纳米TiO<sub>2</sub>对木纤维/聚丙烯复合材料抗紫外老化性能的影响

牟明明; 袁光明; 陈世尧

doi:10.13801/j.cnki.fhclxb.20190929.004

纳米TiO₂对木纤维/聚丙烯复合材料抗紫外老化性能的影响

doi: 10.13801/j.cnki.fhclxb.20190929.004

牟明明¹,
袁光明^{1, 2, ,},
陈世尧¹

1.
中南林业科技大学　材料科学与工程学院，长沙 410004
2.
“木竹资源高效利用”湖南省高校2011协同创新中心，长沙 410004

基金项目: 湖南省科技重大专项(2017NK1010)；国家自然科学基金面上项目（31770606）；国家林业公益性行业科研专项（201504503）

详细信息

通讯作者:
袁光明，教授，博士生导师，研究方向为生物质复合材料　E-mail：ygm@csuft.edu.cn

中图分类号: TB332
计量
- 文章访问数: 874
- HTML全文浏览量: 147
- PDF下载量: 57
- 被引次数: 0
出版历程
- 收稿日期: 2019-06-27
- 录用日期: 2019-08-27
- 网络出版日期: 2019-09-30
- 刊出日期: 2020-06-15

Effect of nano TiO₂ on UV aging resistance of wood fiber/polypropylene composites

1.
School of Materials Science and Engineering, Central South University of Forestry and Technology, Changsha 410004, China
2.
Hu'nan Collaborative Innovation Center for Effective Utilizing of Wood & Bamboo Resource, Changsha 410004, China

摘要

摘要: 木塑复合材料作为室外建筑装饰材料时，暴露在紫外光的照射下,易老化导致其力学性能降低、使用寿命减少。将具有高效紫外线屏蔽能力的金红石型纳米TiO₂经硅烷偶联剂KH-570表面改性后，与木纤维(WF)、聚丙烯(PP)等制备了TiO₂-WF/PP复合材料。对TiO₂-WF/PP复合材料进行了人工加速紫外老化，并利用FTIR、TG、SEM、力学性能分析、颜色变化分析等手段，探究了纳米TiO₂对WF/PP复合材料抗紫外老化的影响。结果表明：改性纳米TiO₂粒子在WF/PP复合材料中均匀分散，无明显团聚，且其加入显著提高了复合材料的热稳定性；TiO₂-WF/PP复合材料随着老化时间的延长，力学性能下降相对较小且颜色变化较小。当纳米TiO₂的质量分数为2 wt%~3 wt%，老化2 000 h时后，TiO₂-WF/PP复合材料的拉伸强度、冲击强度仅分别下降10.0%和12.6%；未加入纳米TiO₂颗粒的WF/PP复合材料，则分别下降20.2%和22.6%。
- 纳米TiO₂ /
- 木纤维(WF) /
- 聚丙烯(PP) /
- 复合材料 /
- 抗紫外老化 /
- 表面改性
Abstract: When wood-plastic composites are used as outdoor building decoration materials, they are exposed to ultraviolet light, resulting in mechanical properties and service life reducing. The rutile nano TiO₂ with high-efficiency ultraviolet shielding ability was surface-modified with a silane coupling agent KH-570, and then TiO₂-WF/PP composites were prepared with wood fiber (WF), polypropylene (PP). The artificial accelerated UV aging of the composites was carried out. The effects of nano TiO₂ on the UV aging of WF/PP composites were investigated by means of FTIR, TG, SEM, mechanical properties analysis and color change analysis. The results show that the modified nano TiO₂ particles can be uniformly dispersed in WF/PP composites without obvious agglomeration, and their addition significantly improves the thermal stability of the composites; with the aging time prolonged, the decrease of the mechanical properties of WF/PP composites is relatively small and the color change scope is small. When the mass fraction of nano TiO₂ particles is 2 wt%-3 wt% and aging for 2 000 h, the tensile strength and impact strength of the TiO₂-WF/PP composites only decrease by 10.0% and 12.6%, respectively, while those without the addition of nano TiO₂ particles decrease by 20.2% and 22.6%, respectively.
- nano TiO₂ /
- wood fiber(WF) /
- polypropylene(PP) /
- composites /
- surface modification /
- anti-ultraviolet aging

HTML全文

图 1 纳米TiO₂的粒径分布

Figure 1. Particle diameter distribution of nano TiO₂

下载: 全尺寸图片幻灯片

图 2 纳米TiO₂的FTIR图谱

Figure 2. FTIR spectra of nano TiO₂

下载: 全尺寸图片幻灯片

图 3 硅烷偶联剂KH-570表面改性纳米TiO₂的机制

Figure 3. Mechanism of surface modification on nano TiO₂ by silane coupling agent KH-570

下载: 全尺寸图片幻灯片

图 4 改性前后纳米TiO₂的SEM图像

Figure 4. SEM images of nano TiO₂before and after modification

下载: 全尺寸图片幻灯片

图 5 TiO₂-WF/PP复合材料紫外加速老化后力学强度变化

Figure 5. Mechanical strength changes of TiO₂-WF/PP composites after ultraviolet-accelerated aging

下载: 全尺寸图片幻灯片

图 6 TiO₂-WF/PP复合材料老化后的SEM图像

Figure 6. SEM images of TiO₂-WF/PP composites after aging

下载: 全尺寸图片幻灯片

图 7 TiO₂-WF/PP复合材料断面的SEM图像

Figure 7. SEM images of fracture surface of TiO₂-WF/PP composites

下载: 全尺寸图片幻灯片

图 8 TiO₂的能谱分析

Figure 8. Energy spectrum analysis of TiO₂

下载: 全尺寸图片幻灯片

图 9 TiO₂-WF/PP复合材料的FTIR图谱

Figure 9. FTIR spectra of TiO₂-WF/PP composites

下载: 全尺寸图片幻灯片

图 10 TiO₂-WF/PP复合材料表面颜色随老化时间的变化

Figure 10. Surface color change of TiO₂-WF/PP composites with aging time

下载: 全尺寸图片幻灯片

图 11 未添加和添加TiO₂的WF/PP复合材料老化1 500 h后表面颜色变化

Figure 11. Surface color change of WF/PP composites without and with TiO₂ after aging for 1 500 h

下载: 全尺寸图片幻灯片

图 12 TiO₂-WF/PP复合材料的TG曲线

Figure 12. TG curves of TiO₂-WF/PP composites

下载: 全尺寸图片幻灯片

表 1 TiO₂-木质纤维/聚丙烯（TiO₂-WF/PP）复合材料的主要成分

Table 1. Ingredients for TiO₂-wood fiber/polypropulene(TiO₂-WF/PP) composites

Sample Modified TiO₂/wt% WF/wt% PP/wt% ZnO/wt% CaCO₃/wt% Stabilizer/wt%

0 0 29 66.5 0.5 3 1
1 1 29 65.5 0.5 3 1
2 2 29 64.5 0.5 3 1
3 3 29 63.5 0.5 3 1
4 4 29 62.5 0.5 3 1
5 5 29 61.5 0.5 3 1

下载: 导出CSV

参考文献(26)

[1]	杨青, 张宝华, 毛志平, 等. 聚丙烯/改性纳米二氧化钛复合材料的制备与性能[J]. 高分子材料科学与工程, 2009, 25(1):48-51. doi: 10.3321/j.issn:1000-7555.2009.01.014 YANG Qing, ZHANG Baohua, MAO Zhiping, et al. Preparation and properties of polypropylene/modified nanometer titania composite[J]. Polymer Materials Science and Engineering,2009,25(1):48-51(in Chinese). doi: 10.3321/j.issn:1000-7555.2009.01.014
[2]	冷李超, 张元明, 韩光亭, 等. 不同受阻胺光稳定剂改性聚丙烯耐光老化性能研究[J]. 应用化工, 2014(5):864-867. LENG Lichao, ZHANG Yuanming, HAN Guangting, et al. Study on photoaging resistance of polypropylene modified with different blocking amine light stabilizers[J]. Applied Chemistry,2014(5):864-867(in Chinese).
[3]	李正印, 王伟宏. 高木材纤维含量聚丙烯基复合材料的制备及其性能[J]. 林业工程学报, 2017, 2(2):9-15. LI Zhengyin, WANG Weihong. Preparation and properties of polypropylene based composites with high wood fibers content[J]. Journal of Forestry Engineering,2017,2(2):9-15(in Chinese).
[4]	侯人鸾, 何春霞, 薛娇, 等. 小麦秸秆/PP复合材料的紫外线加速老化性能[J]. 复合材料学报, 2013, 30(5):86-93. doi: 10.3969/j.issn.1000-3851.2013.05.014 HOU Renluan, HE Chunxia, XUE Jiao, et al. UV accelerated ageing properties of wheat straw/PP wood plastic compo-site[J]. Acta Materiae Compositae Sinica,2013,30(5):86-93(in Chinese). doi: 10.3969/j.issn.1000-3851.2013.05.014
[5]	WEN Jiuqing, LI Xin, LIU Wei. Photocatalysis fundamentals and surface modification of TiO₂ nanomaterials[J]. Chinese Journal of Catalysis,2015,12(36):2049-2070.
[6]	薛娇, 何春霞, 侯人鸾, 等. 百菌清对麦秸秆/PP复合材料耐腐蚀性能的影响[J]. 合成材料老化与应用, 2013, 42(1):6-10. doi: 10.3969/j.issn.1671-5381.2013.01.002 XUE Jiao, HE Chunxia, HOU Renluan, et al. Effects of chlorothalonil on corrosion resistance of wheat straw/PP composites[J]. Synthetic Materials Aging and Appliction,2013,42(1):6-10(in Chinese). doi: 10.3969/j.issn.1671-5381.2013.01.002
[7]	杨守禄, 李丹, 吴义强, 等. 木塑复合材料功能化改性研究进展[J]. 材料导报, 2018, 32(9):3090-3098. YANG Shoulu, LI Dan, WU Yiqiang, et al. Research progress on functional modification of WPC composites[J]. Materials Review,2018,32(9):3090-3098(in Chinese).
[8]	左迎峰, 李文豪, 李萍, 等. 竹纤维/聚乳酸可降解复合材料的增塑改性[J]. 林业工程学报, 2018, 3(1):77-82. ZUO Yingfeng, LI Wenhao, LI Ping, et al. Plastication of bamboo fiber/polylactic acid degradeable composite[J]. Journal of Forestry Engineering,2018,3(1):77-82(in Chinese).
[9]	付自政. HDPE/木粉复合材料的制备及其紫外加速老化性能研究[D]. 武汉: 华中农业大学, 2009. FU Zizheng. Preparation of HDPE/wood flour composite and its UV accelerated aging properties[D]. Wuhan: Huazhong Agricultural University, 2009(in Chinese).
[10]	徐兵, 梅长彤, 刘朝政, 等. 光稳定剂复配对核壳WPC抗紫外老化性能的影响[J]. 工程塑料应用, 2017, 45(4):17-23. doi: 10.3969/j.issn.1001-3539.2017.04.004 XU Bing, MEI Changtong, LIU Zhaozheng, et al. Effect of photostabilizer on anti-ultraviolet aging properties of nuclear WPC[J]. Engineering Plastics Application,2017,45(4):17-23(in Chinese). doi: 10.3969/j.issn.1001-3539.2017.04.004
[11]	ALLEN N S, MCINTYRE R, KERROD J M, et al. Photo-stabilisation and UV blocking efficacy of coated macro and nano-rutile titanium dioxide particles in paints and coatings[J]. Journal of Polymers and the Environment,2018,26(11):4243-4257. doi: 10.1007/s10924-018-1298-0
[12]	REDHWI H H, SIDDIQUI M N, ANDRADY A L, et al. Weatherability of conventional composite and nano-composites of PVC and rutile Titanium Dioxide[J]. Polymer Composites,2018,39(6):2135-2141. doi: 10.1002/pc.24176
[13]	LI C, CHANG S J, TAI M Y. Surface chemistry and dispersion property of TiO₂ nano particles[J]. Journal of the American Ceramic Society,2010,93(12):4008-4010. doi: 10.1111/j.1551-2916.2010.04222.x
[14]	潘其维, 王兵兵, 陈朝晖. 表面接枝防老剂的白炭黑在天然橡胶中的应用[J]. 复合材料学报, 2013, 30(5):1-8. doi: 10.3969/j.issn.1000-3851.2013.05.001 PAN Qiwei, WANG Bingbing, CHEN Zhaohui, et al. Application of antioxidant functionalized silicas in natural rubber[J]. Acta Material Composite Sinica,2013,30(5):1-8(in Chinese). doi: 10.3969/j.issn.1000-3851.2013.05.001
[15]	郭刚, 于杰, 罗筑, 等. 聚丙烯/纳米级金红石型二氧化钛/聚烯烃弹性体复合材料的抗老化性能研究[J]. 高分子学报, 2006(2):119-224. GUO Gang, YU Jie, LUO Zhu, et al. Study on ageing resistance of polyp-ropyene/nano scale rutile titanium dioxide/poepolyolefin elastomer composites[J]. Acta Polymerica Sinica,2006(2):119-224(in Chinese).
[16]	DEVI R R, GOGOI K, KONWAR B K, et al. Synergistic effect of nanoTiO₂ and nanoclay on mechanical, flame retard ancy, UV stability, and antibacterial propertie of wood polymer composites[J]. Polymer Bulletin,2013,70(4):1397-1413. doi: 10.1007/s00289-013-0928-x
[17]	DU H, WANG W, WANG Q, et al. Effects of pigments on the UV degradation of wood-flour/HDPE composites[J]. Journal of Applied Polymer Science,2010,118(2):1068-1076.
[18]	American Society for Testing and Materials International. Standard test method for tensile properties of plastic: ASTM D638—03[S]. West Conshohocken: ASTMInternational, 2015.
[19]	中华人民共和国国家质量监督检验检疫总局.塑料.简支梁冲击性能的测定I:非仪器化冲击试验: GB/T1043.1—2008 [S]. 北京: 中国标准出版社, 2009. Administration of Quality Supervision, Inspection and Quarantine of the People's Republic of China. Plastics. Plastics: Determination of impact performance part1: General principles: GB/T 1040.1-2008[S]. Beijing: China Standards Press, 2009(in Chinese).
[20]	American Society for Testing and Materials International. Standard properties for calculation of color tolerances and color differences from instrumentally measured color coordinates: ASTM D 2244[S]. West Conshohocken: ASTM International, 2007.
[21]	郝喜海, 李慧敏, 李菲, 等. 纳米二氧化钛的表面改性研究[J]. 无机盐工业, 2012, 44(1):30-33. doi: 10.3969/j.issn.1006-4990.2012.01.009 HAO Xihai, LI Huimin, LI Fei, et al. Study on surface modification of nano-sized titania[J]. Iinorganic Chemicals Industry,2012,44(1):30-33(in Chinese). doi: 10.3969/j.issn.1006-4990.2012.01.009
[22]	贺超峰, 曹新鑫, 孙得翔, 等. 紫外光老化TiO₂/聚丙烯复合材料的热降解行为[J]. 高分子材料科学与工程, 2015, 31(7):92-95. HE Chaofeng, CAO Xinxin, SUN Dexiang, et al. Thermal degradation behavior of TiO₂/polypropylene composites after UV aging[J]. Polymer Materials Science&Engineering,2015,31(7):92-95(in Chinese).
[23]	李永峰, 刘一星, 于海鹏, 等. 甲基丙烯酸缩水甘油酯改善木塑复合材料性能[J]. 复合材料学报, 2009, 26(5):1-7. doi: 10.3321/j.issn:1000-3851.2009.05.001 LI Yongfeng, LIU Yixing, YU Haipeng, et al. Property improvement of wood polymer composites with glycidyl methacrylate[J]. Acta Materiae Compositae Sinica,2009,26(5):1-7(in Chinese). doi: 10.3321/j.issn:1000-3851.2009.05.001
[24]	王宣博, 陈小丹, 陈佳伟, 等. 纳米TiO₂含量对PVC/稻壳粉木塑复合材料性能的影响[J]. 工程塑料应用, 2016(7):31-36. doi: 10.3969/j.issn.1001-3539.2016.07.006 WANG Xuanbo, CHEN Xiaodan, CHEN Jiawei, et al. Effect of nano-TiO₂ content on properties of PVC/rice-shell wood-plastic composites[J]. Engineering Plastics Application,2016(7):31-36(in Chinese). doi: 10.3969/j.issn.1001-3539.2016.07.006
[25]	周箭, 张启龙, 杨辉, 等. 抗紫外PV DF基木塑复合材料的热分析[J]. 材料科学与工程学报, 2009, 27(6):845-849. ZHOU Jian, ZHANG Qilong, YANG Hui, et al. Thermal analysis of anti-ultraviolet poly(vinylidene fluoride)/wood flour composites[J]. Journal of Materiaks Science and Engineering,2009,27(6):845-849(in Chinese).
[26]	付菁菁, 何春霞, 常萧楠, 等. 麦秸秆/聚丙烯发泡复合材料的热稳定性与微观结构[J]. 复合材料学报, 2016, 33(3):469-476. FU Jingjing, HE Chunxia, CHANG Xiaonan, et al. Thermostability and microstructure of wheat straw/polypropylene foamed composites[J]. Acta Materiae Compositae Sinica,2016,33(3):469-476(in Chinese).