Rheological Properties of Organoclay Suspensions in Epoxy Network Precursors

This paper deals with the evolution of the state of dispersion of organically modified montmorillonites in epoxy or amine precursors. The epoxy prepolymer is a diglycidyl ether of bisphenol A (DGEBA) and the curing agent is an aliphatic diamine with a polyoxypropylene backbone (Jeffamine D2000). The clay dispersion is evaluated at the platelet scale (nanoscopic scale) from X-ray spectrometry [wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS)] and at the aggregates scale (microscopic scale) from rheological analysis. The organoclays used form gels in the monomers above the percolation threshold if no shear is applied and present a mechanical gel/sol transition when shear stress increases. Gel strength and viscosity at high shear rates are linked to the nanometric state of dispersion and reveal the existence of two different organizations depending on organoclay/monomer interactions: (i) When the clay shows good interactions with the monomer, a significant swelling of the clay galleries by the monomer is obtained. These swollen particles lead to formation of weak gels which after shearing give high relative viscosity fluids. (ii) When the clay develops poor interactions with the monomer, the clay tends to reduce its exchange surface with the monomer and leads to a strongly connected gel. Shear breaks down this physical network leading to a very low relative viscosity fluid composed of nonswollen particles keeping a high aspect ratio. (C) 2003 Elsevier B.V All rights reserved.

Phase behavior, crystallization, and nanostructures in thermoset blends of epoxy resin and amphiphilic star-shaped block copolymers

This article reports thermoset blends of bisphenol A-type epoxy resin (ER) and two amphiphilic four-arm star-shaped diblock copolymers based on hydrophilic poly(ethylene oxide) (PEO) and hydrophobic poly(propylene oxide) (PPO). 4,4'-Methylenedianiline (MDA) was used as a curing agent. The first star-shaped diblock copolymer with 70 wt% ethylene oxide (EO), denoted as (PPO-PEO)(4), consists of four PPO-PEO diblock arms with PPO blocks attached on an ethylenediamine core; the second one with 40 wt% EO, denoted as (PEO-PPO)(4), contains four PEO-PPO diblock arms with PEO blocks attached on an ethylenediamine core. The phase behavior, crystallization, and nanoscale structures were investigated by differential scanning calorimetry, transmission electron microscopy, and small-angle X-ray scattering. It was found that the MDA-cured ER/(PPO-PEO)(4) blends are not macroscopically phase-separated over the entire blend composition range. There exist, however, two microphases in the ER/(PPO-PEO)(4) blends. The PPO blocks form a separated microphase, whereas the ER and the PEO blocks, which are miscible, form another microphase. The ER/(PPO-PEO)(4) blends show composition-dependent nanostructures on the order of 10-30 nm. The 80/20 ER/(PPO-PEO)(4) blend displays spherical PPO micelles uniformly dispersed in a continuous ER-rich matrix. The 60/40 ER/(PPO-PEO)(4) blend displays a combined morphology of worm-like micelles and spherical micelles with characteristic of a bicontinuous microphase structure. Macroscopic phase separation took place in the MDA-cured ER/(PEO-PPO)(4) blends. The MDA-cured ER/(PEO-PPO)(4) blends with (PEO-PPO)(4) content up to 50 wt% exhibit phase-separated structures on the order of 0.5-1 mu m. This can be considered to be due to the different EO content and block sequence of the (PEO-PPO)(4) copolymer. (c) 2006 Wiley Periodicals, Inc.

Phase separation, porous structure, and cure kinetics in aliphatic epoxy resin containing hyperbranched polyester

Thermosetting blends of an aliphatic epoxy resin and a hydroxyl-functionalized hyperbranched polymer (HBP), aliphatic hyperbranched polyester Boltorn H40, were prepared using 4,4'-diaminodiphenylmethane (DDM) as the curing agent. The phase behavior and morphology of the DDM-cured epoxy/HBP blends with HBP content up to 40 wt% were investigated by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and scanning electron microscopy (SEM). The cured epoxy/HBP blends are immiscible and exhibit two separate glass transitions, as revealed by DMA. The SEM observation showed that there exist two phases in the cured blends, which is an epoxy-rich phase and an HBP-rich phase, which is responsible for the two separate glass transitions. The phase morphology was observed to be dependent on the blend composition. For the blends with HBP content up to 10 wt%, discrete HBP domains are dispersed in the continuous cured epoxy matrix, whereas the cured blend with 40 wt% HBP exhibits a combined morphology of connected globules and bicominuous phase structure. Porous epoxy thermosets with continuous open structures on the order of 100-300 nm were formed after the HBP-rich phase was extracted with solvent from the cured blend with 40 wt% HBP. The DSC study showed that the curing rate is not obviously affected in the epoxy/HBP blends with HBP content up to 40 wt %. The activation energy values obtained are not remarkably changed in the blends; the addition of HBP to epoxy resin thus does not change the mechanism of cure reaction of epoxy resin with DDM. (c) 2006 Wiley Periodicals, Inc.

The effect of a curing agent on the thermal degradation of fire retardant brominated epoxy resins

The diglycidyl ether of tetrabromobisphenol A, the diglycidyl ether of bisphenol A and their mixture was cured by 4,4'-diaminodiphenyl methane. The pyrolysis of the obtained epoxy resins was studied by TG, DSC, TG/FTIR as well as FTIR characterization of pyrolysis residues. The gaseous and high boiling pyrolysis products were collected, characterized by GC/MS and their formation is discussed. The brominated epoxy resins are thermally less stable than the non-brominated ones. This effect is caused by the amine-containing hardener. The degradation initiation reaction is associated with the formation of hydrogen bromide which further destabilizes the epoxy network. The effect of the curing agent can be used in recycling of epoxy resins to separate brominated pyrolysis products from non-brominated ones.

Precast Concrete Panel Thickness for Epoxy-Coated Prestressing Strands, HR-353, Interim Report, 1994

A recommended minimum thickness for prestressed concrete (P/C) bridge deck panels containing 3/8-in. diameter, 270-ksi, low-relaxation, grit-impregnated, epoxy-coated prestressing strands is being evaluated by testing prototype panel specimens. As of January 1994, specimens from ten castings have been tested. The specimens in the first five castings were constructed to establish a preliminary minimum thickness for P/C panels. The specimens in the last five castings were constructed to 1) confirm the minimum panel thickness requirement, 2) measure the development length of epoxy-coated strands in specimens containing multiple strands, 3) measure the development length of uncoated strands in specimens containing multiple and single strands, 4) observe if concrete cracks form in thin panel specimens that have a raked top surface and are reinforced with welded wire fabric and either epoxy-coated or uncoated strands, 5) measure the transfer length for specimens containing a single uncoated strand, and 6) observe the seating characteristics of the grips used for uncoated strand and epoxy-coated strands. These tests have produced several initial findings. The preliminary recommended thickness for P/C panels containing grit-impregnated, epoxy-coated strands is 3 in. and the tentative development length for uncoated and coated multiple strands is approximately 45 in. and 24 in., respectively. Further tests will address confirmation of the recommended P/C panel thickness and establish the transfer and development lengths of single and multiple, uncoated and grit-impregnated epoxy-coated strands.

Material Evaluation of an Elastomer, Epoxy and Lightweight Concrete Rail Attachment System for Direct Fixation Light Rail Applications

Thesis (Master's)--University of Washington, 2016-08

Microstructure and tensile properties of carbon-epoxy laminates produced by automated fibre placement: Influence of a caul plate on the effects of gap and overlap embedded defects

Automated fibre placement (AFP) enables the trajectory of unidirectional composite tape to be optimized, but laying down complex shapes with this technology can result in the introduction of defects. The aim of this experimental study is to investigate the influence of gaps and overlaps on the microstructure and tensile properties of carbon-epoxy laminates. First, a comparison between a hand-layup and AFP layup, draped and cured under the same conditions, shows equivalent microstructures and tensile properties. This provides the reference values for the study. Then, gap and overlap embedded defects (more or less severe) are introduced during manufacturing, on two cross-ply layups [(0°/(90°)5/0°] and [(90°/0°)2/90°]. Autoclave cure without a caul plate results in local thickness variation and microstructural changes which depend on the defect type. This has a strong influence on mechanical performance. Use of a caul plate avoids these variations and in this case embedded defects hardly affect tensile properties.

Characterization of sea water ageing effects on mechanical properties of carbon/epoxy composites for tidal turbine blades

In recent years, many tidal turbine projects have been developed using composites blades. Tidal turbine blades are subject to ocean forces and sea water aggressions, and the reliability of these components is crucial to the profitability of ocean energy recovery systems. The majority of tidal turbine developers have preferred carbon/epoxy blades, so there is a need to understand how prolonged immersion in the ocean affects these composites. In this study the long term behaviour of different carbon/epoxy composites has been studied using accelerated ageing tests. A significant reduction of composite strengths has been observed after saturation of water in the material. For longer immersions only small further changes in these properties occur. No significant changes have been observed for moduli nor for composite toughness. The effect of sea water ageing on damage thresholds and kinetics has been studied and modelled. After saturation, the damage threshold is modified while kinetics of damage development remain the same.

Resistance of an epoxy coating with an organic inhibitor to cathodic disbondment in sea water

In this study, the effect of anti-corrosion inhibitor addition to epoxy coating, on the disbanding rate was evaluated. First to determination of mechanism, the bare steel substrates were immersed in the 3.5% NaCl solution and the solution containing 1 mM anti corrosion. The Electrochemical Impedance Spectroscopy was performed after 5 and 24 hour. The results indicated a lower corrosion rate in the presence of inhibitor. During the time, charge transfer resistance, was decreased for the substrates immersed in NaCl solution, and increased for the substrates immersed in NaCl solution containing 1 mM anti corrosion. This result can be related to more stability of corrosion products in presence of anti-corrosion and film formation. The coated substrates, with four different concentration of anticorrosion in coating, were protected under -1.2 voltage in the 3.5% NaCl solution. After 12 and 24 hour, the EIS test and disbanding area measurement, were evaluate. The lower disbanding rate, more charge transfer resistance and less double layer capacitance for the coating containing 0.75w% inhibitor, were observed. The result of Pull-off test after 1 day immersion in 3.5% NaCl solution, showed more wet adhesion for the coating containing 0.75w% inhibitor. The images of FE-SEM electron microscope and surface analyses EDX on the coated substrate after disbanding and the bare substrate immersed in 3.5w% NaCl containing 1 mM inhibitor, were proved the formation of stabilized film.

One-pot synthesis of aminated multi-walled carbon nanotube using thiol-ene click chemistry for improvement of epoxy nanocomposites properties

A non-oxidative method based on thiol-ene click chemistry for functionalization of multi-walled carbon nanotube (CNT) was performed in order to improve the interfacial interactions between epoxy matrix and CNT. In this way, the CNT was aminated using 2-aminoethanethiol hydrochloride radicals thermally produced by a peroxide radical initiator. The aminated CNT (CNT-NH2) was characterized by FTIR, TGA, and solubility evaluations, confirming that thiol radicals are successfully grafted onto the CNT surface with a proper yield. Various percentages of pure CNT (p-CNT) and CNT-NH2 were then incorporated into epoxy matrix to evaluate the effect of the functionalization of CNT on thermal, mechanical, and morphological properties. The nanocomposites were characterized by DMA, tensile testing, and TGA. Results showed that glass transition temperature, tensile properties and thermal stability of epoxy nanocomposites containing CNT-NH2 improves significantly compared to those containing unmodified CNT. These results prove the role of amino-functionalization in improving the interfacial adhesion between epoxy and CNT, which was further confirmed by morphological observations of fracture surfaces of the nanocomposites.