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Cellulose

, Volume 24, Issue 5, pp 1971–1984 | Cite as

Effect of sample moisture content on XRD-estimated cellulose crystallinity index and crystallite size

  • Umesh P. AgarwalEmail author
  • Sally A. Ralph
  • Carlos Baez
  • Richard S. Reiner
  • Steve P. Verrill
Original Paper

Abstract

Although X-ray diffraction (XRD) has been the most widely used technique to investigate crystallinity index (CrI) and crystallite size (L200) of cellulose materials, there are not many studies that have taken into account the role of sample moisture on these measurements. The present investigation focuses on a variety of celluloses and cellulose containing materials—from loblolly pine wood to tunicin, and evaluated moisture-induced changes in CrI and L200. It was observed that upon introduction of a small amount of water (5%) into P2O5 dried samples, for most samples, both absolute intensity of (200) reflection and its full width at half maximum declined. Moreover, (200) peak position (2θ max) increased when the samples became moist. Although the extent of such changes were material dependent, in general, a greater degree of change was associated with lower sample CrI. For CrI, maximum and minimum increases occurred for oven dried NaOH treated red pine holopulp and tunicin, respectively. For L200, maximum and minimum increases were for wood and tunicin, respectively. Moreover, 2θ max position for (200) reflection increased most for the wood and oven dried NaOH treated red pine holopulp (acid chlorite delignified milled-wood) and least for tunicin. The nonparametric statistical test “sign test” further supported these results. Observations from longer duration drying experiments, post moistening, indicated that the changes to the XRD parameters were reversible to some degree. Based on the findings it is concluded that for most cellulose materials with Segal CrI < 90% the moisture content has a significant bearing on the XRD-estimated CrI and L200 data. Consequently, it is essential that when such materials are compared, their diffractograms should be obtained under similar levels of sample moisture content.

Keywords

Cellulose X-ray diffraction Crystallinity Crystallite size Moisture 

Notes

Acknowledgments

The authors thank Dr. Akira Isogai (Tokyo University) for providing Tunicate cellulose. The authors acknowledge Fred Matt of the FPL Analytical Chemistry and Microscopy Laboratory Unit for carrying out the composition analyses of the samples. The authors gratefully acknowledge use of X-ray facilities and instrumentation supported by NSF through the University of Wisconsin Materials Research Science and Engineering Center (DMR-1121288).

Supplementary material

10570_2017_1259_MOESM1_ESM.docx (682 kb)
Supplementary material 1 (DOCX 681 kb)
10570_2017_1259_MOESM2_ESM.xlsx (318 kb)
Supplementary material 2 (XLSX 317 kb)

References

  1. Abe K, Yamamoto H (2005) Mechanical interaction between cellulose microfibril and matrix substance in wood cell wall determination by X-ray diffraction. J Wood Sci 51:334–338CrossRefGoogle Scholar
  2. Abe K, Yamamoto H (2006) Change in mechanical interaction between cellulose microfibril and matrix substance in wood cell wall induced by hygrothermal treatment. J Wood Sci 52:107–110CrossRefGoogle Scholar
  3. Agarwal UP (2016) Evolution of wood-cellulose native structure upon thermal and hydrothermal Treatments. CELL Division Abstract # 202, ACS, 251st meeting, San DiegoGoogle Scholar
  4. Agarwal UP, Reiner RS, Ralph SA (2010) Cellulose I crystallinity determination using FT–Raman spectroscopy: univariate and multivariate methods. Cellulose 17:721–733CrossRefGoogle Scholar
  5. Agarwal UP, Reiner RS, Ralph SA (2013) Estimation of cellulose crystallinity of lignocelluloses using near-IR FT–Raman spectroscopy and comparison of the Raman and Segal-WAXS methods. J Agric Food Chem 61:103–113CrossRefGoogle Scholar
  6. Agarwal UP, Ralph SA, Reiner RS, Moore RK, Baez C (2014) Impacts of fiber orientation and milling on observed crystallinity in jack pine. Wood Sci Technol 48:213–1227CrossRefGoogle Scholar
  7. Agarwal UP, Ralph SA, Reiner RS, Baez C (2016) Probing crystallinity of never-dried wood cellulose with Raman spectroscopy. Cellulose 23:125–144CrossRefGoogle Scholar
  8. Ahvenainen P, Kontro I, Svedstrom K (2016) Comparison of sample crystallinity determination methods by X-ray diffraction for challenging cellulose I materials. Cellulose 23:1073–1086CrossRefGoogle Scholar
  9. Armstrong RC, Wolfram C, de Jong KP, Gross R, Lewis NS, Boardman B, Ragauskas AJ, Ehrhardt-Martinez K, Crabtree G, Ramana MV (2016) The frontiers of energy. Nat Energy 1:15020CrossRefGoogle Scholar
  10. Astley OM, Chanliaud E, Donald AM, Gidley MJ (2001) Structure of acetobacter cellulose composites in the hydrated state. Int J Biol Macromol 29:193–202CrossRefGoogle Scholar
  11. Atalla RH, Whitmore RE (1978) The influence of elevated temperatures on structures in the isolation of native cellulose. J Poly Sci Poly Lett Ed 16:601405Google Scholar
  12. Atalla RS, Crowley MF, Himmel ME, Atalla RH (2014) Irreversible transformations of native celluloses, upon exposure to elevated temperatures. Carbohydr Poly 100:2–8CrossRefGoogle Scholar
  13. Awa K, Shinzawa H, Ozaki Y (2014) An effect of cellulose crystallinity on the moisture absorbability of a pharmaceutical tablet studied by near-infrared spectroscopy. Appl Spectrosc 68:625–632CrossRefGoogle Scholar
  14. Barnette AL, Lee C, Bradley LC, Schreiner EP, Park YB, Shin H, Cosgrove DJ, Park S, Kim SH (2012) Quantification of crystalline cellulose in lignocellulosic biomass using sum frequency generation (SFG) vibration spectroscopy and comparison with other analytical methods. Carbohydr Poly 89:802–809CrossRefGoogle Scholar
  15. Bertran MS, Dale BE (1986) Determination of cellulose accessibility by differential scanning calorimetry. J Appl Poly Sci 32:4241–4253CrossRefGoogle Scholar
  16. Davis MW (1998) A rapid method for compositional carbohydrate analysis of lignocellulosics by high pH anion-exchange chromatography with pulse amperometric detection (HPAE/PAD). J Wood Chem Technol 18:235–252CrossRefGoogle Scholar
  17. Driemeier C, Bragatto J (2013) Crystallite width determines monolayer Hydration across a wide spectrum of celluloses isolated from plants. J Phys Chem B 117:415–421CrossRefGoogle Scholar
  18. Eichhorn SJ (2011) Cellulose nanowhiskers: promising materials for advanced applications. Soft Matter 7:303–315CrossRefGoogle Scholar
  19. Fang L, Catchmark JM (2014) Structure characterization of native cellulose during dehydration and rehydration. Cellulose 21:3951–3963CrossRefGoogle Scholar
  20. Favier V, Chanzy H, Cavaille JY (1995) Polymer nanocomposites reinforced by cellulose whiskers. Macromolecules 28:6365–6367CrossRefGoogle Scholar
  21. Fink HP, Purz HJ, Bohn A, Kunze J (1997) Investigation of the supramolecular structure of never dried bacterial cellulose. J Macromol Symp 120:207–217CrossRefGoogle Scholar
  22. French AD, Santiago Cintrón M (2013) Cellulose polymorphy, crystallite size, and the Segal crystallinity index. Cellulose 20:583–588CrossRefGoogle Scholar
  23. Hill SJ, Kirby NM, Mudie ST, Hawley AM, Ingham B, Franich RA, Newman RH (2010) Effect of drying and rewetting of wood on cellulose molecular packing. Holzforschung 64:421–427Google Scholar
  24. Hollander M, Wolfe DA, Chicken E (2014) Nonparametric statistical methods, 3rd edn. Wiley, HobokenGoogle Scholar
  25. Hu X-P, Hsieh Y-L (2001) Effects of dehydration on the crystalline structure and strength of developing cotton fibers. Text Res J 71:231–239CrossRefGoogle Scholar
  26. Hulleman SHD, Van Hazendonk JM, Van Dam JEG (1994) Determination of crystallinity in native cellulose from higher plants with diffuse reflectance Fourier transform infrared spectroscopy. Carbohydr Res 261:163–172CrossRefGoogle Scholar
  27. Isogai A (2013) Wood nanocelluloses: fundamentals and applications as new bio-based nanomaterials. J Wood Sci 59:449–459CrossRefGoogle Scholar
  28. Klemm D, Kramer F, Moritz S, Lindstrom T, Ankerfors M, Gray D, Dorris A (2011) Nanocelluloses: a new family of nature-based materials. Angew Chem Int Ed 50:5438–5466CrossRefGoogle Scholar
  29. Langan P, Petridis L, O’Neill HM, Pingali SV, Foston M, Nishiyama Y, Schulz R, Lindner B, Hanson BL, Harton S, Heller WT, Urban W, Evans B, Gnanakaran S, Ragauskas AJ, Smith JC, Davison BH (2014) Common processes drive the thermochemical pretreatment of lignocellulosic biomass. Green Chem 16:63–67CrossRefGoogle Scholar
  30. Langford J, Wilson A (1978) Scherrer after sixty years: a survey and some new results in the determination of crystallite size. J Appl Crystallogr 11:102–113CrossRefGoogle Scholar
  31. Larsson PT, Hult E-L, Wickholm K, Pettersson E, Iversen T (1999) 13C-NMR spectroscopy applied to structure and interaction studies on cellulose I. Solid State Nucl Magn Reson 15:31–40CrossRefGoogle Scholar
  32. Lee JM, Pawlak JJ, Heitmann JA (2012) Dimensional and hygroexpansive behaviors of cellulose microfibrils (MFs) from kraft pulp-based fibers as a function of relative humidity. Holzforschung 66:1001–1008Google Scholar
  33. Lindner B, Petridis L, Langan P, Smith JC (2014) Determination of cellulose crystallinity from powder diffraction diagrams. Biopoly 103:67–73CrossRefGoogle Scholar
  34. Miller RG Jr (1981) Simultaneous statistical inference. Springer, New YorkCrossRefGoogle Scholar
  35. Moon RJ, Martini A, Nairn J, Simonsen J, Youngblood J (2011) Cellulose nanomaterials review: structure, properties and nanocomposites. Chem Soc Rev 40:3941–3994CrossRefGoogle Scholar
  36. Nelson ML, O’Connor RT (1964) Relation of certain infrared bands to cellulose crystallinity and crystal lattice type. Part I. Spectra of lattice types I, II, III and of amorphous cellulose. J Appl Poly Sci 8:1311–1324CrossRefGoogle Scholar
  37. Newman RH (1999) Estimation of the lateral dimensions of cellulose crystallites using 13C NMR signal strengths. Solid State Nucl Magn Reson 15:21–29CrossRefGoogle Scholar
  38. Nishimura H, Okano T, Asano I (1981) Fine structure of wood cell walls. I. Structural features of noncrystalline substances in wood cell walls. Mokuzai Gakkaishi 27:611–617Google Scholar
  39. Nishiyama Y, Langan P, Chanzy H (2002) Crystal structure and hydrogen-bonding system in cellulose Iα from synchrotron X-ray and neutron fiber diffraction. J Am Chem Soc 124:9074–9082CrossRefGoogle Scholar
  40. Nishiyama Y, Langan P, O’Neill H, Pingali SV, Harton S (2014) Structural coarsening of aspen wood by hydrothermal pretreatment monitored by small- and wide-angle scattering of X-ray and neutrons on oriented specimens. Cellulose 21:1015–1024CrossRefGoogle Scholar
  41. Oh SY, Yoo DI, Shin Y, Kim HC, Kim HY, Chung YS, Park WH, Youk JH (2005) Crystalline structure analysis of cellulose treated with sodium hydroxide and carbon dioxide by means of X-ray diffraction and FT-IR spectroscopy. Carbohydr Res 340:2376–2391CrossRefGoogle Scholar
  42. Park S, Baker JO, Himmel ME, Parilla PA, Johnson DK (2010) Cellulose crystallinity index: measurement techniques and their impact on interpreting cellulase performance. Biotechnol Biofuels 3:10CrossRefGoogle Scholar
  43. Peciulyte A, Karlström K, Larsson PT, Olsson E (2015) Impact of the supramolecular structure of cellulose on the efficiency of enzymatic hydrolysis. Biotechnol Biofuels 8:56CrossRefGoogle Scholar
  44. Reiner RS, Rudie AW (2013) Process scale-up of cellulose nanocrystal production to 25 kg per batch at the Forest Products Laboratory. In: Postek MT, Moon RJ, Rudie AJ, Bilodeau MA (eds) Production and applications of cellulose materials. TAPPI Press, Atlanta, pp 21–24Google Scholar
  45. Richter U, Krause T, Schempp W (1991) Untersuchungen zur Alkalibehandlung von Cellulosefasern. Teil 1. Infrarotspektroskopische und Ro¨ntgenographische Beurteilung der A¨ nderung des Ordnungszustandes. Angew Makromol Chem 185:155–167CrossRefGoogle Scholar
  46. R Core Team (2013) R: A language and environment for statistical computing. R Foundation for Statistical Computing, Vienna, Austria. http://www.R-project.org
  47. Schenzel K, Fischer S, Brendler E (2005) New method for determining the degree of cellulose I crystallinity by means of FT Raman spectroscopy. Cellulose 12:223–231CrossRefGoogle Scholar
  48. Scherrer P (1918) Bestimmung der Grösse und der inneren Struktur von Kolloidteilchen mittels Röntgenstrahlen. Nachrichten von der Gesellschaft der Wissenschaften, Göttingen, pp 98–100Google Scholar
  49. Segal L, Creely JJ, Martin AE, Conrad CM (1959) An empirical method for estimating the degree of crystallinity of native cellulose using the X-ray diffractometer. Text Res J 29:786–794CrossRefGoogle Scholar
  50. Sisson WA (1933) X-ray analysis of fibers, part I, literature survey. Text Res J 3:295–307CrossRefGoogle Scholar
  51. Sugino H, Sugimoto H, Miki T, Kanayama K (2007) Fine structure changes of wood during moisture adsorption and desorption process analyzed by X-ray diffraction measurement. Mokuzai Gakkaishi 53:82–89CrossRefGoogle Scholar
  52. TAPPI test method (1983) Acid insoluble lignin in wood and pulp; official test method T-222 (Om). TAPPI, AtlantaGoogle Scholar
  53. Toba K, Yamamoto H, Yoshida M (2013) Crystallization of cellulose microfibrils in wood cell wall by repeated dry-and-wet treatments, using X-ray diffraction technique. Cellulose 20:633–643CrossRefGoogle Scholar
  54. Tokoh C, Takabe K, Fujita M, Saiki H (1998) Cellulose synthesized by Acetobacter xylinum in the presence of acetyl glucomannan. Cellulose 5:249–261CrossRefGoogle Scholar
  55. Vieira FS, Pasquini C (2014) Determination of cellulose crystallinity by terahertz-time domain spectroscopy. Anal Chem 86:3780–3786CrossRefGoogle Scholar
  56. Wormald P, Wickholm K, Larsson PT, Iversen T (1996) Conversions between ordered and disordered cellulose. Effects of mechanical treatment followed by cyclic wetting and drying. Cellulose 3:141–152CrossRefGoogle Scholar
  57. Zabler S, Paris O, Burgert I, Fratzl P (2010) Moisture changes in the plant cell wall force cellulose crystallites to deform. J Struct Biol 171:133–141CrossRefGoogle Scholar
  58. Zhu H, Luo W, Ciesielski PN, Fang Z, Zhu JY, Henriksson G, Himmel ME, Hu L (2016) Wood-derived materials for green electronics, biological devices, and energy applications. Chem Rev 116:9305–9374CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht (outside the USA) 2017

Authors and Affiliations

  • Umesh P. Agarwal
    • 1
    Email author
  • Sally A. Ralph
    • 1
  • Carlos Baez
    • 1
  • Richard S. Reiner
    • 1
  • Steve P. Verrill
    • 1
  1. 1.Forest Products LaboratoryUSDA FSMadisonUSA

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