Hostname: page-component-78c5997874-fbnjt Total loading time: 0 Render date: 2024-11-05T04:51:17.734Z Has data issue: false hasContentIssue false

Indentation of polydimethylsiloxane submerged in organic solvents

Published online by Cambridge University Press:  11 January 2011

Yuhang Hu
Affiliation:
School of Engineering and Applied Sciences, Kavli Institute, Harvard University, Cambridge, Massachusetts 02138
Xin Chen
Affiliation:
Department of Chemistry and Chemical Biology, Kavli Institute, Harvard University, Cambridge, Massachusetts 02138
George M. Whitesides
Affiliation:
Department of Chemistry and Chemical Biology, Kavli Institute, Harvard University, Cambridge, Massachusetts 02138
Joost J. Vlassak
Affiliation:
School of Engineering and Applied Sciences, Kavli Institute, Harvard University, Cambridge, Massachusetts 02138
Zhigang Suo*
Affiliation:
School of Engineering and Applied Sciences, Kavli Institute, Harvard University, Cambridge, Massachusetts 02138
*
a)Address all correspondence to this author. e-mail: [email protected]
Get access

Abstract

This work uses a method based on indentation to characterize a polydimethylsiloxane (PDMS) elastomer submerged in an organic solvent (decane, heptane, pentane, or cyclohexane). An indenter is pressed into a disk of a swollen elastomer to a fixed depth, and the force on the indenter is recorded as a function of time. By examining how the relaxation time scales with the radius of contact, one can differentiate the poroelastic behavior from the viscoelastic behavior. By matching the relaxation curve measured experimentally to that derived from the theory of poroelasticity, one can identify elastic constants and permeability. The measured elastic constants are interpreted within the Flory–Huggins theory. The measured permeability indicates that the solvent migrates in PDMS by diffusion, rather than by convection. This work confirms that indentation is a reliable and convenient method to characterize swollen elastomers.

Type
Articles
Copyright
Copyright © Materials Research Society 2011

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

REFERENCES

1.Duncan, R.: The dawning era of polymer therapeutics. Nat. Rev. Drug Discovery 2, 347 (2003).CrossRefGoogle ScholarPubMed
2.Jeong, B., Bae, Y.H., Lee, D.S., and Kim, S.W.: Biodegradable block copolymers as injectable drug delivery systems. Nature 388, 860 (1997).CrossRefGoogle ScholarPubMed
3.Langer, R.: Drug delivery and targeting. Nature 392, 5 (1998).Google ScholarPubMed
4.Luo, Y. and Shoichet, M.S.: A photolabile hydrogel for guided three-dimensional cell growth and migration. Nat. Mater. 3, 249 (2004).CrossRefGoogle ScholarPubMed
5.Nowak, A.P., Breedveld, V., Pakstis, L., Ozbas, B., Pine, D.J., Pochan, D., and Deming, T.J.: Rapidly recovering hydrogel scaffolds from self-assembling diblock copolypeptide amphiphiles. Nature 417, 424 (2002).CrossRefGoogle ScholarPubMed
6.Beebe, D.J., Moore, J.S., Bauer, J.M., Yu, Q., Liu, R.H., Devadoss, C., and Jo, B.H.: Functional hydrogel structures for autonomous flow control inside microfluidic channels. Nature 404, 588 (2000).CrossRefGoogle ScholarPubMed
7.Tokeshi, M., Minagawa, T., Uchiyama, K., Hibara, A., Sato, K., Hisamoto, H., and Kitamori, T.: Continuous-flow chemical processing on a microchip by combining microunit operations and a multiphase flow network. Anal. Chem. 74, 1565 (2002).CrossRefGoogle Scholar
8.Cai, S., Lou, Y., Ganguly, P., Robisson, A., and Suo, Z.: Force generated by a swelling elastomer subject to constraint. J. Appl. Phys. 107, 103535 (2010).CrossRefGoogle Scholar
9.Zhao, X., Huebsch, N., Mooney, D.J., and Suo, Z.: Stress-relaxation behavior in gels with ionic and covalent crosslinks. J. Appl. Phys. 107, 063509 (2010).CrossRefGoogle ScholarPubMed
10.Oliver, W.C. and Pharr, G.M.: An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments. J. Mater. Res. 7, 1564 (1992).CrossRefGoogle Scholar
11.Ebenstein, D.M. and Pruitt, L.A.: Nanoindentation of soft hydrated materials for application to vascular tissues. J. Biomed. Mater. Res. Part A 69, 222 (2004).CrossRefGoogle ScholarPubMed
12.Kaufman, J.D., Miller, G.J., Morgan, E.F., and Klapperich, C.M.: Time-dependent mechanical characterization of poly(2-hydroxyethyl methacrylate) hydrogels using nanoindentation and unconfined compression. J. Mater. Res. 23, 1472 (2008).CrossRefGoogle ScholarPubMed
13.Constantinides, G., Kalcioglu, Z.I., McFarland, M., Smith, J.F., and Van Vliet, K.J.: Probing mechanical properties of fully hydrated gels and biological tissues. J. Biomech. 41, 3285 (2008).CrossRefGoogle ScholarPubMed
14.Galli, M., Comley, K.S.C., Shean, T.A.V., and Oyen, M.L.: Viscoelastic and poroelastic mechanical characterization of hydrated gels. J. Mater. Res. 24, 973 (2009).CrossRefGoogle Scholar
15.Galli, M. and Oyen, M.L.: Spherical indentation of a finite poroelastic coating. Appl. Phys. Lett. 93, 031911 (2008).CrossRefGoogle Scholar
16.Galli, M. and Oyen, M.L.: Fast indentation of poroelastic parameters from indentation tests. CMES 48, 241 (2009).Google Scholar
17.Chiravarambath, S., Simha, N.K., Namani, R., and Lewis, J.L.: Poroviscoelastic cartilage properties in the mouse from indentation. J. Biomech. Eng. 131, 011004 (2009).CrossRefGoogle ScholarPubMed
18.Lin, W.C., Shull, K.R., Hui, C.Y., and Lin, Y.Y.: Contact measurement of internal fluid flow within poly(n-isopropylacrylamide) gels. J. Chem. Phys. 127, 094906 (2007).CrossRefGoogle ScholarPubMed
19.Hui, C.Y., Lin, Y.Y., Chuang, F.C., Shull, K.R., and Ling, W.C.: A contact mechanics method for characterizing the elastic properties and permeability of gels. J. Polym. Sci., Part B: Polym. Phys. 43, 359 (2006).CrossRefGoogle Scholar
20.Lin, Y.Y. and Hu, B.W.: Load relaxation of a flat rigid circular indenter on a gel half space. J. Non-Cryst. Solids 352, 4034 (2006).CrossRefGoogle Scholar
21.Hu, Y., Zhao, X., Vlassak, J.J., and Suo, Z.: Using indentation to characterize the poroelasticity of gels. Appl. Phys. Lett. 96, 121904 (2010).CrossRefGoogle Scholar
22.Toepke, M.W. and Beebe, D.J.: PDMS absorption of small molecules and consequences in microfluidic applications. Lab Chip 6, 1484 (2006).CrossRefGoogle ScholarPubMed
23.Lee, J.N., Park, C., and Whitesides, G.M.: Solvent compatibility of poly(dimethylsiloxane)-based microfluidic devices. Anal. Chem. 75, 6544 (2003).CrossRefGoogle ScholarPubMed
24.Hong, W., Zhao, X., Zhou, J., and Suo, Z.: A theory of coupled diffusion and large deformation in polymeric gels. J. Mech. Phys. Solids 56, 1779 (2008).CrossRefGoogle Scholar
25.Doi, M.: Gel dynamics. J. Phys. Soc. Jpn. 78, 052001 (2009).CrossRefGoogle Scholar
26.Terzaghi, K.: The calculation of permeability numbers of the clay out of the process of the hydrodynamic phenomenon tension. Sitzungsber. Akad. Wiss. Wien Math.–Naturewiss. Kl., Abt. IIa 132, 125 (1923).Google Scholar
27.Biot, M.A.: General theory of three-dimensional consolidation. J. Appl. Phys. 12, 155 (1941).CrossRefGoogle Scholar
28.Sneddon, I.N.: The relation between load and penetration in the axisymmetric Boussinesq problem for a punch of arbitrary profile. Int. J. Eng. Sci. 3, 47 (1965).CrossRefGoogle Scholar
29.Li, Y. and Tanaka, T.: Kinetics of swelling and shrinking of gels. J. Chem. Phys. 92, 1365 (1990).CrossRefGoogle Scholar
30.Vanlandingham, M.R., Chang, N-K., Drzal, P.L., White, C.C., and Chang, S-H.: Viscoelastic characterization of polymers using instrumented indentation. I. Quasi-static testing. J. Polym. Sci., Part B: Polym. Phys. 43, 1794 (2005).CrossRefGoogle Scholar
31.Lin, I-K., Ou, K-S., Liao, Y-M., Liu, Y., Chen, K-S., and Zhang, X.: Viscoelastic characterization and modeling of polymer transducers for biological applications. J. Microelectromech. Syst. 18, 1087 (2009).Google Scholar
32.Ferry, J.D.: Viscoelastic Properties of Polymers, 3rd ed. (John Wiley and Sons, New York, 1980).Google Scholar
33.Johnson, K.J.: Contact Mechanics (Cambridge University Press, New York, 1987).Google Scholar
34.Douglass, D.C. and McCall, D.W.: Diffusion in paraffin hydrocarbons. J. Phys. Chem. 62, 1102 (1958).CrossRefGoogle Scholar
35.Fishman, E.: Self-diffusion in liquid n-pentane and n-heptane. J. Phys. Chem. 59, 469 (1955).CrossRefGoogle Scholar
36.Holz, M., Heil, S.R., and Sacco, A.: Temperature-dependent self-diffusion coefficients of water and six selected molecular liquids for calibration in accurate H NMR PFG measurements. Phys. Chem. Chem. Phys. 2, 4740 (2000).CrossRefGoogle Scholar
37.Geissler, E. and Hecht, A. M.: The Poisson ratio in polymer gels. 2. Macromolecules 14, 185 (1981).CrossRefGoogle Scholar
38.Hirotsu, S.: Softening of bulk modulus and negative Poisson’s ratio near the volume phase transition of polymer gels. J. Chem. Phys. 94, 3949 (1991).CrossRefGoogle Scholar
39.Tang, J., Tung, M.A., Lelievre, J., and Zeng, Y.: Stress–strain relationships for gellan gels in tension, compression and torsion. J. Food Eng. 31, 511 (1997).CrossRefGoogle Scholar
40.Paul, D.R. and Ebra-Lima, O.M.: Pressure-induced diffusion of organic liquids through highly swollen polymer membranes. J. Appl. Polym. Sci. 14, 2201 (1970).CrossRefGoogle Scholar
41.Paul, D.R. and Ebra-Lima, O.M.: The mechanism of liquid transport through swollen polymer membranes. J. Appl. Polym. Sci. 15, 2199 (1971).CrossRefGoogle Scholar
42.Paul, D.R.: Further comments on the relation between hydraulic permeation and diffusion. J. Polym. Sci., Polym. Phys. Ed. 12, 1221 (1974).CrossRefGoogle Scholar
43.Paul, D.R.: Reformulation of the solution-diffusion theory of reverse osmosis. J. Membr. Sci. 241, 371 (2004).CrossRefGoogle Scholar
44.Meares, P.: On the mechanism of desalination by reversed osmotic flow through cellulose acetate membranes. Eur. Polym. J. 2, 241 (1966).CrossRefGoogle Scholar
45.Peterlin, A. and Yasuda, H.: Comments on the relation between hydraulic permeability and diffusion in homogeneous swollen membranes. J. Polym. Sci., Polym. Phys. Ed. 12, 1215 (1974).CrossRefGoogle Scholar
46.Yasuda, H. and Peterlin, A.: Diffusive and bulk flow transport in polymers. J. Appl. Polym. Sci. 17, 433 (1973).CrossRefGoogle Scholar
47.Wijmans, J.G. and Baker, R.W.: The solution-diffusion model: A review. J. Membr. Sci. 107, 1 (1995).CrossRefGoogle Scholar
48.Tanaka, T. and Fillmore, D.J.: Kinetics of swelling of gels. J. Chem. Phys. 70, 1214 (1979).CrossRefGoogle Scholar
49.Yamaue, T. and Doi, M.: Swelling dynamics of constrained thin-plate gels under an external force. Phys. Rev. E: Stat. Nonlinear Soft Matter Phys. 70, 011401 (2004).CrossRefGoogle ScholarPubMed
50.Hajsz, T., Csetneki, I., Filipcsei, G., and Zrinyi, M.: Swelling kinetics of anisotropic filler loaded PDMS networks. Phys. Chem. Chem. Phys. 8, 977 (2006).CrossRefGoogle ScholarPubMed
51.Flory, P.J.: Principles of Polymer Chemistry (Cornell University, Ithaca, NY, 1953).Google Scholar
52.Flory, P.J.: Thermodynamics of high polymer solutions. J. Chem. Phys. 10, 51 (1942).CrossRefGoogle Scholar
53.Huggins, M.L.: Solutions of long chain compounds. J. Chem. Phys. 9, 440 (1941).CrossRefGoogle Scholar
54.Braden, M., Latham, D., and Patel, M.P.: Observations on the swelling of cross-linked poly(dimethylsiloxane) networks by solvents. Eur. Polym. J. 41, 3069 (2005).CrossRefGoogle Scholar
55.Gottlieb, M. and Herskowitz, M.: Estimation of the χ parameter for poly(dimethylsiloxane) solutions by the UNIFAC group contribution method. Macromolecules 14, 1468 (1981).CrossRefGoogle Scholar
56.Flory, P.J.: Thermodynamics of polymer solutions. Fifteenth spiers memorial lectures. Discuss. Faraday Soc. 49, 7 (1970).CrossRefGoogle Scholar
57.Flory, P.J. and Shih, H.: Thermodynamics of solutions of poly(dimethylsiloxane) in benzene, cyclohexane, and chlorobenzene. Macromolecules 5, 761 (1972).CrossRefGoogle Scholar
58.Kuwahara, N., Okazawa, T., and Kaneko, M.: Osmotic pressures of moderately concentrated polydimethylsiloxane solutions. J. Polym. Sci., Part C 23, 543 (1968).CrossRefGoogle Scholar
59.Schurz, J.: Rheology of polymer solutions of the network type. Prog. Polym. Sci. 16, 1 (1991).CrossRefGoogle Scholar
60.Grassi, M., Sandolo, C., Perin, D., Coviello, T., Lapasin, R., and Grassi, G.: Structural characterization of calcium alginate matrices by means of mechanical and release tests. Molecules 14, 3003 (2009).CrossRefGoogle ScholarPubMed
61.Vadakan, W.V. and Scherer, G.W.: Measuring permeability of rigid materials by a beam-bending method: II, Porous glass. J. Am. Ceram. Soc. 83, 2240 (2000).CrossRefGoogle Scholar
62.Boontheekul, T., Kong, H-J., and Mooney, D.J.: Controlling alginate gel degradation utilizing partial oxidation and bimodal molecular-weight distribution. Biomaterials 26, 2455 (2005).CrossRefGoogle ScholarPubMed