Determination and modelling of the cure shrinkage of epoxy vinylester resin and associated composites by considering thermal gradients

Quantification and understanding of the evolution of chemical shrinkage of thermoset polymers is of crucial importance for modelling of residual strains and stresses. Thermal properties of resin and the strong coupling between chemical reactions and thermal fields lead to non-negligible thermal and curing degree gradients in the part. In this paper, modelling of the volume chemical shrinkages of an unsaturated epoxy vinylester resin and associated glass fibre composites is proposed, by taking into account the coupling between volume variation and thermal gradients. Modelling is also compared with the measurements done with a home-made instrument (PVT-alpha). Results suggest that chemical shrinkage is non linear as a function of degree of cure. Moreover, for an equal mass of resin, chemical shrinkage of resin carrying fibres is lesser than the neat resin.

[1]  Harald E.N. Bersee,et al.  Shrinkage determination of a reactive polymer with volumetric dilatometry , 2010 .

[2]  N. Boyard,et al.  A Device to Measure the Shrinkage and Heat Transfers during the Curing Cycle of Thermoset Composites , 2011 .

[3]  D. Delaunay,et al.  Behaviour of a moulded composite part: Modelling of dilatometric curve (constant pressure) or pressure (constant volume) with temperature and conversion degree gradients , 2007 .

[4]  Harald E.N. Bersee,et al.  Measurement of (post-)curing strain development with fibre Bragg gratings , 2010 .

[5]  Isaac M Daniel,et al.  Determination of Chemical Cure Shrinkage in Composite Laminates , 1990 .

[6]  C. Jochum,et al.  A FEM coupling model for properties prediction during the curing of an epoxy matrix , 2009 .

[7]  Philippe Olivier,et al.  A note upon the development of residual curing strains in carbon/epoxy laminates. Study by thermomechanical analysis , 2006 .

[8]  K. Jansen,et al.  Characterization and modeling the thermo-mechanical cure-dependent properties of epoxy molding compound , 2012 .

[9]  Andrea Cusano,et al.  Real time monitoring of cure and gelification of a thermoset matrix , 2006 .

[10]  David Salmon,et al.  REVIEW ARTICLE: Thermal conductivity of insulations using guarded hot plates, including recent developments and sources of reference materials , 2001 .

[11]  Didier Delaunay,et al.  Heat transfer with mechanically driven thermal contact resistance at the polymer–mold interface in injection molding of polymers , 2004 .

[12]  J. D. Russell.  Cure shrinkage of thermoset composites , 1993 .

[13]  Gary W. Poehlein,et al.  A kinetic model for curing reactions of epoxides with amines , 1987 .

[14]  Takeshi Morita,et al.  IWPMA 2012 9th international workshop on piezoelectric materials and applications in actuators , 2013 .

[15]  James E. Martin,et al.  Calculation of Stresses in Crosslinking Polymers , 1996 .

[16]  N. Boyard,et al.  Measurement and Modelling of Chemical Shrinkage of Thermoset Composites , 2012 .

[17]  Minhat Ade Erawan,et al.  Comparison Studies of Electrical Discharge Machining (EDM) Process Model for Low Gap Current , 2012 .

[18]  Jan-Anders E. Månson,et al.  Residual stress build-up in thermoset films cured above their ultimate glass transition temperature , 1995 .

[19]  I. Alig,et al.  Time‐resolved method for the measurement of volume changes during polymerization , 2005 .

[20]  S. Hoa,et al.  Determination of Shrinkage and Modulus Development of Thermosetting Resins , 2009 .

[21]  Musa R. Kamal,et al.  Kinetics and thermal characterization of thermoset cure , 1973 .

[22]  M. Vayer,et al.  Analysis and modeling of PVTX diagram of an unsaturated polyester resin, thermoplastic additive, and mineral fillers blend , 2003 .

[23]  James M. Caruthers,et al.  A thermodynamically consistent, nonlinear viscoelastic approach for modeling glassy polymers , 2004 .

[24]  K. Schoch,et al.  Real-time measurement of resin shrinkage during cure , 2004 .

[25]  L. J. Lee,et al.  Dilatometric study of low profile unsaturated polyester resins , 1995 .

[26]  G. Q. Zhang,et al.  Effect of filler concentration of rubbery shear and bulk modulus of molding compounds , 2007, Microelectron. Reliab..

[27]  Yan-Jyi Huang,et al.  Volume shrinkage characteristics in the cure of low-shrink unsaturated polyester resins , 1996 .

[28]  R. Bruce Prime,et al.  Differential scanning calorimetry of the epoxy cure reaction , 1973 .

[29]  M. Vayer,et al.  Modeling PVTX diagrams: Application to various blends based on unsaturated polyester-influence of thermoplastic additive, fillers, and reinforcements , 2004 .

[30]  Antonello Cutolo,et al.  Monitoring by a single fiber Bragg grating of the process induced chemo-physical transformations of a model thermoset , 2004 .

[31]  S. Chatel,et al.  Material characterization and residual stresses simulation during the manufacturing process of epoxy matrix composites , 2010 .

[32]  Horng-Jer Tai,et al.  Chemical shrinkage and diffusion-controlled reaction of an epoxy molding compound , 2000 .

[33]  Optimisation du cycle de cuisson de pieces epaisses en materiau composite. Application a un preimpregne resine epoxyde / fibres de verre , 1997 .

[34]  J. D. Russell,et al.  A New Method to Reduce Cure-Induced Stresses in Thermoset Polymer Composites, Part I: Test Method , 2000 .

[35]  L. J. Lee,et al.  Development of a dilatometer and its application to low-shrink unsaturated polyester resins , 1992 .

[36]  Arnaud Millischer.  Transferts thermiques dans le procede d'injection bmc (bulk molding compound) , 2000 .

[37]  Yasir Nawab,et al.  Evolution of chemical and thermal curvatures in thermoset-laminated composite plates during the fabrication process , 2013 .

[38]  A. Snow,et al.  A simple dilatometer for thermoset cure shrinkage and thermal expansion measurements , 1994 .

[39]  Joël Cugnoni,et al.  Monitoring of process induced strains in a single fibre composite using FBG sensor: A methodological study , 2008 .

[40]  F. van der Graaf.  Heat Flux Sensors , 2008 .

[41]  Christopher W. Macosko,et al.  Heat transfer and curing in polymer reaction molding , 1976 .

[42]  Roberto J. J. Williams,et al.  Cure of epoxy resins containing epoxidized polyols , 1992 .

[43]  Michael R Wisnom,et al.  In-situ measurement of chemical shrinkage of MY750 epoxy resin by a novel gravimetric method , 2004 .

[44]  Darshil U. Shah,et al.  Evaluation of cure shrinkage measurement techniques for thermosetting resins , 2010 .

[45]  A. Vautrin,et al.  A Fresnel's Reflection Optical Fiber Sensor for Thermoset Polymer Cure Monitoring , 2004 .