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Table 4. The plant fibres cellulose crystallinity, calculated by Rietveld refinement, (g/100 g cellulose) and chemical composition measured by comprehensive fibre analysis (g/100 g dry matter) (Paper III and IV). Material Cellulose Cellulose Sample Amorphous Residual crystallinity crystallity cellulose components g/100 g cellu. g/100 g DM g/100 g DM g/100 g DM g/100 g DM Hemp fibres 94 64 60 4 36 Norway spruce 67 49 33 16 51 Barley straw 100 43 43 0 57 Corn stover 100 33 33 0 67 Sample crystallinity [g/100 g DM] ... Corn stover Norway spruce Norway spruce (ref 1) Barley straw Filter paper Norway spr.pulp(ref 2) Hemp fibres Avicel cellulose 100 80 60 40 20 0 0 20 40 60 80 100 Cellulose content [g/100 g DM] Figure 14. Sample crystallinity determined by Rietveld refinement compared to the cellulose content. The relationship for non-woody materials (full drawn line) and the relationship for wood based materials (dotted line) are shown (ref 1 = Andersson et al. (2003); ref 2 = Liitia et al,( 2003); Paper III; Paper IV). 5.3.2 Hemicellulose Hemicellulose in hemp and straw fibres are short and highly branched polymers of pentoses such as xylose and arabinose (Puls and Schuseil, 1993). Hemicellulose contains also substituents like acetyl groups and glucoronic acid (Figure 15). The degree of polymerisation is much lower than in cellulose ranging from 20 to 300. By attached ferulic acid and p-coumaric residues, hemicellulose can form covalent bonds to lignin (Bjerre and Schmidt, 1997). Hydrogen bonds are formed between xylan and cellulose. Due to this linking effect of hemicellulose, hemicellulose degradation leads to disintegration of the fibres into cellulose microfibrils resulting in lower fibre bundle strength (Morvan et al., 1990). Mainly the acid residues attached to hemicellulose make it highly hydrophilic and increase the fibres water uptake, which increases the risk of microbiological fibre degradation. It has been found that hemicellulose is thermally degraded at lower temperature (150-180°C) than cellulose (200-230°C) by wet oxidation (Bjerre et al., 1996) and composite manufacturing (Madsen, 2004). 28 Risø-PhD-11
Figure 15. The structure of hemicellulose in non-woody fibres (grasses) showed as the acetylated xylan chain with α-1,2 bond to 4-O-methyl glucuronic acid (left side group) and with α-1,3 bond to L-arabinofuranose, which also is linked to phenolic acid (right side group) (Puls and Schuseil, 1993). 5.3.3 Lignin Together with cellulose, lignin is the most abundant and important polymeric organic substance in the plant world. Lignin increases the compression strength of plant fibres by gluing the fibres together to form a stiff structure, making it possible for trees of 100 meters to remain upright. Lignin is a very complex three dimensional polymer, made of different phenylpropane units, which are bound together by ether and carbon-carbon bonds (Fan et al., 1982). Since hemp belongs to the Angiosperm phylum, it contains hardwood lignin of coniferyl alcohol, sinapyl alcohol and a minor content of p-coumaryl alcohol (Paper II). It was shown by treatment of hemp with P. radiata Cel 26, that degradation of lignin and pectin presumeably reduces the fibre bundle tensile strength slightly (Paper II). Therefore lignin seems to act like a matrix material within the fibres, making stress transfer on microfibril scale and single fibre scale possible. 5.3.4 Pectin Pectin is a heterogeneous structure of acidic structural polysaccharides, found in fruits and bast fibres (Table 3). The majority of the structure consists of homopolymeric partially methylated poly-α-(1→4)-D-galacturonic acid residues but there are substantial 'hairy' non-gelling areas of alternating α-(1→2)-L-rhamnosyl-α-(1→4)-D-galacturonosyl sections containing branch-points with mostly neutral side chains (1-20 residues) of mainly L-arabinose and D-galactose (rhamnogalacturonan I). Pectin is the most hydrophilic compound in plant fibres due to the carboxylic acid groups and was easily degraded by defibration with fungi (Paper IV). Tests of hemp fibres as single fibres and fibre bundles showed that treatment with pectinase enzymes and thereby pectin degradation decreases the fibre strength slightly (Paper II; Madsen et al., 2003). Risø-PhD-11 29
Page 1 and 2: Risø-PhD-11(EN) Properties of hemp
Page 3 and 4: Contents Preface 6 1 Resumé 7 2 Li
Page 5 and 6: PhD thesis: Properties of hemp fibr
Page 7 and 8: 1 Resumé Karakterisering af hampef
Page 9 and 10: 2.4 Oral presentations Anders Thyge
Page 11 and 12: 4 Introduction Hemp (Cannabis sativ
Page 13 and 14: 4.2 The outline of the thesis The f
Page 15 and 16: The only fertilizer used was 360/48
Page 17 and 18: Temperature [ o C] 35 30 25 20 15 1
Page 19 and 20: A B Figure 7. A: Model of transvers
Page 21 and 22: Figure 8. Lignin (a), pectin (b) an
Page 23 and 24: Figure 11. Microfibril angles (MFA)
Page 25 and 26: Teleman, 1997). The crystal structu
Page 27: to the computing effort and the sub
Page 31 and 32: fibre mats, which are made by air-d
Page 33 and 34: Figure 18. From fibre filament to a
Page 35 and 36: A B C D Figure 20. Chemical structu
Page 37 and 38: water vapour and air are removed fr
Page 39 and 40: 7 Defibration methods Defibration m
Page 41 and 42: Table 5. Fibre yield and cellulose
Page 43 and 44: a b c Composition [% w/w] 100 Compo
Page 45 and 46: 8 Fibre strength in hemp The streng
Page 47 and 48: 8.2 Effect of pre-treatment of hemp
Page 49 and 50: E-modulus [GPa] 90 80 70 60 50 40 3
Page 51 and 52: Second mode: Failure is controlled
Page 53 and 54: structure, which made much higher f
Page 55 and 56: Table 7. Porosity factors determine
Page 57 and 58: Thereby, the effective fibre streng
Page 59 and 60: a b Composite tensile strength σcu
Page 61 and 62: Table 9. Mechanical properties in a
Page 63 and 64: a σ c/ρ c [10 3 m 2 /s 2 ] b Ec/
Page 65 and 66: Fibre strength σ f [MPa] Fibre sti
Page 67 and 68: 11 References Andersen TL, Lilholt
Page 69 and 70: Kaar WE, Cool LG, Merriman MM, Brin
Page 71 and 72: Stowell EZ, Liu TS, 1961. On the Me
Page 73 and 74: Appendix A: Comprehensive composite
Page 75 and 76: The porosity constants can now be d
Page 77 and 78: Appendix D: Density and mechanical
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Paper I Changes in chemical composi
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Paper II Hemp fiber microstructure
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ABSTRACT Characterization of hemp f
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METHODS AND TECHNIQUES Treatment of
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2000) and their orientation gave th
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By TEM microscopy, the single fiber
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Table 1. Chemical composition of th
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Table 2. Tensile strength (σ) and
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Morvan, C., Jauneau, A., Flaman, A.
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Paper IV Comparison of composites m
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ABSTRACT Aligned epoxy-matrix compo
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the calculation of volume fractions
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solution (pH 4) for 4 h at 85°C. L
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E ⎛ dσ c ⎞ = ⎜ ⎟ ⎝ dε
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Table 2. Chemical composition, stru
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transverse section of the small hem
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Long fibres that pass through the e
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Figure 6. Effect of composite fabri
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DISCUSSION The defibration of hemp
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This investigation showed that the
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Bos, H.L., Molenveld, K., Teunissen
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Thygesen, A., 2006. Properties of h
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Risø-PhD-11 145
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Risø’s research is aimed at solv
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