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Gel Point (gel + point)
Selected AbstractsSimultaneous light and small-angle neutron scattering on aggregating concentrated colloidal suspensionsJOURNAL OF APPLIED CRYSTALLOGRAPHY, Issue 1 2003Sara Romer A new sample environment has been developed in order to perform light and small-angle neutron scattering (SANS) simultaneously on colloidal systems. The combination of SANS and diffusing wave spectroscopy (DWS) is of particular use in the high-concentration regime. DWS provides information on the local dynamic properties of the individual particles, whereas SANS gives access to the structural properties on similar length scales. The combination of both methods thus allows one to obtain structural and dynamic information over a very large range of length and time scales. Using this new setup, the onset of aggregation and the sol,gel transition in concentrated destabilized polystyrene sphere suspensions have been investigated. At the gel point, a dramatic change of the particle dynamics from diffusion to a subdiffusive arrested motion is observed. However, while the DWS measurements indicate that dramatic changes in the local dynamics occur over a long period, the SANS pattern quickly reaches its final appearance. The SANS experiments thus indicate that a fluid-like structure is arrested in the course of the gel formation. The data are found to be in good qualitative agreement with computer simulations. [source] Estimation of the hindered settling function R(,) from batch-settling testsAICHE JOURNAL, Issue 4 2005Daniel R. Lester Abstract The hindered settling function R(,) is a material function that quantifies the interphase drag of colloidal suspensions for all solids volume fractions ,. A method is presented to estimate R(,) from batch-settling tests for solids volume fractions between the initial solids volume fraction, ,0, and the solids volume fraction at which the suspension forms a continuously networked structure, ,g, known as the gel point. The method is based on an analytic solution of the associated inverse problem. Techniques are presented to address initialization mechanics observed in such tests as well as experimental noise and discrete data. Analysis of synthetic and experimental data suggests that accurate estimates of R(,) are possible in most cases. These results provide scope for characterization of suspension dewaterability from batch-settling tests alone. © 2005 American Institute of Chemical Engineers AIChE J, 2005 [source] Confined space regulated polymerizationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 5 2008Ye-Zi You Abstract The confined space produced during the polymerization has access for all small organic molecules or oligomers with small size to enter this confined space; however, it can prevent the macromolecules with big size from entering. Therefore, the reaction between two branched macromolecules is excluded in A2+B3 polymerization system, resulting uncrosslinked branched polymers, and there was no gel point observed throughout the polymerization. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1730,1737, 2008 [source] Crosslinking polymerization leading to interpenetrating polymer network formation.JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 21 2003Abstract As part of our continuing studies concerned with the elucidation of the crosslinking polymerization mechanism leading to interpenetrating polymer network (IPN) formation, in which IPNs consist of both polymethacrylates and polyurethane (PU) networks, this article explores the polyaddition crosslinking reactions of multifunctional poly(methyl methacrylate- co -2-methacryloyloxyethyl isocyanate) [poly(MMA- co -MOI)] [MMA/MOI = 90/10] with various diols leading to PU network formation. Thus, the equimolar polyaddition crosslinking reactions of poly(MMA- co -MOI) with ethylene glycol (EG), 1,6-hexane diol, and 1,10-decane diol (DD) were carried out in N -methyl pyrrolidone at a 0.25 mol/L isocyanate group concentration at 80 °C. The second-order rate constants decreased from EG to DD. The deviation of the actual gel point from the theoretical one was smaller from EG to DD. The intrinsic viscosity of resulting prepolymer demonstrated almost no variation with progressing polymerization for the EG system, whereas it gradually increased with conversion for the DD system. Close to the gel point conversion it increased rather drastically for both systems. The swelling ratio of resulting gel was higher from EG to DD. These are discussed mechanistically in terms of the significant occurrence of intramolecular cyclization and intramolecular crosslinking reactions leading to shrinkage of the molecular size. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3243,3248, 2003 [source] Crosslinking polymerization leading to interpenetrating polymer network formation.JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 4 2003Abstract At the start of our research program concerned with the elucidation of the crosslinking polymerization mechanism leading to interpenetrating polymer network (IPN) formation, in which IPNs consist of both polymethacrylates and polyurethane (PU) networks, this article deals with the polyaddition crosslinking reaction leading to PU network formation. Therefore, 2-methacryloyloxyethyl isocyanate (MOI) was radically copolymerized with methyl methacrylate (MMA) in the presence of CBr4 as a chain-transfer agent. The resulting poly(MMA- co -MOI)s, having pendant isocyanate (NCO) groups as novel multifunctional polyisocyanates, were used for polyaddition crosslinking reactions with ethylene glycol as a typical diol. The second-order rate constants depended on both the functionality of poly(MMA- co -MOI) and the NCO group concentration. The actual gel points were compared with the theoretical ones calculated according to Macosko's equation; the deviation of the actual gel point from the theoretical value became more remarkable for a greater functionality of poly(MMA- co -MOI) and at a lower NCO group concentration or at a lower poly(MMA- co -MOI) concentration. These are discussed mechanistically, with consideration given to the significance of intramolecular cyclization and intramolecular crosslinking reactions leading to the shrinkage of the molecular size of the prepolymer, along with the data of the intrinsic viscosities of resulting prepolymers and the swelling ratios of resulting gels. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 606,615, 2003 [source] Kinetic Modeling of Thiol-Ene Reactions with Both Step and Chain Growth AspectsMACROMOLECULAR THEORY AND SIMULATIONS, Issue 4 2005Oguz Okay Abstract Summary: A kinetic model is presented for thiol-ene cross-linking photopolymerizations including the allowance for chain growth reaction of the ene, i.e., homopolymerization. The kinetic model is based on a description of the average chain lengths derived from differential equations of the type of Smoluchowski coagulation equations. The method of moments was applied to obtain average properties of thiol-ene reaction systems. The model predicts the molecular weight distribution of active and inactive species in the pre-gel regime of thiol-enes, as well as the gel points depending on the synthesis parameters. It is shown that, when no homopolymerization is allowed, the average molecular weights and the gel point conversion are given by the typical equations valid for the step-growth polymerization. Increasing the extent of homopolymerization also increases the average molecular weights and shifts the gel point toward lower conversions and shorter reaction times. It is also shown that the ratio of thiyl radical propagation to the chain transfer kinetic parameter (kp1/ktr) affects the gelation time, tcr. Gelation occurs earlier as the kp1/ktr ratio is increased due to the predominant attack of thiyl radicals on the vinyl groups and formation of more stable carbon radicals. The gel point in thiol-ene reactions is also found to be very sensitive to the extent of cyclization, particularly, if the monomer functionalities are low. Number-average chain length of carbon radicals (solid curves) and thiyl radicals (dashed curves) plotted against the vinyl group conversion, xM, during thiol-ene polymerization. Calculations were for six different kp/ktr ratios. [source] Reconstruction of the Chain Length Distribution for Vinyl-Divinyl Copolymerization Using the Numerical Fractionation TechniqueMACROMOLECULAR THEORY AND SIMULATIONS, Issue 8 2003Georgia Papavasiliou Abstract A proposed theory for evaluating the chain length distribution (CLD) using the numerical fractionation (NF) technique was extended to the vinyl-divinyl (VDV) copolymerization. The CLD is reconstructed for this system, in which pendant double bond propagation leads to crosslinking and gel formation. The method was earlier developed for a non-linear free-radical polymerization scheme where chain transfer to polymer and termination by combination resulted in gel formation. The VDV study presented indicates that the proposed method of weighted summation (WS) accurately predicts the resulting CLDs evaluated using NF. Comparison of the overall polymer NF and the direct solution CLDs near the gel point. [source] Properties of new nanocomposite triblock copolymer gels based on expandable graphite,POLYMER ENGINEERING & SCIENCE, Issue 9 2008Marissa A. Paglicawan In this work, we investigated the effect of expandable graphite (EG) on the property of triblock copolymer prepared from a poly(styrene- b -(ethylene- co -butylene)- b -styrene) (SEBS) imbibed with an EB-compatible hydrocarbon oil. The rheological properties showed that at a temperature between 30 and 40°C below the gel point, the triblock copolymer gels had a dynamic storage modulus (G,) greater than loss modulus (G,), thereby indicating that at ambient temperature, a physical network is still present in spite of the addition of nanoparticles. Dynamic rheological measurements of the resultant nanocomposite triblock copolymer gels confirmed that the addition of EG affects the linear viscoelastic properties and maximum operating temperature of the parent triblock copolymer gels. The mechanical properties showed only marginal increase, which can be attributed to the poor dispersion that leads to agglomeration of particle into micrometer size stacks, and thus the particles behave only as inorganic fillers. The morphology and X-ray diffraction revealed that the EG used to generate nanocomposite triblock copolymer gels is dispersed generally within the swollen copolymer and/or solvent. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers [source] Formation of a fibrillar morphology of crosslinked epoxy in a polystyrene continuous phase by reactive extrusionPOLYMER ENGINEERING & SCIENCE, Issue 4 2004Françoise Fenouillot An immiscible polymer blend where the dispersed phase is fibrillar was prepared by in situ crosslinking of the minor phase. A model polystyrene/epoxy-amine blend was selected on the basis of rheological (achievement of the fibrillar structure) and reactivity (fast crosslinking) criteria. The system was a polystyrene/diglycidyl ether of bisphenol A (DGEBA)-aminoethyl piperazine (AEP) blend. At the temperature of extrusion, 180°C, the DGEBA is immiscible in PS and heterogeneous material is obtained. The elongational flow imposed by drawing the extrudate at the die exit permitted controlled generation of a fibrillar morphology of the dispersed epoxy phase, with a fiber diameter of 1 ,m and an aspect ratio greater than 100. It was shown that when the amine comonomer was injected into the extruder, its reactivity with DGEBA at high temperature was high enough to ensure partial crosslinking of the epoxy. The fibrils were formed even though the gel point of the epoxy phase was exceeded. However, above a certain critical insoluble fraction that we estimated to be between 45% and 70%, a coarsening of the structure appeared, caused by the decreasing deformability of the domains and their coalescence. Finally, for our system, the crosslinking of the dispersed phase up to 90% of insoluble fraction did not totally stabilize the morphology after the second processing step (injection molding). Polym. Eng. Sci. 44:625,637, 2004. © 2004 Society of Plastics Engineers. [source] Preparation and properties of silicone-containing poly(methyl methacrylate) gelsPOLYMER INTERNATIONAL, Issue 11 2005Hamid Javaherian Naghash Abstract Poly(methyl methacrylate) (PMMA) gels with varying amounts of silicone and solvent and constant amounts of crosslinker were prepared by solution free radical crosslinking copolymerization of methyl methacrylate (MMA), ethylene glycol dimethacrylate (EGDM), tetraethoxysilane (TEOS) and vinyltriethoxysilane (VTES) comonomer systems. They were then studied in benzene at a total monomer concentration of 3.5 mol L,1 and 70 °C. The conversion of monomer, volume swelling ratio, weight fraction and gel point were measured as a function of the reaction time, silicone concentration and benzene content up to the onset of macrogelation. Structural characteristics of the gels were examined by using equilibrium swelling in benzene, gel fraction and Fourier-transform infrared (FTIR) analysis. The morphology of the copolymers was also investigated by SEM. Based on the obtained results, it was concluded that the FTIR data did not have the capacity to show the presence of the VTES or TEOS moiety in these kinds of copolymers. On the other hand, the variation of weight fraction of gel, Wg, and its equilibrium volume swelling ratio in benzene, qv, exhibited the same behaviour as that of MMA/EGDM copolymers. Also, the dilution of the monomer mixture resulted in an increase in the gel point and swelling degree and a decrease in the percent of conversion and gel fraction. Finally, TEOS is not an ideal silicone compound for reaction in the MMA/EGDM copolymerization system, whereas VTES is a suitable silicone comonomer for this system and it has been proved useful. Copyright © 2005 Society of Chemical Industry [source] Characterization of gelatin nanofibers electrospun using ethanol/formic acid/water as a solventPOLYMERS FOR ADVANCED TECHNOLOGIES, Issue 2 2009Hsin-Chieh Chen Abstract Gelatin nanofibers were prepared via electrospinning using aqueous solutions of formic acid and ethanol as the solvent instead of cytotoxic solvents. The resulting mat was further crosslinked with glutaraldehyde (GTA). The influence of the storing time on the viscosity and gel point of the solution was investigated. The gelatin nanofibers were examined using a field emission scanning electron microscope (FESEM) for the fiber size and morphology. The lowest diameter of gelatin fiber (85,nm, without beads) was achieved when the gelatin concentration was 20,wt% and electrospinning was conducted with a voltage of 20,kV over a distance of 10,cm at ambient temperature. The results from differential scanning calorimetry (DSC) showed that the softening temperature of gelatin nanofibers crosslinked with GTA was elevated. In addition, GTA-crosslinked gelatin nanofibers exhibited cell compatibility for mouse mesangial cells (CRL 1927). Copyright © 2008 John Wiley & Sons, Ltd. [source] Gel point prediction of metal-filled castor oil-based polyurethanes system,POLYMERS FOR ADVANCED TECHNOLOGIES, Issue 10-12 2002Anil Srivastava Abstract Prediction of gel point conversion and network formation is of great importance in polycondensation during synthesis as well as processing. It enables one to estimate the safe conversions for reactor operation without gelation and the cycle time during processing, and plays an important role in controlling the molding parameters used for reinforced reaction injection molding (RRIM), reaction injection molding (RIM) and compression molding. Theories of gelation have been extensively published in the literature and supported by experimental data for various polycondensation systems. However, most such studies relate to unfilled systems. In this work, metal-filled polyurethanes have been synthesized in bulk by reacting toluene di-isocyanate with castor oil and its polyols possessing different hydroxyl values. Metallic aluminum powder (10,40% by weight) was dispersed thoroughly in castor oil and its polyols before reacting at different temperatures (30,60,°C) in a moisture-free, inert environment. The gel point conversions were measured experimentally and an empirical model from the experimental data has been developed to predict the gelation behavior. The proposed model could be of immense importance in the paints, adhesives and lacquers industries, which use castor oil in bulk. From these experiments it was concluded that: (i) fine metal powder gives a rise in viscosity; (ii) metal fillers not only restrict the molecular motion due to the increase in viscosity, but also lower the conversion; (iii) the vegetable oil and its polyols have a number of bulky groups, which also impart the delay tendency in gel time; (iv) there is a change in gelation dynamics at 50,°C , this is due to the change in reactivity of di-isocyanates; (v) the presence of metal filler does not initiate the intermolecular condensation; (vi) there is a gap between theoretical and experimental gel point owing to the unequal reactivity of the secondary alcohol position; (vii) there is an inverse relationship of gel time with the reaction temperature and hydroxyl value of polyols. An empirical model based on process parameters, i.e., hydroxyl value, temperature, shape factor and filler concentration, has been derived and found to be adequate for the metal-filled system. The correlation coefficient on the data is on the lower side in some cases because the following were not taken into account: (i) the first-order kinetics followed by the reaction in the second half while it is tending towards gelation; (ii) the error in observing the gel point viscosity; (iii) errors in assuming the spherical shape of aluminum metal powder; (iv) errors due to failure to maintain the constant speed in agitation. Copyright © 2003 John Wiley & Sons, Ltd. [source] Kinetic Modeling of Thiol-Ene Reactions with Both Step and Chain Growth AspectsMACROMOLECULAR THEORY AND SIMULATIONS, Issue 4 2005Oguz Okay Abstract Summary: A kinetic model is presented for thiol-ene cross-linking photopolymerizations including the allowance for chain growth reaction of the ene, i.e., homopolymerization. The kinetic model is based on a description of the average chain lengths derived from differential equations of the type of Smoluchowski coagulation equations. The method of moments was applied to obtain average properties of thiol-ene reaction systems. The model predicts the molecular weight distribution of active and inactive species in the pre-gel regime of thiol-enes, as well as the gel points depending on the synthesis parameters. It is shown that, when no homopolymerization is allowed, the average molecular weights and the gel point conversion are given by the typical equations valid for the step-growth polymerization. Increasing the extent of homopolymerization also increases the average molecular weights and shifts the gel point toward lower conversions and shorter reaction times. It is also shown that the ratio of thiyl radical propagation to the chain transfer kinetic parameter (kp1/ktr) affects the gelation time, tcr. Gelation occurs earlier as the kp1/ktr ratio is increased due to the predominant attack of thiyl radicals on the vinyl groups and formation of more stable carbon radicals. The gel point in thiol-ene reactions is also found to be very sensitive to the extent of cyclization, particularly, if the monomer functionalities are low. Number-average chain length of carbon radicals (solid curves) and thiyl radicals (dashed curves) plotted against the vinyl group conversion, xM, during thiol-ene polymerization. Calculations were for six different kp/ktr ratios. [source] | |||||||||||||