Dielectric thermal analysis as a tool for quantitative-evaluation of the viscosity and the kinetics of epoxy resin cure

Dielectric thermal analysis has been proved as a valuable tool for monitoring the epoxy curing process and the related rheological properties in the fabrication of polymer-matrix composite materials. This technique also has the potential to be applied in the monitoring of magnet impregnation processes as well as in quality control. In this work we present the quantitative evaluation of the viscosity changing and the curing kinetics for a commercial Stycast epoxy resin system at different temperatures through the impedance analysis. The results showed correlation between the real component of the complex impedance and the isothermal reaction extent. Comparing the dielectric analysis result with the viscosity measured by rotational rheometer we observed a similar behavior reported for dynamic mechanic analysis. The results comparison have shown that the kinetics parameters obtained from DSC and DETA analysis showed different sensitivities related to the characteristics of curing stages. We concluded that the dielectric thermal analysis should be applied in quantitative evaluation of cure kinetics.

The effect of the ocean water immersion and UV ageing on the dynamic mechanical properties of the PPS/glass fiber composites

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Influence of different organoclays on the curing, morphology, and dynamic mechanical properties of an epoxy adhesive

The thermal, mechanical, and adhesive properties of nanoclay-modified adhesives were investigated. Two organically modified montmorillonites: Cloisite 93A (C93A) and Nanomer I.30E (I.30E) were used as reinforcement of an epoxy adhesive. C93A and I.30E are modified with tertiary and primary alkyl ammonium cations, respectively. The aim was to study the influence of the organoclays on the curing, and on the mechanical and adhesive properties of the nanocomposites. A specific goal was to compare their behavior with that of Cloisite30B/epoxy and Cloisite15A/ epoxy nanocomposites that we have previously studied. Both C30B and C15A are modified with quaternary alkyl ammonium cations. Differential scanning calorimetry results showed that the clays accelerate the curing reaction, an effect that is related to the chemical structure of the ammonium cations. The three Cloisite/nanocomposites showed intercalated clay structures,the interlayer distance was independent of the clay content. The I.30E/epoxy nanocomposites presented exfoliated structure due to the catalytic effect of the organic modifier. Clay-epoxy nanocompo-sites showed lower glass transition temperature (Tg) and higher values of storage modulus than neat epoxy thermoset, with no significant differences between exfoliated or intercalated nanocom-posites. The shear strength of aluminum joints using clay/epoxy adhesives was lower than with the neat epoxy adhesive. The wáter aging was less damaging for joints with I.30E/epoxy adhesive.

Thermal analysis during bone drilling using rigid polyurethane foams: numerical and experimental methodologies

Osteotomy or bone cutting is a common procedure in orthopaedic surgery, mainly in the treatment of fractures and reconstructive surgery. However, the excessive heat produced during the bone drilling process is a problem that counters the benefits of this type of surgery, because it can result in thermal osteonecrosis, bone reabsorption and damage the osseointegration of implants. The analysis of different drilling parameters and materials can allow to decrease the temperature during the bone drilling process and contribute to a greater success of this kind of surgical interventions. The main goal of this study was to build a numerical three-dimensional model to simulate the drilling process considering the type of bone, the influence of cooling and the bone density of the different composite materials with similar mechanical properties to the human bone and generally used in experimental biomechanics. The numerical methodology was coupled with an experimental methodology. The use of cooling proved to be essential to decrease the material damage during the drilling process. It was concluded that the materials with less porosity and density present less damage in drilling process. The developed numerical model proved to be a great tool in this kind of analysis. © 2016, The Brazilian Society of Mechanical Sciences and Engineering.

Thermal analysis in the drilling of solid rigid foam materials and ex-vivo bovine bones

Bone is a dynamic, highly vascularized tissue with a unique capacity to heal and regenerate without scarring. However, drilling remains a concern in several clinical procedures due to thermal damage of the bone and surrounding tissue. The success of this surgeries is dependent of many factors and also in temperature generation during the drilling bone. When an excessive heat is produced during the drilling, thermal necrosis can occur and the bone suffers injuries. Studies have shown that the increased temperature is directly related with the drilling parameters, particularly, the drill speed, feed-rate, applied force, the depth of cut, the geometry of the drill bit, the use or not of a cooling system and also the type of bone.

The effect of polypropylene-graft-maleic anhydride on the morphology and dynamic mechanical properties of polypropylene/polystyrene blends

Polypropylene (PP) and polystyrene (PS) blends were prepared by melt processing in a haake at 180 °C. PP/PS blends are immiscible and the blend morphologies were characterized by scanning electron microscopy. The viscoelastic properties were characterized using dynamic mechanical analysis (DMA) with reference to blend ratio. The blend morphologies such as matrix droplet and phase inverted morphologies were observed. The storage modulus of the blends increased with increase in PS content and the value was maximum for neat PS. DMA showed changes in the polystyrene glass transition temperatures (Tg) over the entire composition range. There was a sharp increase in the Tg of PS with increasing PP content in the blend and a 12 °C elevation in Tg was observed. The increase in Tg was explained by proposing a new model based on the physical interaction between the blend components. It is assumed that the different effects by the PP phase resulted in the formation of constrained PS chains leading to high Tg values. The addition of PP-g-MAH has a positive effect on the morphology, increases the storage modulus, and decreases the Tg till 80/20 blends. However, for PP/PS blends with higher concentrations of PS, the PP-g-MAH has little effect or adverse effect on the morphology, and storage modulus, but decreases the Tg.

Raman microscopy of formamide-intercalated kaolinites treated by controlled-rate thermal analysis technology

Raman spectroscopy of formamide-intercalated kaolinites treated using controlled-rate thermal analysis technology (CRTA), allowing the separation of adsorbed formamide from intercalated formamide in formamide-intercalated kaolinites, is reported. The Raman spectra of the CRTA-treated formamide-intercalated kaolinites are significantly different from those of the intercalated kaolinites, which display a combination of both intercalated and adsorbed formamide. An intense band is observed at 3629 cm-1, attributed to the inner surface hydroxyls hydrogen bonded to the formamide. Broad bands are observed at 3600 and 3639 cm-1, assigned to the inner surface hydroxyls, which are hydrogen bonded to the adsorbed water molecules. The hydroxyl-stretching band of the inner hydroxyl is observed at 3621 cm-1 in the Raman spectra of the CRTA-treated formamide-intercalated kaolinites. The results of thermal analysis show that the amount of intercalated formamide between the kaolinite layers is independent of the presence of water. Significant differences are observed in the CO stretching region between the adsorbed and intercalated formamide.

Thermal analysis and hot stage Raman spectroscopy of the basic copper arsenate mineral : euchroite

The thermal analysis of euchroite shows two mass loss steps in the temperature range 100 to 105°C and 185 to 205°C. These mass loss steps are attributed to dehydration and dehydroxylation of the mineral. Hot stage Raman spectroscopy (HSRS) has been used to study the thermal stability of the mineral euchroite, a mineral involved in a complex set of equilibria between the copper hydroxy arsenates: euchroite Cu2(AsO4)(OH).3H2O → olivenite Cu2(AsO4)(OH) → strashimirite Cu8(AsO4)4(OH)4.5H2O → arhbarite Cu2Mg(AsO4)(OH)3. Hot stage Raman spectroscopy inolves the collection of Raman spectra as a function of the temperature. HSRS shows that the mineral euchroite decomposes between 125 and 175 °C with the loss of water. At 125 °C, Raman bands are observed at 858 cm-1 assigned to the ν1 AsO43- symmetric stretching vibration and 801, 822 and 871 cm-1 assigned to the ν3 AsO43- (A1) antisymmetric stretching vibration. A distinct band shift is observed upon heating to 275 °C. At 275 °C the four Raman bands are resolved at 762, 810, 837 and 862 cm-1. Further heating results in the diminution of the intensity in the Raman spectra and this is attributed to sublimation of the arsenate mineral. Hot stage Raman spectroscopy is most useful technique for studying the thermal stability of minerals especially when only very small amounts of mineral are available.

Thermal analysis of synthetic reevesite and cobalt substituted reevesite (Ni,Co)6Fe2(OH)16(CO3)•4H2O

The mineral reevesite and the cobalt substituted reevesite have been synthesised. The d(003) spacings of the minerals ranged from 7.54 to 7.95 Å. The maximum d(003) value occurred at around Ni:Co 0.4:0.6. This maximum in interlayer distance is proposed to be due to a greater number of carbonate anions and water molecules intercalated into the structure. The stability of the reevesite and cobalt doped reevesite was determined by thermogravimetric analysis. The maximum temperature of the reevesite occurs for the unsubstituted reevesite and is around 220°C. The effect of cobalt substitution results in a decrease in thermal stability of the reevesites. Four thermal decomposition steps are observed and are attributed to dehydration, dehydroxylation and decarbonation, decomposition of the formed carbonate and oxygen loss at ~807 °C. A mechanism for the thermal decomposition of the reevesite and the cobalt substituted reevesite is proposed.

Synthesis and thermal analysis of Indium based hydrotalcites of formula Mg6In2(CO3)(OH)16•4H2O

Insight into the unique structure of layered double hydroxides has been obtained using a combination of X-ray diffraction and thermal analysis. Indium containing hydrotalcites of formula Mg4In2(CO3)(OH)12•4H2O (2:1 In-LDH) through to Mg8In2(CO3)(OH)18•4H2O (4:1 In-LDH) with variation in the Mg:In ratio have been successfully synthesised. The d(003) spacing varied from 7.83 Å for the 2:1 LDH to 8.15 Å for the 3:1 indium containing layered double hydroxide. Distinct mass loss steps attributed to dehydration, dehydroxylation and decarbonation are observed for the indium containing hydrotalcite. Dehydration occurs over the temperature range ambient to 205 °C. Dehydroxylation takes place in a series of steps over the 238 to 277 °C temperature range. Decarbonation occurs between 763 and 795 °C. The dehydroxylation and decarbonation steps depend upon the Mg:In ratio. The formation of indium containing hydrotalcites and their thermal activation provides a method for the synthesis of indium oxide based catalysts.

Thermal analysis and infrared emission spectroscopic study of halloysite-potassium acetate intercalation compound

The thermal decomposition of halloysite-potassium acetate intercalation compound was investigated by thermogravimetric analysis and infrared emission spectroscopy. The X-ray diffraction patterns indicated that intercalation of potassium acetate into halloysite caused an increase of the basal spacing from 1.00 to 1.41 nm. The thermogravimetry results show that the mass losses of intercalation the compound occur in main three main steps, which correspond to (a) the loss of adsorbed water (b) the loss of coordination water and (c) the loss of potassium acetate and dehydroxylation. The temperature of dehydroxylation and dehydration of halloysite is decreased about 100 °C. The infrared emission spectra clearly show the decomposition and dehydroxylation of the halloysite intercalation compound when the temperature is raised. The dehydration of the intercalation compound is followed by the loss of intensity of the stretching vibration bands at region 3600-3200 cm-1. Dehydroxylation is followed by the decrease in intensity in the bands between 3695 and 3620 cm-1. Dehydration was completed by 300 °C and partial dehydroxylation by 350 °C. The inner hydroxyl group remained until around 500 °C.

Thermal analysis of hydrotalcite synthesised from aluminate solutions

The aluminate hydrotalcites are proposed to have either of the following formulas: Mg4Al2(OH)12(CO3 2-)·xH2O or Mg4Al2(OH)12(CO3 2-, SO4 2-)·xH2O. A pure hydrotalcite phase forms when magnesium chloride and aluminate solns. are mixed at a 1:1 volumetric ratio at pH 14. The synthesis of the aluminate hydrotalcites using seawater results in the formation of an impurity phase bayerite. Two decompn. steps have been identified for the aluminate hydrotalcites: (1) removal of interlayer water (230 °C) and (2) simultaneous dehydroxylation and decarbonation (330 °C).