau of Standards, 1975), resulting in the development of epoxy-coated reinforcing bars, which were used in bridge decks beginning in 1973. While corrosion-related deterioration has been prevalent on bridge decks with uncoated reinforcing bars in northern climates where the use of deicing salts is common, bridge decks constructed after 1973 with epoxy-coated reinforcing have shown good corrosion resistance with only limited exceptions. On the whole, previous laboratory and field studies regarding the performance of epoxy-coated reinforcing bars are very promising; however, some laboratory and field studies have yielded differing results. In recent years, maintenance personnel for the Iowa Department of Transportation (Iowa DOT) have reportedly performed patch repairs to some bridge decks reinforced with epoxy-coated bars. At one such bridge, the southbound US 65 bridge (Bridge No. 7788.5L065) over the Union Pacific Railroad near Bondurant in Polk County, Iowa, deck repairs were performed by Iowa DOT maintenance personnel in the Spring of 2010, based on our communications regarding this topic with Mr. Gordon Port of the Iowa DOT. These repairs were observed by engineers from the Iowa DOT Office of Bridges and Structures, who reported that significant corrosion was found at a number of epoxy-coated reinforcing bars uncovered during this patch work. These repairs were reportedly performed at spalls and delaminated areas corresponding to cracks over transverse reinforcing bars, and involved careful removal of the concrete from over the bars. Figures 1 through 4 contain photographs provided by Iowa DOT personnel showing the removal process (Figure 1), the conditions encountered (Figures 2 and 3), and close-up views of the corroded reinforcing (Figure 4). As a result of these observations, the Iowa Department of Transportation has requested this study to gain further understanding of the long-term performance of bridge decks reinforced with epoxy-coated bars. The two main objectives of this study are to determine the long-term effectiveness of the epoxy coatings and to determine the potential causes for the deterioration at locations where corrosion has occurred. Wiss, Janney, Elstner Associates, Inc. (WJE) and the Iowa DOT identified eight different bridge decks across Iowa for this study that were constructed using epoxy-coated reinforcing bars. A field investigation consisting of visual inspections, a delamination survey, a concrete cover survey, electrical testing for susceptibility to corrosion, and concrete sampling was conducted within a survey area deemed to be representative of the condition of each bridge deck. Laboratory testing, including chloride ion content testing, characterization of the extracted bars, petrographic examination of the concrete, and carbonation testing, was conducted on the core samples taken from each bridge deck.