The cure of polydicyclopentadiene conducted by ring-opening metathesis polymerisation in the presence of a Grubbs catalyst was studied using non-invasive Raman spectroscopy. The spectra of the monomer precursor and polymerised product were fully characterised and all stages of polymerisation monitored. Because of the monomer's high reactivity, the cure process is adaptable to reaction injection moulding and reactive rotational moulding. The viscosity of the dicyclopentadiene undergoes a rapid change at the beginning of the polymerisation process and it is critical that the induction time of the viscosity increase is determined and controlled for successful manufacturing. The results from this work show non-invasive Raman spectroscopic monitoring to be an effective method for monitoring the degree of cure, paving the way for possible implementation of the technique as a method of real-time analysis for control and optimisation during reactive processing. Agreement is shown between Raman measurements and ultrasonic time of flight data acquired during the initial induction period of the curing process. 相似文献
Air-coupled ultrasound in one-side transmission mode has been applied to monitor the curing process of an unsaturated polyester resin, commonly used as a matrix in glass reinforced composites. The evolution of the resin mechanical properties during cure has been measured from the variation of longitudinal velocity. The technique has demonstrated to be a very powerful tool for detecting the structural changes occurring at gelation and vitrification. The no-contact ultrasonic results have been compared with those obtained using conventional contact ultrasonic measurements, characterized by direct coupling between the transducer and the resin, and with the rheological measurements. The good agreement among the results of the different techniques demonstrates the reliability of air-coupled ultrasound in monitoring the changes of viscoelastic properties occurring during the cure of thermosetting polymers. A further advantage of the proposed one-side ultrasonic technique is the absence of physical contact between the transducers and the sample, which is relevant during composite manufacturing, where probe contact could adversely affect the part quality or access from both sides is not practicable. No-contact ultrasonic cure monitoring is suitable for both stationary and moving liquid or solid samples in several process conditions such as moulding, filament winding, etc., opening the way to new applications of ultrasound in the composite industry. 相似文献
Simultaneous dielectric and near infrared measurements have been performed in “real-time” to follow polymerisation reactions on blends of a diglycidyl ether of bisphenol-A epoxy resin with 4,4′-diaminodiphenylmethane hardener and different amounts of poly(methylmethacrylate) as modifier. The effect of the modifier amount on the polymerisation reactions has been studied, as well as that of the curing temperature. Epoxy and amine conversions have been followed by near infrared spectroscopy (NIR), while changes in molecular mobility in the reaction mixture have been analysed by dielectric relaxation spectroscopy (DRS). Evolutions of ionic conductivity and α-relaxation have been analysed and vitrification times have been obtained. The relaxational behaviour has been analysed through curing in the frequency domain, being the change of the main relaxation indicative of the cure reaction advancement. DRS data are also presented as complex impedance Z(ω). Vitrification times, obtained by dielectrometry have been compared with those obtained by rheological measurements and gelation times obtained by NIR have been compared with those obtained by solvent extraction. 相似文献
Photo-DSC was used to investigate the cure kinetics of a photo-initiated resin. The exothermal photo-polymerization reactions were performed in isothermal mode. The irradiation of photo-initiated resin was studied under different conditions of temperature, UV lamp intensity, and reaction atmosphere (nitrogen and air). The results obtained by photo-DSC allowed us to determine kinetic data of the photo-polymerized reactions: the global activation energy and reaction enthalpy, and the conversion as a function of time and temperature. Modulated temperature DSC measurements were carried out to verify whether vitrification occurs during polymerization. The conversion at the top and bottom of irradiated samples was obtained by FT-IR spectroscopy before and after photo-polymerization. A non-homogenous photo-polymerization into the material was observed, probably because of the light absorptions effects within the uppermost layers. 相似文献
The process of vitrification that occurs during the isothermal cure of a cross-linking system at temperatures below Tg∞, the glass transition temperature of the fully cured resin, has been studied by TOPEM, a new temperature modulated DSC (TMDSC)
technique based upon the use of stochastic temperature pulses. A comparison is made between TOPEM and another TMDSC technique,
and some advantages of TOPEM are considered. The TOPEM technique is used to show that the mobility factor is not always a
reliable approach to predicting the cure rate during vitrification, in view of its frequency dependence. Also, the dependence
of the apparent vitrification time on frequency is examined. There appears to be a non-linear relationship between the apparent
vitrification time and log(frequency), which is further discussed in the second part of this series. 相似文献
This paper tries to assess simply and quantitatively the link between classical adsorption theories and dielectric spectroscopy, in order to demonstrate that dielectric spectroscopy can be used as a tool of determination of surface energy variations due to movements of charge carriers at the surface of solids. A simple theory is developed to analyze hops of cations at the surface of mordenite, which are detected by complex impedance spectroscopy during adsorption of water. An energy of extraction of the cation can be determined from measurements and its dependence on the quantity of water molecules adsorbed is shown and qualitatively and quantitatively explained, using relationships developed in order to interpret adsorption phenomena generally. The agreement with other determinations of the adsorption energies and solid surface energy is correct. 相似文献
The dielectric properties of concentrated w/o-emulsions have been investigated, both at rest and during shear. The volume fraction water ranged from 0.50 to 0.95. The time domain dielectric spectroscopy techniques (TDS) was used to record the dielectric spectra, which covered the frequency region from 25 MHz to 2 GHz. In order to simultaneously record rheological and dielectric data a modified viscometer of the coaxial cylinder type was applied.A close connection between the viscosity and the dielectric properties of w/o emulsions is demonstrated. The very large effects of shear both on the static permittivity and the dielectric relaxation time for the emulsion can partially be ascribed to the degree of flocculation in the system. At high shear rates, at which the emulsions are expected to have a low degree of flocculation, the observed dielectric properties differ from those expected from a theoretical model for spherical emulsion droplets. 相似文献
Thermal diffusivity was measured online during cure of an epoxy composite using a method somewhat similar to the Ångström Method. It is shown that a simple experimental setup can be used, thus avoiding expensive instrumentation. The experimental instrumentation is explained in detail. The measurements show an increase of thermal diffusivity during the cure of composite material. Using modulated differential scanning calorimetry (MDSC), heat capacity was measured online during the cure of an epoxy composite. Combining thermal diffusivity measurements with MDSC measurements, the thermal conductivity was found to change during the cure process, similar to the measurements of heat capacity. These changes are referred to vitrification at the end of the cure process. 相似文献
Summary: We report a new methodology to determine the gelation and vitrification of a thermosetting material during the polymerization process by detecting the evolution of cure shrinkage through a thermomechanical analyzer (TMA) and a differential scanning calorimeter (DSC). The gelation and vitrification determined by the evolution of cure shrinkage correspond favorably with that measured by conventional rheological techniques. The isoconversional phenomenon at gelation point was further confirmed by monitoring cure shrinkage at temperatures ranging from 90 to 110 °C. Whereas, vitrification was observed to occur at higher degrees of cure with increasing cure temperatures. Inhibited cure shrinkage was also observed in the vitrification region where the reaction transitioned from chemical to diffusion controlled.
Combination of dimension change detected by DMA and heat flow detected by DSC for determining the relationship of cure shrinkage and degree of cure. 相似文献
A comparison of NaCl transport across two dense cellulosic membranes from different suppliers is presented. Hydraulic and diffusional permeabilities were determined from volume flow-applied pressure and concentration-time relationships, while cation transport number and membrane conductivity were determined from electromotrice force and impedance spectroscopy measurements, respectively. Chemical surface differences between both membranes are correlated to transport parameters and morphology, but differences in elastic properties of both membranes might also be considered in order to get a more complete picture of membrane behaviors and to obtain structural-transport parameters correlations. 相似文献
In this study the correlations between protein contents of different kinds of natural rubber were considered with rheological behavior, compression set and hardness of rubber compounds based on natural rubber. At the first stage, protein contents were obtained by Kjeldahl method and correlated with normalized absorbance of amine band in NR's attenuated total reflection Fourier transform infrared spectra and shown linear behavior. At the second stage, correlations between the protein contents obtained by the spectra were considered with rheological behavior, compression set and hardness of rubber compounds and shown second order fitting models. The introduced models were applied to predict these features in case studies. Results were shown that Mooney viscosity, torque difference, optimum cure time, scorch time, cure rate index and hardness can be predicted by lower than 10% while compression set can be estimated by lower than 20% error. This significant attitude is a nondestructive and fast technique that uses little quantity of NR for prediction of some NR based compounds properties, before compounding. 相似文献
The thermal cure kinetics of an epoxidized linseed oil with methyl nadic anhydride as curing agent and 1-methyl imidazole
as catalyst was studied by differential scanning calorimetry (DSC). The curing process was evaluated by non-isothermal DSC
measurements; three iso-conversional methods for kinetic analysis of the original thermo-chemical data were applied to calculate
the changes in apparent activation energy in dependence of conversion during the cross-linking reaction. All three iso-conversional
methods provided consistent activation energy versus time profiles for the complex curing process. The accuracy and predictive
power of the kinetic methods were evaluated by isothermal DSC measurements performed at temperatures above the glass transition
temperature of the completely cured mixture (Tg∞). It was found that the predictions obtained from the iso-conversional method by Vyazovkin yielded the best agreement with
the experimental values. The corresponding activation energy (Ea) regime showed an increase in Ea at the beginning of the curing which was followed by a continuous decrease as the cross-linking proceeded. This decrease
in Ea is explained by a diffusion controlled reaction kinetics which is caused by two phenomena, gelation and vitrification. Gelation
during curing of the epoxidized linseed/methyl nadic anhydride system was characterized by rheological measurements using
a plate/plate rheometer and vitrification of the system was confirmed experimentally by detecting a significant decrease in
complex heat capacity using alternating differential scanning calorimetry (ADSC) measurements. 相似文献
We investigated the effects of cysteine on β-lactoglobulin interactions using ultrasound spectroscopy, rheological measurements,
and differential scanning calorimetry. Changes in ultrasonic velocity and attenuation were monitored using ultrasound spectroscopy,
and we discuss the effects of cysteine on gel formation together with the results obtained using other methods. A decrease
in ultrasonic velocity occurred around 54 °C, suggesting that the compressibility of the system increases at approximately
this temperature. An increase in ultrasonic attenuation was observed at approximately 54 °C, which is much lower than the
commonly observed denaturation temperature of 75–80 °C. The temperature coincided with the onset of phase transition by differential
scanning calorimetry and the initial rise in temperature of dynamic modulus for rheological measurements under heat treatment.
We conclude that cysteine promotes the polymerization processes of denatured proteins during the initial stage of gelation.
The ultrasonic spectroscopic analysis is a useful tool to monitor protein molecule interactions prior to gelation. 相似文献
Simultaneous dielectric and near infrared measurements were performed in “real-time” to follow polymerisation reactions on blends of a diglycidyl ether of bisphenol A (DGEBA) epoxy resin with 4,4′-diaminodiphenylmethane (DDM) hardener and a mixture of polysulphone (PSU) and polyetherimide (PEI) as modifier. All the blends had a 10 wt% of PSU/PEI mixture. The effect of the PEI/PSU ratio in the mixture was studied. Monitoring of the α-relaxation (related to vitrification) was performed by dielectric measurements, while epoxy conversion was followed by near infrared spectroscopy. The effect of the PEI/PSU ratio on this behaviour was studied, as well as that of the curing temperature. Obtained results were compared with that of the blends with neat PSU and PEI as modifiers. 相似文献
This paper describes a new method for measuring the attachment of bacteria, specifically Escherichia coli on platinum electrodes using impedance spectroscopy. Impedance spectroscopy measurements showed that the double layer capacitance of the electrode was very sensitive both to the concentration of bacteria in the solution and to the attachment time. Impedance measurements of E. coli were compared with classical measurements of bacterial attachment on identical electrodes such as staining/microscopy and bacterial removal by sonication and plating onto agar. The relationship between the measured impedance of the electrode during attachment and the biophysical processes involved is discussed. 相似文献