磁控溅射法制备纳米氧化锌/木材复合材料及其物理性能变化
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摘要
【目的】为了改善木材表面物理性能,探索制备纳米氧化锌/木材复合材料的方法。【方法】以31年树龄的樟子松木单板作为研究对象,采用磁控溅射法制备纳米氧化锌/木材复合材料,对木材进行功能性改良,利用X射线衍射仪(XRD)、纳米压痕仪、接触角测量仪和扫描电镜(SEM)对样品结构、弹性模量、硬度、表面润湿性和微观形貌等进行表征。【结果】纳米氧化锌/木材复合材料XRD谱图显示:在2θ等于17. 0°、22. 5°、35. 0°附近仍具有木材纤维素3个结晶面(101、002和040)的特征峰;在2θ等于31. 8°、36. 3°附近出现了ZnO(100)、ZnO(101)的特征衍射峰。在基底温度为200℃溅射条件下,木材纤维素结晶度下降23. 1%。纳米压痕载荷-压入深度曲线形状变化较大,弹性模量增大了6. 6倍,硬度增大了23%;纳米氧化锌/木材复合材料表面水接触角为140. 2°;表面的纳米氧化锌粒径较小,分散性较好,在木材单板表面分布平整均匀。【结论】磁控溅射法制备纳米氧化锌/木材复合材料对木材结晶区没有形成影响,依然存在木材纤维素特征衍射峰,纤维素的结晶结构没有遭到破坏,但衍射峰强度有所降低;在木材单板表面生长氧化锌薄膜增大了木材表面的弹性模量和硬度,使木材表面润湿性能从亲水性变为疏水性,接近氧化锌材料的超疏水性能;木材表面生长的氧化锌薄膜均匀,排列致密,表面平整,无裂痕。可见,利用磁控溅射法在木材单板表面生长氧化锌薄膜,能够制备理想的纳米氧化锌/木材复合材料。
[Objective] In order to improve the physical properties of wood surface,methods are explored for preparing nano ZnO/wood composite. [Method] The 31-year-old Pinus sylvestris wood veneer was taken as the research object. Nano ZnO was deposited on the wood surface by magnetron sputtering to improve the wood function. Based on X-ray diffractometer( XRD),nanoindenter,contact angle measuring instrument and scanning electron microscope( SEM), the structure, modulus of elasticity,hardness,surface wettability and microstructure of the wood samples were investigated.[Result] XRD test results showed that when the diffraction angle 2θ was about 17. 0°,22. 5° and35. 0°,there were still the characteristic peaks of three crystal faces( 101,002 and 040) of woodcellulose; the characteristic diffraction peaks of ZnO( 100) and ZnO( 101) appeared near the diffraction angles 31. 8° and 36. 3°. The relative crystallinity decreased by 23. 1% when the magnetron sputtering substrate temperature was 200 ℃. The shape of the nanoindentation load-pressed depth curve changed greatly. The elastic modulus increased by 6. 6 times,and the hardness increased by 23%. The water contact angle of the nano ZnO/wood composite surface was 140. 2°. The nano ZnO of the surface had small particle size,good dispersion,flat distribution on the surface of the wood. [Conclusion]The nano ZnO deposited on the wood surface by magnetron sputtering does not affect the crystallization zone of the wood. There are still wood cellulose characteristic diffraction peaks,meaning that the crystalline structure of the wood cellulose is not damaged,but the intensity of the wood cellulose characteristic diffraction peak decreases. The ZnO film on wood veneer surface increases the elastic modulus and hardness of wood veneer surface. The surface wetting property changes from hydrophilic to hydrophobic,closes to the superhydrophobic property of ZnO. The nano ZnO film on the surface of the wood is uniform,smooth,densely arranged and without cracks. The ideal nano ZnO/wood composite with improved physical properties can be obtained by depositing nano ZnO on the wood surface using magnetron sputtering.
[Objective] In order to improve the physical properties of wood surface,methods are explored for preparing nano ZnO/wood composite. [Method] The 31-year-old Pinus sylvestris wood veneer was taken as the research object. Nano ZnO was deposited on the wood surface by magnetron sputtering to improve the wood function. Based on X-ray diffractometer( XRD),nanoindenter,contact angle measuring instrument and scanning electron microscope( SEM), the structure, modulus of elasticity,hardness,surface wettability and microstructure of the wood samples were investigated.[Result] XRD test results showed that when the diffraction angle 2θ was about 17. 0°,22. 5° and35. 0°,there were still the characteristic peaks of three crystal faces( 101,002 and 040) of woodcellulose; the characteristic diffraction peaks of ZnO( 100) and ZnO( 101) appeared near the diffraction angles 31. 8° and 36. 3°. The relative crystallinity decreased by 23. 1% when the magnetron sputtering substrate temperature was 200 ℃. The shape of the nanoindentation load-pressed depth curve changed greatly. The elastic modulus increased by 6. 6 times,and the hardness increased by 23%. The water contact angle of the nano ZnO/wood composite surface was 140. 2°. The nano ZnO of the surface had small particle size,good dispersion,flat distribution on the surface of the wood. [Conclusion]The nano ZnO deposited on the wood surface by magnetron sputtering does not affect the crystallization zone of the wood. There are still wood cellulose characteristic diffraction peaks,meaning that the crystalline structure of the wood cellulose is not damaged,but the intensity of the wood cellulose characteristic diffraction peak decreases. The ZnO film on wood veneer surface increases the elastic modulus and hardness of wood veneer surface. The surface wetting property changes from hydrophilic to hydrophobic,closes to the superhydrophobic property of ZnO. The nano ZnO film on the surface of the wood is uniform,smooth,densely arranged and without cracks. The ideal nano ZnO/wood composite with improved physical properties can be obtained by depositing nano ZnO on the wood surface using magnetron sputtering.
引文
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[13]彭琎,陈广琦,宋宜驰,等.聚酰亚胺柔性基底上磁控溅射金属铜膜的电学性能研究[J].物理学报,2014,63(13):138101.Peng J, Chen G Q, Song Y C, et al. Study on electrical performance of metal copper films deposited by magnetron sputtering on polyimide flexible substrates[J]. Acta Physica Sinica,2014,63(13):138101.
[14] Segal L,Creely J J,Martin Jr A E,et al. An empirical method for estimating the degree of crystallinity of native cellulose using the Xray diffractometer[J]. Textile Research Journal,1959,29(10):786--794.
[15] Mwaikambo L Y,Ansell M P. Chemical modification of hemp,sisal,jute, and kapok fibers by alkalization[J]. Journal of Applied Polymer Science,2002,84(12):2222-2234.
[16] Zhang P P,Tong D S,Lin C X,et al. Effects of acid treatments on bamboo cellulose nanocrystals[J]. Asia-Pacific Journal of Chemical Engineering,2014,9(5):686--695.
[17] Oliver W C,Pharr G M. An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments[J]. Journal of Materials Research,1992,7(6):1564--1583.
[18]徐垚,王占山,徐敬,等.用X射线反射测量法表征双层结构中低原子序数材料的特性[J].光学精密工程,2007,15(12):1838-1843.Xu Y,Wang Z S,Xu J,et al. Characterization of low-Z material layer profiles in bilayer structures by X-ray reflectivity measurement[J]. Optics and Precision Engineering,2007,15(12):1838--1843.
[19]吕文华,赵广杰.杉木木材/蒙脱土纳米复合材料的结构和表征[J].北京林业大学学报,2007,29(1):131--135.LüW H, Zhao G J. Structure and characterization of Cunninghamia lanceolata wood-MMT inter-calation nanocomposite(WMNC)[J]. Journal of Beijing Forestry University,2007,29(1):131--135.
[20]彭晓瑞,张占宽.等离子体处理对6种木材表面润湿性能的影响[J].林业科学,2018,54(1):90-98.Peng X R,Zhang Z K. Influence of plasma treatment on six kinds of wood surface wettability[J]. Scientia Silvae Sinicae,2018,54(1):90-98.
[21]程瑞香,顾继友.落叶松、桦木和柞木木材表面的润湿性[J].东北林业大学学报,2002,30(3):29-31.Cheng R X,Gu J Y. Wettability of larch,birch and oak[J].Journal of Northeast Forestry University,2002,30(3):29--31.
[2]常焕君,刘思辰,王小青,等.木材表面纳米Ti O2疏水薄膜的构建及抗光变色性能[J].南京林业大学学报(自然科学版),2015,39(4):116--120.Chang H J, Liu S C, Wang X Q, et al. Construction of hydrophobic nano-TiO2on wood surface and analysis of its antiphotodiscoloration performance[J]. Journal of Nanjing Forestry University(Natural Sciences Edition),2015,39(4):116-120.
[3]杨亭亭,刘长松,张德建,等.氧化锌超疏水薄膜的制备及其耐久性[J].材料保护,2017,50(4):30--34.Yang T T,Liu C S,Zhang D J,et al. Fabrication of ZnO superhydrophobic surface and its durability[J]. Materials Protection,2017,50(4):30--34.
[4] Liu Y,Das A,Xu S,et al. Hybridizing ZnO nanowires with micropyramid silicon wafers as superhydrophobic high-efficiency solar cells[J]. Advanced Energy Materials,2012,2(1):47-51.
[5]刘红芹,徐文国,王彦斌,等.超疏水氧化铜薄膜的制备及表征[J].腐蚀与防护,2010,31(2):107--110.Liu H Q, Xu W G, Wang Y B, et al. Fabrication and characterization of stable super hydrophobic cupric oxide films[J].Corrosion&Protection,2010,31(2):107--110.
[6] Zhao G J,Lu W H. Nanoscale in wood,nanowood and woodinorganic nanocomposites[J]. Forestry Studies in China,2003,5(1):44-48.
[7]赵广杰.木材中的纳米尺度、纳米木材及木材--无机纳米复合材料[J].北京林业大学学报,2002,24(增刊1):204--207.Zhao G J. Nano-dimensions in wood, nano-wood, wood and inorganic nano-composites[J]. Journal of Beijing Forestry University,2002,24(Suppl. 1):204-207.
[8]郭伟,牛晓霆,李伟,等.纳米ZnO改性蜂蜡处理缅甸花梨木材表面性能[J].北京林业大学学报,2016,38(2):113--119.Guo W,Niu X T,Li W,et al. Surface properties of Bruma rosewood polished using beewax modified by nano-ZnO[J].Journal of Beijing Forestry University,2016,38(2):113-119.
[9]江泽慧,孙丰波,余雁,等.竹材的纳米Ti O2改性及防光变色性能[J].林业科学,2010,46(2):116--121.Jiang Z H,Sun F B,Yu Y,et al. Modification of nano Ti O2on bamboo and its anti-photodiscoloration performance[J]. Scientia Silvae Sinicae,2010,46(2):116-121.
[10]王佳贺.纳米氧化铜与纳米氧化锌复合防腐剂制备及木材防腐性能研究[D].哈尔滨:东北林业大学,2013.Wang J H. Nano copper oxide and nano Zinc oxide composite material preparation and wood preservation performance study[D]. Harbin:Northeast Forestry University,2013.
[11]高鹤,梁大鑫,李坚,等.纳米Ti O2-ZnO二元负载木材的制备及性质[J].高等学校化学学报,2016,37(6):1075--1081.Gao H,Liang D X,Li J,et al. Preparation and properties of nano Ti O2-ZnO binary collaborative wood[J]. Chemical Journal of Chinese Universities,2016,37(6):1075-1081.
[12]孙丽丽.新型化学镀法制备木质电磁屏蔽材料的研究[D].哈尔滨:东北林业大学,2013.Sun L L. Study on the preparation of wood-based electromagnetic shielding material via novel electroless plating methods[D].Harbin:Northeast Forestry University,2013.
[13]彭琎,陈广琦,宋宜驰,等.聚酰亚胺柔性基底上磁控溅射金属铜膜的电学性能研究[J].物理学报,2014,63(13):138101.Peng J, Chen G Q, Song Y C, et al. Study on electrical performance of metal copper films deposited by magnetron sputtering on polyimide flexible substrates[J]. Acta Physica Sinica,2014,63(13):138101.
[14] Segal L,Creely J J,Martin Jr A E,et al. An empirical method for estimating the degree of crystallinity of native cellulose using the Xray diffractometer[J]. Textile Research Journal,1959,29(10):786--794.
[15] Mwaikambo L Y,Ansell M P. Chemical modification of hemp,sisal,jute, and kapok fibers by alkalization[J]. Journal of Applied Polymer Science,2002,84(12):2222-2234.
[16] Zhang P P,Tong D S,Lin C X,et al. Effects of acid treatments on bamboo cellulose nanocrystals[J]. Asia-Pacific Journal of Chemical Engineering,2014,9(5):686--695.
[17] Oliver W C,Pharr G M. An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments[J]. Journal of Materials Research,1992,7(6):1564--1583.
[18]徐垚,王占山,徐敬,等.用X射线反射测量法表征双层结构中低原子序数材料的特性[J].光学精密工程,2007,15(12):1838-1843.Xu Y,Wang Z S,Xu J,et al. Characterization of low-Z material layer profiles in bilayer structures by X-ray reflectivity measurement[J]. Optics and Precision Engineering,2007,15(12):1838--1843.
[19]吕文华,赵广杰.杉木木材/蒙脱土纳米复合材料的结构和表征[J].北京林业大学学报,2007,29(1):131--135.LüW H, Zhao G J. Structure and characterization of Cunninghamia lanceolata wood-MMT inter-calation nanocomposite(WMNC)[J]. Journal of Beijing Forestry University,2007,29(1):131--135.
[20]彭晓瑞,张占宽.等离子体处理对6种木材表面润湿性能的影响[J].林业科学,2018,54(1):90-98.Peng X R,Zhang Z K. Influence of plasma treatment on six kinds of wood surface wettability[J]. Scientia Silvae Sinicae,2018,54(1):90-98.
[21]程瑞香,顾继友.落叶松、桦木和柞木木材表面的润湿性[J].东北林业大学学报,2002,30(3):29-31.Cheng R X,Gu J Y. Wettability of larch,birch and oak[J].Journal of Northeast Forestry University,2002,30(3):29--31.