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Zirconium tungstate reinforced cyanate ester composites with enhanced dimensional stability

  • Prashanth Badrinarayanan, Ben Mac Murray and Michael R. Kessler (a1)


Zirconium tungstate (ZrW2O8) is a unique ceramic material characterized by isotropic negative thermal expansion behavior over a wide temperature range. Incorporation of ZrW2O8 is expected to improve the dimensional stability of polymers by reducing the overall coefficient of thermal expansion (CTE). In this work, the thermal and dynamic mechanical properties of a bisphenol E cyanate ester reinforced with various loadings of ZrW2O8 are examined. Thermomechanical analysis indicates that the incorporation of ZrW2O8 results in a decrease in CTE at temperatures above and below the glass transition temperature (Tg) of the neat resin. The dynamic storage moduli of the composites reinforced with ZrW2O8 are found to increase with increasing filler loading. Furthermore, the various phase behaviors exhibited by ZrW2O8 are also examined by differential scanning calorimetry measurements.


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1Sleight, A.W.: Isotropic negative thermal expansion. Annu. Rev. Mater. Sci. 28, 29 (1998).
2Mary, T.A., Evans, J.S.O., Vogt, T., and Sleight, A.W.: Negative thermal expansion from 0.3 to 1050 K in ZrW2O8. Science 272, 90 (1996).
3Evans, J.S.O., Hu, Z., Jorgensen, J.D., Argyriou, D.N., Short, S., and Sleight, A.W.: Compressibility, phase transitions, and oxygen migration in zirconium tungstate. Science 275, 61 (1997).
4Jorgensen, J.D., Hu, Z., Teslic, S., Argyriou, D.N., Short, S., Evans, J.S.O., and Sleight, A.W.: Pressure induced cubic to orthorhombic phase transition in ZrW2O8. Phys. Rev. B 59, 215 (1999).
5Figueiredo, C.A., Catafesta, J., Zorzi, J.E., Salvador, L., Baumvol, J.R., Gallas, M.R., Jornada, J.A.H. da, and Perottoni, C.A.: Compression mechanism and pressure induced amorphization of ZrW2O8. Phys. Rev. B 76, 184201 (2007).
6Perottoni, C.A., Zorzi, J.E., and Jornada, J.A.H. da: Entropy increase in amorphous to crystalline phase transition in zirconium tungstate. Solid State Commun. 134, 319 (2005).
7Cross, W.M., Henderson, B.D., Weyer, W.C., Kroetch, C., Kjerentroen, L., Welsh, J., and Kellar, J.J.: Functional fillers for dimensional stability, in Functional Fillers and Nanoscale Minerals, edited by Kellar, J.J. (SME Inc., Littleton, CO, 2006), p. 127.
8Sleight, A.W., Evans, J.S.O., and David, W.I.F.: Structural investigation of the negative thermal expansion material ZrW2O8. Acta Crystallogr., Sect. B 55, 333 (1999).
9Pryde, A.K.A., Hammonds, K.D., Dove, M.T., Heine, V., Gale, J.D., and Warren, M.C.: Origin of negative thermal expansion in ZrW2O8 and ZrV2O7. J. Phys.: Condens. Matter 8, 10973 (1996).
10Shi, J.D., Pu, Z.J., and Wu, K.H.: Composites with adjustable thermal expansion for electronic applications, in Electronic Packaging Materials Science IX, edited by Groothuis, S.K., Ho, P.S., Ishida, K., and Wu, T. (Mater. Res. Soc. Symp. Proc. 445, Warrendale, PA, 1997), p. 229.
11Weyer, W.C., Cross, W.M., Henderson, B., Kellar, J.J., Kjerentroen, L., Welsh, J., and Starkovich, J.: Achieving dimensional stability using functional fillers, in Proceedings of the Structural Dynamics and Materials Conference (Austin, TX, 2005), p. 2091.
12Sullivan, L.M. and Lukehart, C.M.: Zirconium tungstate/polyimide nanocomposites exhibiting reduced coefficient of thermal expansion. Chem. Mater. 17, 2136 (2005).
13Tani, J.I., Kimura, H., Hiorata, K., and Kido, H.: Thermal expansion and mechanical properties of phenolic resin/ZrW2O8 composites. J. Appl. Polym. Sci. 106, 3343 (2007).
14Miller, W., Smith, C.W., Dooling, P., Burgess, A.N., and Evans, K.E.: Tailored thermal expansivity in particulate composites for thermal stress management. Phys. Status Solidi 245, 552 (2006).
15Goertzen, W.K. and Kessler, M.R.: Thermal and mechanical behavior of cyanate ester composites with low temperature processability. Composites Part A 779, 38 (2007).
16Sheng, X., Akinc, M., and Kessler, M.R.: Cure kinetics of thermosetting bisphenol E cyanate ester. J. Therm. Anal. Calorim. 93, 77 (2008).
17Goertzen, W.K. and Kessler, M.R.: Dynanmic mechanical analysis of fumed silica cyanate ester nanocomposites. Composites Part A 761, 39 (2008).
18Goertzen, W.K., Sheng, X., Akinc, M., and Kessler, M.R.: Rheology and curing kinetics of fumed silica cyanate ester nanocomposites. Polym. Eng. Sci. 48, 875 (2008).
19Sheng, X., Akinc, M., and Kessler, M.R.: The effects of alumina nanoparticles on the cure kinetics of bisphenol E cyanate ester. Polym. Eng. Sci. (submitted, 2009).
20Goertzen, W.K. and Kessler, M.R.: Three phase cyanate ester composites with fumed silica and negative CTE reinforcements. J. Therm. Anal. Calorim. 93, 87 (2008).
21De Meyer, C.D., Vandperre, L., Driessche, I. Van, Bruneel, E., and Hoste, S.: Processing effects observed during the densification of the negative CTE compound ZrW2O8. Cryst. Eng. 5, 468 (2002).
22Holzer, H. and Dunand, D.C.: Phase transformation and thermal expansion of Cu/ZrW2O8 metal matrix composites. J. Mater. Res. 14, 780 (1999).
23Haman, K.J., Badrinarayanan, P., and Kessler, M.R.: Effect of zirconium tungstate filler on the cure behavior of a cyanate ester. App. Mater. Int. (in press, 2009) DOI: 10.1021/am900051g.
24Qiu, J., Zhang, C., Wang, B., and Liang, R.: Carbon nanotube integrated multifunctional multiscale composites. Nanotechnology 18, 275708 (2007).
25Goertzen, W.K. and Kessler, M.R.: Thermal expansion of fumed silica cyanate ester nanocomposites. J. Appl. Polym. Sci. 109, 647 (2008).
26Wong, C.P. and Bollampally, R.S.: Thermal conductivity, elastic modulus, and coefficient of thermal expansion of polymer composites filled with ceramic particles for electronic packaging. J. Appl. Polym. Sci. 74, 3396 (1999).
27Vo, H.T., Todd, M., Shi, F.G., Shapiro, A.A., and Edwards, M.: Towards model based engineering of underfill materials: CTE modeling. Microelectron. J. 32, 331 (2001).
28Schapery, R.A.: Thermal expansion coefficients of composite materials based on energy principles. J. Compos. Mater. 2, 380 (1968).
29Drymiotis, F.R., Ledbetter, H., Betts, J.B., Kimura, T., Lashley, J.C., Migliori, A., Ramirez, A.P., Kowach, G.R., and Duijn, J. Van: Monocrystal elastic constants of the negative-thermal-expansion compoundzirconium tungstate (ZrW2O8). Phys. Rev. Lett. 93, 25502 (2004).


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Zirconium tungstate reinforced cyanate ester composites with enhanced dimensional stability

  • Prashanth Badrinarayanan, Ben Mac Murray and Michael R. Kessler (a1)


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