A Device to Measure the Shrinkage and Heat Transfers during the Curing Cycle of Thermoset Composites


Article Preview

Residual stresses development during manufacturing of composites depends mostly on the shrinkage behaviour of the polymer matrix from the point where stresses cannot be relaxed anymore. The matrix shrinkage may have a thermal and/or chemical origin and can leads to dimensional instability, ply cracking, delamination and fibre buckling. The approaches for measuring cure shrinkage can be classified as volume and non-volume dilatometry. Each technique has corresponding advantages and drawbacks but volume dilatometry is the one that is mostly used. In the present article, we report a home-built apparatus, named PVT-a mould, on which temperature, volume change and reaction conversion degree are measured simultaneously for an applied pressure. It can also be used to study the composite during curing and for the bulk samples having several millimetre thicknesses. The instrument is preferred over other techniques as it works in conditions close to the industrial ones. This device was used to measure cure shrinkage of resin and thermoset composite material with different fibre fractions as a function of temperature and reaction conversion degree. The heat of cure of the resin measured by PVT-a mould was compared to the results obtained by DSC.



Edited by:

Arshad Munir and Zaffar M. Khan




Y. Nawab et al., "A Device to Measure the Shrinkage and Heat Transfers during the Curing Cycle of Thermoset Composites", Advanced Materials Research, Vol. 326, pp. 19-28, 2011

Online since:

September 2011




[1] Li, C., et al., In-situ measurement of chemical shrinkage of MY750 epoxy resin by a novel gravimetric method. Composites Science and Technology, 64(1) (2004) 55-64.

DOI: https://doi.org/10.1016/s0266-3538(03)00199-4

[2] Haider, M., P. Hubert, and L. Lessard, Cure shrinkage characterization and modeling of a polyester resin containing low profile additives. Composites Part A: Applied Science and Manufacturing, 38(3) (2007) 994-1009.

DOI: https://doi.org/10.1016/j.compositesa.2006.06.020

[3] Shah, D.U. and P.J. Schubel, Evaluation of cure shrinkage measurement techniques for thermosetting resins. Polymer Testing. 29(6) 629-639.

DOI: https://doi.org/10.1016/j.polymertesting.2010.05.001

[4] Cook, W.D., M. Forrest, and A.A. Goodwin, A simple method for the measurement of polymerization shrinkage in dental composites. Dental Materials, 15(6) (1999) 447-449.

DOI: https://doi.org/10.1016/s0109-5641(99)00073-1

[5] Schoch, K.F., P.A. Panackal, and P.P. Frank, Real-time measurement of resin shrinkage during cure. Thermochimica Acta, 417(1) (2004) 115-118.

DOI: https://doi.org/10.1016/j.tca.2003.12.027

[6] Parlevliet, P.P., H.E.N. Bersee, and A. Beukers, Measurement of (post-)curing strain development with fibre Bragg gratings. Polymer Testing, 29(3) (2010) 291-301.

DOI: https://doi.org/10.1016/j.polymertesting.2009.12.002

[7] Hong, Y., G.M. Subodh, and W. Ee Hua, Observations of Gelation and Vitrification of a Thermosetting Resin during the Evolution of Polymerization Shrinkage. Macromolecular Rapid Communications, 26(18) (2005) 1483-1487.

DOI: https://doi.org/10.1002/marc.200500333

[8] Tai, H.J. and H.L. Chou, Chemical shrinkage and diffusion-controlled reaction of an epoxy molding compound. European Polymer Journal, 36 (2000) 2213-2219.

DOI: https://doi.org/10.1016/s0014-3057(99)00278-5

[9] Zarrelli, M., I.K. Partridge, and A. D'Amore, Warpage induced in bi-material specimens: Coefficient of thermal expansion, chemical shrinkage and viscoelastic modulus evolution during cure. Composites Part A: Applied Science and Manufacturing, 37(4) (2006).

DOI: https://doi.org/10.1016/j.compositesa.2005.05.012

[10] Lange, J., et al., Residual stress build-up in thermoset films cured above their ultimate glass transition temperature. Polymer, 36(16) (1995) 3135-3141.

DOI: https://doi.org/10.1016/0032-3861(95)97876-h

[11] Hoa, S.V., P. Ouellette, and T.D. Ngo, Determination of Shrinkage and Modulus Development of Thermosetting Resins. Journal of Composite Materials, 43(7) (2009) 783-803.

DOI: https://doi.org/10.1177/0021998308102035

[12] Arthur, W.S. a.J.P.A., Dilatometry on Thermoset Resins Naval Research Laboratry (1991).

[13] Yan-Jyi, H. and L. Chiou-Ming, Volume shrinkage characteristics in the cure of low-shrink unsaturated polyester resins. Polymer, 37 (1996) 401-412.

DOI: https://doi.org/10.1016/0032-3861(96)82909-0

[14] Li, W. and L.J. Lee, Low temperature cure of unsaturated polyester resins with thermoplastic additives: I. Dilatometry and morphology study. Polymer, 41(2) (2000) 685-696.

DOI: https://doi.org/10.1016/s0032-3861(99)00177-9

[15] Madhukar, M.S., M.S. Genidy, and J.D. Russell, A New Method to Reduce Cure-Induced Stresses in Thermoset Polymer Composites, Part I: Test Method. Journal of Composite Materials, 34(22) (2000) 1882-(1904).

DOI: https://doi.org/10.1106/hucy-dy2b-2n42-ujbx

[16] Russell, J.D., et al., A New Method to Reduce Cure-Induced Stresses in Thermoset Polymer Composites, Part III: Correlating Stress History to Viscosity, Degree of Cure, and Cure Shrinkage. Journal of Composite Materials, 34(22) (2000) 1926-(1947).

DOI: https://doi.org/10.1106/uy9u-f2qw-2fkk-91kg

[17] Zoller, P.B., P.; Pahud, V.; Ackermann, H., Apparatus for measuring pressure-volume-temperature relationships of polymers to 350 °C and 2200 kg/cm2. Rev. Sci. Instrum., 47(8) (1976).

DOI: https://doi.org/10.1063/1.1134779

[18] Mark, K., M. Shailesh, and L.J. Lee, Dilatometric study of low profile unsaturated polyester resins. Polymer Engineering & Science, 1995. 35(10): pp.823-836.

DOI: https://doi.org/10.1002/pen.760351005

[19] Ramos, J.A., et al., Cure kinetics and shrinkage model for epoxy-amine systems. Polymer, 46(10) (2005) 3323-3328.

DOI: https://doi.org/10.1016/j.polymer.2005.02.069

[20] Mark, K. and L.J. Lee, Development of a dilatometer and its application to low-shrink unsaturated polyester resins. Journal of Applied Polymer Science, 45(1) (1992) 37-50.

DOI: https://doi.org/10.1002/app.1992.070450105

[21] Boyard, N., et al., Behaviour of a moulded composite part: Modelling of dilatometric curve (constant pressure) or pressure (constant volume) with temperature and conversion degree gradients. Composites Science and Technology, 67(6) (2007).

DOI: https://doi.org/10.1016/j.compscitech.2006.07.004

[22] Boyard, N., et al., Analysis and modeling of PVTX diagram of an unsaturated polyester resin, thermoplastic additive, and mineral fillers blend. Journal of Applied Polymer Science, 88(5) (2003)1258-1267.

DOI: https://doi.org/10.1002/app.11830