Molecular deformation of single spruce wood fibres followed by Raman microscopy Notburga Gierlinger, Michaela Eder and Ingo Burgert Max-Planck Institute of Colloids and Interfaces Department of Biomaterials Johannes Kepler University Linz Institute of Polymer Science
AIM AIM AND APPROACH changes on the molecular level during - tensing - changing environment better understanding of the micromechanics and cell wall polymer properties APPROACH tensile testing of wood tissues and single fibres + Raman microscopy
RAMAN EFFECT SIR CHANDRASEKHARA VENKATA RAMAN Rayleigh Scatter (elastic, same wavelength as incident light) Raman Scatter (inelastic, new wavelength)
RAMAN- and IR- spectroscopy Virtual hυ 0 h(υ 0 -υ 1 ) h(υ 0 +υ 1 ) excited state ground state 1 0 hυ 1 IR Rayleigh Stokes Anti-Stokes RAMAN ABSORPTION change in dipolmoment SCATTERING change in polarisability
RAMAN- and IR- spectroscopy wood spectra OH arom C-C, C-O Raman Intensity Absorbance CH Raman FT-IR 3500 3000 2500 2000 1500 1000 cm -1
Effect of orientation on Raman band intensity of wood spectra Raman Intensity [CCD cts] 4000 3000 2000 1000 1657 1600 1339 1122 1095 red = 0, 3, 6, 9 pink = 12, 15, 18, 21 turkis = 24, 27, 30, 33 blue = 36, 39, 42, 45 light green= 48, 51, 54, 57 green = 60, 63, 66, 69 grey = 72, 75, 78, 81 black = 84, 87, 90, 93 1377 378 437 1416 1272 458 330 1457 499 997 898 517 latewood single fibre (MFA<10 ) 0 1600 1400 1200 1000 800 600 400 wavenumber [cm -1 ] Gierlinger, N; Luss, S.; König, Ch.; Konnerth, J.; Eder, M.; Fratzl, P. 2009 Cellulose microfibril orientation of Picea abies and its variability on the micron-level determined by Raman imaging. Journal of Experimental Botany: in print
Prediction of cellulose orientation by band height ratios y= y 0 +ax+bx 2 R 2 Std Err y 0 a b PRESS 1122/1095 0.991 8 1377/1095 0.996 1 378/1095 0.994 2 0.0335 3.507-5.602 2.208 0.0727 0.0229 2.1324-4.6192 2.4624 0.0341 0.0281 1.654-3.084 1.445 0.0517 Gierlinger, N; Luss, S.; König, Ch.; Konnerth, J.; Eder, M.; Fratzl, P. 2009 Cellulose microfibril orientation of Picea abies and its variability on the micron-level determined by Raman imaging. Journal of Experimental Botany: in print
Prediction of cellulose orientation by PLS models factor R 2 (CAL ) R 2 (CV) RMSECV R 2 (TS) RMSEP 3 0.999 0.999 0.0087 0.999 0.0098 1 0.998 0.998 0.0147 0.998 0.0148 Gierlinger, N; Luss, S.; König, Ch.; Konnerth, J.; Eder, M.; Fratzl, P. 2009 Cellulose microfibril orientation of Picea abies and its variability on the micron-level determined by Raman imaging. Journal of Experimental Botany: in print
Prediction of cellulose orientation by Raman compared to X-ray sample layer MFA x-ray 1377/ 1095 1122/ 1095 378/ 1095 PLS_3 PLS_1 mean latewood (LW00) S2 rad 0 1.79 9.9 11.76 10.79 6.86 0 S2 tang 0 1.34 9.41 10.41 6.64 5.56 S1 tang 36.80 48.88 50.05 50.06 47.12 46.58 - S1 rad 34.03 47.95 52.78 51.99 47.50 46.85 latewood (LW20) opposite (OW) wood S2 tang 20 14.06 24.40 26.34 27.66 26.79 23.85 S1 tang - 41.05 54.66 60.15 54.43 52.58 52.57 S2 tang 35 32.80 37.26 37.17 41.73 41.36 38.06 S1 tang - 39.13 49.52 53.33 54.89 52.18 49.80 compression wood (CW) S2 tang 50 30.21 40.34 49.37 49.29 48.28 43.51 S1 tang - 32.81 64.98 63.84 67.60 65.24 58.90 Gierlinger, N; Luss, S.; König, Ch.; Konnerth, J.; Eder, M.; Fratzl, P. 2009 Cellulose microfibril orientation of Picea abies and its variability on the micron-level determined by Raman imaging. Journal of Experimental Botany: in print
Effect of tensile load on the Raman spectra low and high stress level) 12000 A 1602 Raman Intensity [CCD cts] 10000 8000 6000 arom. aryl str. lignin OH cellulose 3375 1097 C-C, C-O 3600 3400 3200 1600 1400 1200 wavenumber [cm -1 ] Gierlinger, N.; Schwanninger, M.; Reinecke, A.; Burgert, I. 2006: Molecular changes during tensile deformation of single wood fibers followed by Raman microscopy. Biomacromolecules, 7 (7): 2077-2081
Gierlinger, N.; Schwanninger, M.; Reinecke, A.; Burgert, I. 2006: Molecular changes during tensile deformation of single wood fibers followed by Raman microscopy. Biomacromolecules, 7 (7): 2077-2081 Effect of tensile load on the Raman spectra low and high stress level) 10000 B 1097 1092 Raman Intensity [CCD cts] 9000 8000 7000 1127 1124 6000 1160 1140 1120 1100 1080 1060 wavenumber [cm -1 ]
Position and Intensity of the Raman bands is influenced by Composition of the sample (lignin, cellulose, hemicelluloses, extractives) Orientation of the molecules within the sample in respect to the laser polarisation direcetion Status (load) and environment (Dry wet) of the sample APPROACH tensile testing of wood tissues and single fibres + Raman microscopy Stress and reorientation on the molecular level
TENSILE TESTER load cell motor water reservoir fibre
SPRUCE LATEWOOD: tissue vs single fibre
SPRUCE LATEWOOD: tissue vs single fibre Gierlinger, N., Burgert, I. 2006: Secondary cell wall polymers studied by Confocal Raman microscopy: Spatial distribution, orientation and molecular deformation. New Zealand Journal of Forestry Science, 36 (1): 60-71
SINGLE SPRUCE FIBRES adult and juvenile latewood 1.4 adult 1.2 1.0 juvenile MFA~5 stress [GPa] 0.8 0.6 0.4 0.2 MFA~15 0.0 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 strain [-]
SINGLE SPRUCE FIBRES adult and juvenile latewood 1100 1100 1098 latewood juvenile wood 1098 latewood juvenile wood wavenumber [cm -1 ] 1096 1094 1092 b[0] = 1097.53 b[1] = -128.93 r ² = 0.95 wavenumber [cm -1 ] 1096 1094 1092 b[0] = 1098.06 b[1] = -7.71 r ² = 0.98 1090 1088 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 strain [-] b[0] = 1098.24 b[1] = -210.16 r ² = 0.97 1090 b[0] = 1097.68 b[1] = -8.20 r ² = 0.95 1088 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 stress [GPa]
SINGLE SPRUCE FIBRES adult and juvenile - earlywood and latewood adult latewood juvenile latewood MFA~5 1.4 MFA~15 1.2 1.0 LW21 JW5 JW05_0 05 stress [GPa] adult earlywood 0.8 0.6 0.4 juvenile earlywood 0.2 EW1 0.0 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 strain [ ]
SINGLE SPRUCE FIBRES adult and juvenile - earlywood and latewood 1100 1100 wavenumber [cm -1 ] 1098 1096 1094 1092 1090 adult juvenile adult early adult late juv late juv early wavenumber [cm -1 ] 1098 1096 1094 1092 1090 earlywood latewood adult early adult late juv late juv early 1088 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 strain [-] MFA 1088 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 stress [GPa] Geometry?
SINGLE SPRUCE FIBRES juvenile latewood: dry-wet 100 TENS STOP TENS STOP TENS 1096 80 1094 force [mn] 60 40 20 H 2 0 1092 1090 wavenumber [cm -1 ] 1088 0 1086 0 200 400 600 800 time [s]
SINGLE SPRUCE FIBRES juvenile latewood: dry-wet 100 TENS STOP TENS STOP TENS 1096 100 TENS STOP TENS STOP TENS 40 80 1094 80 force [mn] 60 40 20 H 2 0 1092 1090 1088 wavenumber force [mn] [cm -1 ] 60 40 20 H 2 0 30 20 10 MFA [ ] 0 0 1086 0 200 400 600 800 time [s] cellulose load 0 0 200 400 600 800 time [s] microfibril orientation
CONCLUSIONS Much higher shifts (loads) in single fibre than in wood tissues Molecular cellulose load correlates across different samples (juvenile, adult, tissue, fibre) with macroscopic stress.except earlywood Monitoring changes in molecular load and orientation simultaneously Wetting of the fibre: Load release through swelling induced change in orientation?
...and you for your ATTENTION THANKS Biomaterial group (MPI Golm) Financial support: Max Planck Society Austrian Academy of Sciences (APART programme) Ingo Burgert Michaela Eder Peter Fratzl
INTITUTE OF POLYMER SCIENCE (Head: Prof. Sabine Hild) Polymeric materials Flow characteristics rheology Solidification characteristics crystallization Microstructural characterization with respect to material properties Biological materials Microstructure, local chemical composition and mechanical properties Mineralized tissues, plant cell wall cotton linter cotton linter microtomy, light microscopy Raman-microscopy combined with AFM (PFM) AFM, nanointendation Extruder, Spin coater, DSC, Rheometer Raman AFM
Samples under load RAMIE single fibre 0.6 1097 25 stress [GPa] 0.5 0.4 0.3 0.2 0.1 1096 1095 1094 1093 wavenumber [cm-1} shift [cm-1] 20 15 10 5 0-5 1411cm 1381cm 1095cm 997cm 896cm 459cm 380cm 3378cm OH str 0.0 1092 0.00 0.01 0.02 0.03 0.04 0.05 0.06 strain [] 1 0.00 0.01 0.02 0.03 0.04 0.05 0.06 strain change in stress strain curve change in the hydrogen network change in load distribution gliding of fibrils shift [cm-1] 0-1 -2-3 -4-5 1411cm (HCC, HCO, HOC bending) 1095cm (COC) glycosid 459cm (CCO) ring 380cm (CCC) ring -6-0.01 0.00 0.01 0.02 0.03 0.04 0.05 0.06 strain
Polymer composition and orientation in plant fibres RAMIE 0/0 (parallel) 90/90 0/90 90/0
Polymer composition and orientation in plant fibres Ramie fiber 0/0 90/90 0/90 90/0 1096 R 1 = I (0/90) /I (0/0) = 0.07 R 2 = I (90/0) /I (90/90) = 0.53 Depolarisation ratios Bacterial cellulose film R 1 = 0.19 R 2 = 0.2 Order parameters P2 and P4 Probable orientation distribution function
MOLECULAR DEFORMATION IN WOOD STUDIED BY RAMAN MICROSCOPY Wiley and Atalla (1987) Agarwal and Ralph (1997)