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Effect of heat treatment on physical and mechanical properties of wood and recycled wood-plastic composite
|關鍵字:||熱處理;Heat treatment;木材塑膠複合材;阿瑞尼斯方程式;活化能;界面性質;Wood plastic composite;Arrhenius equation;Activation energy;Interfacial interaction||出版社:||森林學系所||引用:||林曉洪、林盈宏（2011）熱處理木材之性質。林業研究季刊 33(1)：91–108。 Akgül, M., E. Gümüskaya and S. Korkut (2007) Crystalline structure of heat-treated Scors pine [Pinus sylvestris L.] and Uludağ fir [Abies nordmanniana (Stev.) subsp. Bornmuelleriana (Mattf.)] wood. Wood Sci. Technol. 41:281–289. Bekhta, P. and P. Niemz (2003) Effect of high temperature on the change in color, dimensional stability and mechanical properties of spruce wood. Holzforschung 57:539–546. Bhuiyan, M. T. R. and N. H. N. Sobue (2000) Changes of crystallinity in wood cellulose by heat treatment under dried and moist condition. J. Wood Sci. 46:431–436. Boonstra, M. J. and B. Tjeerdsma (2006) Chemical analysis of heat treated softwoods. Eur. J. Wood Wood Prod. 64:204–211. Brebu, M. and C. Vasile (2010) Thermal degradation of lignin–a review. Cell. Chem. Technol. 44:454–363. 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本研究係利用不同溫度（120–260oC）、環境（空氣及氮氣）及持溫時間（2h）對柳杉（Cryptomeria japonica）及山毛櫸（Fagus sylvatica）進行熱處理，並將熱處理後之木粒片與回收型高密度聚乙烯（Recycled high density polyethylene，rHDPE）製備成木材塑膠再生複合材（Wood plastic recycled composite，WPC），同時，利用萬能強度試驗機、動態機械分析儀、全反射式傅立葉紅外線光譜儀、X-ray繞射儀、固態核磁共振儀、色差計等儀器，探討熱處理對木材及木材塑膠複合材物理機械及熱性質之影響。試驗結果顯示，木材之質量損失率及尺寸收縮率隨著熱處理溫度之提高而增加。另外，經由浸水試驗結果亦得知，熱處理後之木材具有較高之疏水性及尺寸安定性。至於機械性質方面，於空氣環境下，當熱處理溫度超過200oC時，試材之抗彎強度則有顯著性的下降；而當熱處理溫度達260oC時，試材之抗彎性質最差。而在木材表面性質方面，經過熱處理後之木材表面顏色變深，且呈現較平滑之表面。另一方面，試材經過熱處理後，會因其非結晶區中多醣類成分的降解，而增加試材結晶度，同時，由NMR試驗結果得知，木質素會發生熱交聯及熱縮合反應。此外，試驗結果亦發現，全反射式傅立葉轉換紅外線光譜儀（Attenuated total reflectance–Fourier transforminfrared spectroscopy，ATR–FTIR）結合主成分分析（Principle component analysis，PCA），能有效區分不同程度之柳杉熱處理材。
由動態機械分析儀試驗結果亦得知，試材之儲存模數（Storage modulus，E’）與熱處理溫度具關聯性。以山毛櫸為例，於氮氣環境下，當熱處理溫度低於160oC時，儲存模數損失率（Decrease rate of storage modulus，E’D）之自然對數值（ln E’D）與熱處理之絕對溫度的倒數（1/K）間並無顯著相關性；然當溫度超過160oC後，二者之間則呈一線性相關（R2 = 0.995）。而進一步經由阿瑞尼斯方程式（Arrhenius equation）計算後得知，山毛櫸於有氧環境下之熱降解活化能（141.3 kJ/mol）明顯低於氮氣環境者（150 kJ/mol）。
另一方面，以熱處理木粒片所製備之木材塑膠複合材，其吸水率及吸水厚度膨脹率隨處理溫度提高而降低，而抗彎性質及木螺釘保持力則與對照組間無顯著差異。至於內聚強度方面，當熱處理溫度為120oC時，即能有效提升複合材之內聚強度，由未處理之1.5 MPa提高至2.0 MPa。顯示，木粒片透過熱處理後，確實能有效提高木粒片與塑膠相容性以及二者間之界面性質。
In this study, Cryptomeria japonica (Sugi) and Fagus sylvatica (Beech) were heat treated during 2h by different temperatures (120–260oC) and gas atmosphere (air and nitrogen), and then heat treated particles and recycled high density polyethylene (rHDPE) were used as raw materials to manufacture wood-plastic composites (WPC). Effects of heat treatment on physicomechanical and thermal-properties of woods and WPC were evaluated by universal testing machine, dynamic mechanical analyzer, attenuated total refletcion–Fourier transform infrared spectroscopy (ATR–FTIR), X–ray diffractometer, 13C CP/MAS nuclear magnetic resonance spectrometer (13C CP/MAS NMR), and color difference meter. These results showed that the mass loss and dimensional shrinkage percentage of heat treated woods increased with increasing treated temperatures. As the results of soaking test, woods exhibited better dimensional stability and hydrophobic properties during heat treatment. As for mechanical properties, the modulus of rupture (MOR) of wood had significant decreased when heat treatment was performed at temperature exceed 200oC under air atmosphere. And then, the flexural properties of wood exhibited the worst at 260oC. For surface properties, the color of wood became darker during heat treatment, and the surface of heat treated wood was smoother. On the other hand, the crystallinity of heated wood increased due to the polysaccharides of amorphous region were degraded. In addition, lignin occurred thermal condensation and thermal cross-linking reaction at the same time according to NMR analysis. Furthermore, in this study, the combinations of ATR–FTIR and principle component analysis (PCA) is succeeded to discriminate different degrees of heat treated Sugi.
Results from dynamic mechanical analyzer revealed that there was a high correlation between the storage modulus (E’) and treated temperatures. As an example of beech wood, there is no significant correlation between the natural log of decrease rate of storage modulus (E’D) and reciprocal absolute temperature when the heat treatment was performed at temperature below 160oC under a nitrogen atmosphere. However, a linear correlation between ln E’D and 1/K was observed (R2 = 0.995) when the temperature exceeded 160oC. Moreover, according to Arrhenius equation, the activation energy of beech wood under an air atmosphere was calculated as 141.3 kJ/mol which was lower than that of wood under a nitrogen atmosphere (150 kJ/mol).
Results also showed that the water absorption and thickness swelling of WPC made by heat treated particles decreased with increasing treated temperature. Furthermore, the flexural properties and wood screw-holding strength of WPC had no significant difference between untreated and heat treated ones. However, internal bond strength of WPC were significantly increased after heat treatment, even though the treated temperature was 120oC, the internal bond strength of untreated and heat treated WPC were 1.5 MPa and 2.0 MPa, respectively. Accordingly, the result indicates that the compatibility and interfacial interaction between the wood particles and the polymeric matrix could be improved by heat treated process.
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