Photocuring of cycloaliphatic epoxy formulations using polyesters with multiarm star topology as additives

Multiam star polyesters were synthesized by growing poly(ε‐caprolactone) (PCL) arms from hyperbranched polyesters cores of different molecular weight and used as polymeric modifiers in UV‐curable cationic formulations based on a biscycloaliphatic epoxy resin. The effect of the multiarm stars on the curing kinetics has been investigated by real‐time FTIR. The thermal‐mechanical properties of the photocured thermosets have been studied with calorimetry and dynamomechanical and thermogravimetric analysis. Impact strength tests have been performed to assess their effect on the toughness of the cured materials. An accelerative effect of these modifiers has been observed as a consequence of the participation of the hydroxyl groups of the modifiers in the cationic curing of the epoxy resin. A modest increase in toughness accompanied by a decrease in the glass transition are observed, as a consequence of the incorporation of the modifiers into the network structure, leading to homogeneous, in situ reinforced materials. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40005.     

Parametric Estimation of Affine Transformations: An Exact Linear Solution

We consider the problem of estimating the geometric deformation of an object, with respect to some reference observation on it. Existing solutions, set in the standard coordinate system imposed by the measurement system, lead to high-dimensional, non-convex optimization problems. We propose a novel framework that employs a set of non-linear functionals to replace this originally high dimensional problem by an equivalent problem that is linear in the unknown transformation parameters. The proposed solution includes the case where the deformation relating the observed signature of the object and the reference template is composed both of the geometric deformation due to the affine transformation of the coordinate system and a constant amplitude gain. The proposed solution is unique and exact and is applicable to any affine transformation regardless of its magnitude.     

Crosslinking of mixtures of diglycidylether of bisphenol‐A with 1,6‐dioxaspiro[4.4] nonan‐2,7‐dione initiated by tertiary amines: III. Effect of hydroxyl groups on network formation

BACKGROUND: Blends of epoxy resin oligomers, diglycidylether of bisphenol‐A (DGEBA), and a bislactone, 1,6‐dioxaspiro[4.4]nonan‐2,7‐dione (s(γBL)), were anionically copolymerized using two tertiary amines as anionic initiators. Their curing rheology and gelation behaviour were studied to provide a more comprehensive knowledge of the curing of these previously studied systems. RESULTS: The activation energy for gelation was found to be similar to that previously measured using differential scanning calorimetry and appeared to increase in the presence of the bislactone. The reaction rate during copolymerization of DGEBA with s(γBL) was slower than DGEBA homopolymerization alone because the alkoxide attack on the epoxide is faster than the reaction of the carboxylate ion and the epoxy group. The effect of the initiator type on the gel conversion was small and was presumably due to differences in the kinetic chain length caused by amine regeneration from the quaternary amine. For the same initiator and at a constant ratio of DGEBA/s(γBL), an increase in the hydroxyl concentration of the DGEBA oligomer raised the gel conversion. For a DGEBA oligomer with low hydroxyl levels, an increase in the concentration of s(γBL) increased the gel conversion; however, for a DGEBA oligomer with high hydroxyl levels, increasing s(γBL) concentration decreased the gel conversion. CONCLUSION: These results are interpreted in terms of the effect of initiation rate and chain transfer rate on the kinetic chain length. The glass transition temperature of the gel was found to be controlled by the fraction of the aliphatic s(γBL) and the amount of plasticizing sol in the matrix. Copyright © 2009 Society of Chemical Industry     

Maximum likelihood parameter estimation of textures using aWold-decomposition based model

We present a solution to the problem of modeling, parameter estimation, and synthesis of natural textures. The texture field is assumed to be a realization of a regular homogeneous random field, which can have a mixed spectral distribution. On the basis of a 2-D Wold-like decomposition, the field is represented as a sum of a purely indeterministic component, a harmonic component, and a countable number of evanescent fields. We present a maximum-likelihood solution to the joint parameter estimation problem of these components from a single observed realization of the texture field. The proposed solution is a two-stage algorithm. In the first stage, we obtain an estimate for the number of harmonic and evanescent components in the field, and a suboptimal initial estimate for the parameters of their spectral supports. In the second stage, we refine these initial estimates by iterative maximization of the likelihood function of the observed data. By introducing appropriate parameter transformations the highly nonlinear least-squares problem that results from the maximization of the likelihood function, is transformed into a separable least-squares problem. The solution for the unknown spectral supports of the harmonic and evanescent components reduces the problem of solving for the transformed parameters of the field to a linear least squares. Solution of the transformation equations then provides a complete solution of the field-model parameter estimation problem. The Wold-based model and the resulting analysis and synthesis algorithms are applicable to a wide variety of texture types found in natural images.     

New thermosets obtained by cationic copolymerization of DGEBA with γ‐caprolactone with improvement in the shrinkage. II. Time–temperature–transformation (TTT) cure diagram

Mixtures of diglycidylether of bisphenol A (DGEBA) with different proportions of γ‐caprolactone (γ‐CL) were cured with ytterbium triflate as initiator. The curing was studied with differential scanning calorimetry (DSC) and thermo mechanical analysis (TMA). The results are presented in the form of a time–temperature–transformation diagram. The kinetic analysis was performed by means of the isoconversional integral procedure and the kinetic model was also determined using the Coats–Redfern method. Gelation was determined by means of combined experiences of DSC and TMA. The relationship between the glass transition temperature (T_g) and the degree of conversion α was determined by DSC. Using the isoconversional lines and the T_g‐α relationship, the vitrificacion curve was obtained. The methodology developed makes it possible to obtain the TTT diagram using only no‐isothermal experiments with equivalent results to those using classical isothermal procedures. The addition of γ‐CL accelerates the curing and reduces the shrinkage after gelation and consequently the internal stresses in the material. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Adaptive restoration of textured images with mixed spectra

We consider the adaptive restoration of inhomogeneous textured images, where the individual regions are modeled using a Wold-like decomposition. A generalized Wiener filter is developed to accommodate mixed spectra, and unsupervised restoration is achieved by using the expectation-maximization (EM) algorithm to estimate the degradation parameters. This algorithm yields superior results when compared with supervised Wiener filtering using autoregressive (AR) image models.     

Bounds on the accuracy of estimating the parameters of discretehomogeneous random fields with mixed spectral distributions

This paper considers the achievable accuracy in jointly estimating the parameters of a real-valued two-dimensional (2-D) homogeneous random field with mixed spectral distribution, from a single observed realization of it. On the basis of a 2-D Wold-like decomposition, the field is represented as a sum of mutually orthogonal components of three types: purely indeterministic, harmonic, and evanescent. An exact form of the Cramer-Rao lower bound on the error variance in jointly estimating the parameters of the different components is derived. It is shown that the estimation of the harmonic component is decoupled from that of the purely indeterministic and the evanescent components. Moreover, the bound on the parameters of the purely indeterministic and the evanescent components is independent of the harmonic component. Numerical evaluation of the bounds provides some insight into the effects of various parameters on the achievable estimation accuracy     

Sensitivity analysis of distributed environmental simulation models: understanding the model behaviour in hydrological studies at the catchment scale

The development of new hydrological simulation tools allows for the modelling of large hydrological catchments, with the aim of comprehensive management of the water resources, control of diffuse pollution processes, such as the fate of agricultural fertilizants and finally, with purposes of economical optimization of the crop yields as a function of the expected climate, the watershed characteristics and the socio-economical conditions of the region where the catchment is located. This paper describes the sensitivity analysis of a hydrological distributed model applied in one large European watershed by using a two-step procedure. Firstly, it allows for the consideration of a huge input parameter data set by using an implementation of the Morris screening procedure, eschewing the huge computational requirements arising from the necessary repetitive simulations. In the second step it provides quantitative estimations of sensitivity in terms of variance decomposition procedures based upon the FAST method for both the hydrological and the water quality determinants.     

Modification of epoxy–anhydride thermosets using a hyperbranched poly(ester‐amide): I. Kinetic study

An epoxy‐anhydride formulation used for the coating of electrical devices was modified with a commercially available hyperbranched poly(ester‐amide), Hybrane? S2200, in order to improve the thermal degradability of the resulting thermoset and thus facilitate the recovery of substrate materials after use of the component. The curing kinetics of the unmodified and modified formulations were studied in detail with differential scanning calorimetry, Fourier transform infrared spectroscopy and rheology. The results suggest that S2200 gets incorporated into the network structure and the curing kinetics are accelerated by the presence of hydroxyl groups from S2200. Copyright © 2012 Society of Chemical Industry     

Estimating the orientation of planar surfaces: algorithms andbounds

This paper presents a computationally and statistically efficient parametric solution to the problem of estimating the orientation in space of a planar textured surface from a single, noisy, observed image of it. The coordinate transformation from surface to image coordinates, due to the perspective projection, transforms each homogeneous sinusoidal component of the surface texture into a sinusoid whose frequency is a function of location. The functional dependence of the sinusoid phase in location is uniquely determined by the tilt and slant angles of the surface. From the physical model of the perspective projection, we derive the Cramer-Rao lower bound on the error variance of estimating the tilt and slant of the observed surface in the presence of observation noise. It is shown in this paper that the phase of each of the sinusoids can be expressed as a linear function of some variables that are related to the surface tilt and slant angles. Using the phase differencing algorithm, we fit a polynomial phase model to a sinusoidal component of the observed texture. Substituting in the derived linear relation, the unknown phase with the one estimated using the phase differencing algorithm, we obtain a closed-form, analytic, and computationally efficient solution to the problem of estimating the tilt and slant angles. The algorithm performance is shown to be close to the Cramer-Rao bound, even for low signal-to-noise ratios, at computational complexity which is considerably lower than that of any existing algorithm