A Review of Nondestructive Characterization of Composites Using NMR

  • George A. Matzkanin

Abstract

Nuclear Magnetic Resonance (NMR) is a nondestructive evaluation technique useful for characterizing organic matrix composites and other polymer based materials. NMR depends on the interaction between the nuclear magnetic moment and a magnetic field and thus it is sensitive to localized field variations caused by molecular motions, changes in molecular or crystal structure, and chemical composition differences. Application of NMR to composites and polymers involves measurement of the hydrogen nucleus (proton) NMR signal. Fortunately, the proton NMR signal is very strong and easily measured. Much of the physical and chemical information available through the use of NMR is associated with the relaxation characteristics of the nuclear magnetic moments, which can be measured using pulsed NMR techniques. The energy exchange between nuclear moments and the surrounding lattice is characterized by the spin-lattice relaxation time, T1, while the energy exchange among nudear magnetic moments is described by the spin-spin relaxation time, T2. These relaxation times are very sensitive to molecular motions and structural changes and can be used to provide both qualitative and quantitative information on the dynamic environment in which the nuclei are located. For application to composites and polymers, hydrogen NMR has been used to characterize water absorption, molecular diffusion, environmental degradation, aging, degree of cure, and modulus variations.

Keywords

Porosity Migration Graphite Benzene Attenuation 

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References

  1. 1.
    Summerscales, J.; Short, D.: Chemical spectroscopy. Non-Destructive Testing of Fibre-Reinforced Plastics Composites. London: Elsevier Applied Science, (1987) 207–270.Google Scholar
  2. 2.
    Matzkanin, G.A.: Applications of nuclear magnetic resonance to the NDE of composites. Proceedings of the 14th Symposium on NDE, Nondestructive Testing Information Analysis Center, San Antonio, Texas (1983) 270–286.Google Scholar
  3. 3.
    Batra, N.K.; Graham, T.P.: Measurement of moisture in hygrothermally degraded fiber-reinforced epoxy composites by continuous wave (CW) nudear magnetic resonance (NMR). Br. J. Non-destr. Test 25 (Jan. 1983) 21–23.Google Scholar
  4. 4.
    Shuford, RJ.; Murray, T.J.; Hinton, Y.L.; Brockelman, R.H.: Advanced NDE techniques for composites. 1986 SME Manufacturing Technology Review, May 28–30, 1986 (1987) 101–112.Google Scholar
  5. 5.
    Matzkanin, G.A.; De Los Santos, A.: Nondestructive characterization of Kevlar composites using pulsed NMR. Nondestructive Characterization of Materials II. New York, New York: Plenum Press (1986) 29–37.Google Scholar
  6. 6.
    Shuford, RJ.; Murray, T.J.; Bostic, M.T.; Brockelman, R.H.; Hinton, Y.L.: Evaluation of nondestructive evaluation techniques for detecting moisture in composite materials. Proc. of the 11th World Conference on NDT, Las Vegas, NV, 3–8 Nov. 1985, 1366–1473.Google Scholar
  7. 7.
    Matzkanin, G.A.; De Los Santos, A.: NDE of moisture absorption in composites using nudear magnetic resonance. Composites Evaluation (1987) 23–27.Google Scholar
  8. 8.
    Fornes, R.E.; Memory, J.D.; Gilbert, RD.: Studies of epoxy resin–grpahit fiber composites using NMR, ESR, and DSC. Third Annual Army Composites Research Review, Williamstown, MA, October 29–31, 1980.Google Scholar
  9. 9.
    Lawing, D.; Fornes, R.E.; Gilbert, RD.; Memory, J.D.: Temperature dependence of broadline NMR spectra of water-soaked epoxy-graphite composites. J. Appl. Phys. 52 (Oct. 1981) 5906–5907.CrossRefGoogle Scholar
  10. 10.
    Matzkanin, G.A.; De Los Santos, A.; King, J.D.: Nondestructive evaluation of adhesive bonds using nuclear magnetic resonance. Proceedings of the Fifth International Joint Military/Government-Industry Symposium on Structural Adhesive Bonding, Dover, New Jersey, November 3–5, 1987 (1987) 397–403.Google Scholar
  11. 11.
    Memory, J.D.; Lawing, D.: Broadline NMR of polymers. Mag. Resonace Rev. 5 (1979) 69–73.Google Scholar
  12. 12.
    Fuller, R.T.; Fornes, R.E.; Memory, J.D.: NMR study of water absorbed by epoxy resin. J. Appl. Polymer Sci. 23 (1979) 1871–1874.CrossRefGoogle Scholar
  13. 13.
    Lind, A.C.: NMR study of inhomogeneities in amine cured epoxies. Polymer Preprints 103 (1981) 333–334.Google Scholar
  14. 14.
    Vinson, J.R. (ed.): Advanced composite materials-environmental effects. ASTM STP 658, American Society for Testing and Materials (1978).Google Scholar
  15. 15.
    Garza, R.G.; Pruneda, C.O.; Morgan, R.J.: Polymer Preprints 22 (1981).Google Scholar
  16. 16.
    Carlson, D.J.; Wiles, D.M.: Degradation. Encyclopedia of Polymer Science and Engineering Vol. 4. New York, New York: Wiley-Intersdence (1986) 630–696.Google Scholar
  17. 17.
    Kowalska, M.; Wirsen, A.: Chemical analysis of epoxy prepregs-market survey and batch control. 25th National SAMPE Symposium, San Diego, May 1980, 389–402.Google Scholar
  18. 18.
    Happe, J.A.; Morgan, R.J.; Walkup, C.M.: NMR characterisation of BF3 amine catalysts used in the cure of carbon fibre/epoxy prepregs. Composites Technology Review 6 (Summer 1984 ) 77–82.Google Scholar
  19. 19.
    Brown, I.M.; Lind, A.C.: Study of the glass transition in crosslinked polymers using nuclear and electron magnetic resonance. Final Report (1977), Contract No.: N00019–76-C-0565.Google Scholar
  20. 20.
    Banks, L.; Ellis, B.: The glass transition temperatures of highly crosslinked networks: cured epoxy resins. Polymer 23 (Sept. 2981) 1466–1472.CrossRefGoogle Scholar
  21. 21.
    Bryden, WA.; Poehler, T.O.: Nondestructive testing of nylon ropes using magnetic resonance techniques. Proc. of the 11th World Conference on NDT, Las Vegas, NV, 3–8 Nov. 1985, 1746–1750.Google Scholar
  22. 22.
    Brown, H.R.: A theory of the environmental stress cracking polyethylene. Polymer 19 (1978) 1186–1188.CrossRefGoogle Scholar
  23. 24.
    Colletti, R.F.; Mathias, L.J.: Solid state C-13 NMR characterization of textiles: Qualitative and quantitative analysis. Technical Report No. 3, Aug. 1986 - Aug. 1987 (Report No. AD-A184349): Contract No. N00014–86-K-0659.Google Scholar
  24. 25.
    Muller, K.; Schleicher, A.; Kothe, G.: Two-dimensional NMR relaxation spectroscopy of liquid crystal polymers. Mol. Cryst. Liq. Cryst. 153 (Dec. 1987) 117–131.Google Scholar
  25. 26.
    Kintanar, A.; Jelinski, L.W.; Gancarz, I.; Koberstein, J.T.: Complex molecular motions in bulk hard segment polyurethanes: A deuterium NMR study. Technical Report, Sept. 1985 (Report No. AD-A159760; TR-2): Contract No. N00014–84-K-0534.Google Scholar
  26. 27.
    Runt, J.: Crystallinity determination. Encyclopedia of Polymer Science and Engineering Vol. 4. New York, New York: Wiley-Interscience (1986) 482–519.Google Scholar
  27. 28.
    Havens, J.R.; Vanderhart, D.L.: Multiple-pulse proton NMR of pressure-crystallized linear polyethylene. J. Magn. Resonance, 61 (Feb. 1985) 389–391.CrossRefGoogle Scholar
  28. 29.
    Zupancic, I.; Lanhajnar, G.; Blinc, R; Reneker, D.H.; Peterlin, A.; NMR studiy of diffusion of butane in linear polyethylene. J. Poly. Sci., Poly. Phys. Ed. 16 (1978) 1399–1407.Google Scholar
  29. 30.
    Tanaka, H.; Nishi, T.: Spin diffusion in block copolymers as studies by pulsed NMR. Phys. Rev. B 33 (Jan. 1986) 32–42.CrossRefGoogle Scholar
  30. 31.
    Brown, I.M.; Lind, A.C.; Sandrecski, T.C.: Magentic resonance studies of epoxy resins and polyurethanes. Final Report (1979) Contract No.: N00019–78-C-0031.Google Scholar
  31. 32.
    Hewitt, R.R.; Mazelsky, B.: Nuclear quadrupole resonance as a nondestructive probe in polymers. J. Appl. Phys. 43 (Aug. 1972) 3386–3392.CrossRefGoogle Scholar
  32. 33.
    Vanderhart, D.L.; Wang, F.W.; Eby, R.K.; Fanconi, B.M.; Devries, K.L.: Exploration of advanced characterization techniques for molecular composites. Final Report, Feb. 1984 - Jan. 1985 (Report No. AFWAL-TR-85–4137): Contract No. MIPRFY1457–84-N-5019.Google Scholar
  33. 34.
    Inglefield, P.R.; Jones, A.A.: Chain dynamics and structure property relation in high impact strength polycarbonate plastic. Final Report, Nov. 1981- Nov. 1984 (Report No. ARO-18501.7-CH-H): Contract No.: DAAG29–82-G-001.Google Scholar
  34. 35.
    Paetzold, R.F.; Matzkanin, G.A.; Los Santos, A. De: Surface soil water content measurement using pulsed nudear magnetic resonance techniques. Soil Sci. Soc. Am. J. 49 (May-June 1985) 537–540; also, Paetzold, R.F.; Los Santos, A. De; Matzkanin, G.A.: Pulsed nuclear magnetic resonance instrument for soil-water content measurement: sensor configurations. Soil Sci. Soc. Am. J. 51 (March-April 1987 ) 287–290.Google Scholar
  35. 36.
    Matzkanin, G.A.; Los Santos, A. De; Whiting, D.A.; Determination of moisture levels in structural concrete using pulsed NMR. FHWA/RD-82/008 (Apri11982).Google Scholar
  36. 37.
    Matzkanin, G.A.: Application of spatially localized NMR to nondestructive evaluation. Proceedings of the 11th World Conference on NDT, Las Vegas, Nevada, November 1985 (1985) 1607–1614.Google Scholar
  37. 38.
    Matzkanin, G.A.: Nondestructive evaluation of composites using pulsed NMR. Proceedings of the Society of Plastics Engineers 45th Annual Technical Conference, Los Angeles, California, May 4–7, 1987 (1987) 1060–1063.Google Scholar
  38. 39.
    Glover, G.H.: Magnetic resonance imaging in medicine: quantitative tissue characterization. Rev. of Prog. in Quantitative NDE 4A (1985) 1–10.Google Scholar
  39. 40.
    Vinegar, H.J.: Use of MRI and x-ray CT in core analysis. S.P.E.J., February 1986.Google Scholar
  40. 41.
    Rothwell, W.P.; Gentempo, P.P.: Non-radial applications of NMR imaging. Bruker Report (Jan. 1985) 46–51.Google Scholar
  41. 42.
    Garroway, A.N.; Baum, J.; Murowitz, M.G.; Pines, A.: NMR imaging in solids by multiple quantum resonance. J. Mag. Res. 60 (1984) 337–341.CrossRefGoogle Scholar
  42. 43.
    Wind, R.A.; Yannoni, C.S.: Selective spin imaging in solids. J. Mag. Res. 36 (Oct. 1979) 269–272.CrossRefGoogle Scholar
  43. 44.
    Ellingson, W.A.; Ackerman, J.L.; Gronemeyer, S.; Garrido, L.: Nuclear magnetic resonance imaging for detecting binder/plasticizers in green-state structural ceramics. Proceedings of 16th Symposium on Nondestructive Evaluation, San Antonio, Texas, April 21–23, 1987 (1987) 231–240.Google Scholar
  44. 45.
    Ackerman, J.L.; Ellingson, W.A.; Koutcher, J.A.; Rosen, B.R.: Development of nuclear magnetic resonance imaging techniques for characterizing green-state ceramic materials. Proceedings of the 2nd International Symposium on the Nondestrucive Characterization of Materials, Montreal, Canada, July 21–23, 1986 (1986), 129–137.Google Scholar
  45. 46.
    Welch, L.B.; Gronczy, S.T.; Mitsche, M.T.; Bauer, L.J.; Dworkin, J.; Giambalvo, A.: Proton NMR imaging of green-state ceramics. Proceedings Quantitative NDE Conference, La Jolla, CA, Plenum Press, New York (1987) 441–456.Google Scholar
  46. 47.
    Ellingson, W.A.; Ackerman, J.L.; Garrido, L.; Wong, P.S.; Gronemeyer, S.: Development of nuclear magnetic resonance (NMR) imaging technology for advanced ceramics. November 1988 (Report No. ANL-87–53): Contract No.: ACK-85234.Google Scholar
  47. 48.
    Blackband, S.; Mansfield, P.: Diffusion in liquid-solid systems by NMR imaging. J. Phys. C 19 (Jan. 1986) L49–52.CrossRefGoogle Scholar
  48. 49.
    Rothwell, W.P.; Holecek, D.R.; Kershaw, J.A.: NMR imaging: Study of fluid absorption by polymer composites. J. Polym. Sci. Polym. Lett. (22) (May 1984 ) 24 1247.Google Scholar
  49. 50.
    Crowley, J.D.; Branman, S.K.: Nuclear magnetic resonance imaging. 4th NASA Nondestructive Evaluation Workshop (March 7, 1985 ).Google Scholar
  50. 51.
    Miller, J.B.; Garroway, A.N.: Multinudear NMR imaging of solids. Review of Progress in Quantitative NDE, Vol. 8A, New York, New York: Plenum Press (1989) 567–574.Google Scholar
  51. 52.
    Miller, J.B.; Garroway, J.: 1H refocused gradient imaging of solids. Submitted to J. Magn. Resonance (1988).Google Scholar
  52. 53.
    Miller, J.B.; Garroway, A.N.: NMR imaging of solids. Review of Progress in Quantitative Nondestructive Evaluation 7A (1988) 287–294.Google Scholar
  53. 54.
    Miller, J.B.; Garroway, A.N.: NMR imaging of solids with a surface coil. J. Mag. Resonance 77 (1988) 187–191.CrossRefGoogle Scholar
  54. 55.
    Lind, A.; Fry, C.: Private communication. McDonnell Douglas Research Laboratories, work funded by the Air Force Materials Laboratory.Google Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 1989

Authors and Affiliations

  • George A. Matzkanin
    • 1
  1. 1.Texas Research International, Inc.AustinUSA

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