Effect of nano-hydroxyapatite micromorphology on the properties and stability of superhydrophobic layers of wood
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摘要: 对木材表面进行超疏水改性是降低木材干缩湿胀，延长木制品使用寿命的一种有效手段，但木材表面超疏水改性的实际应用受限于涂层较差的稳定性。木材表面超疏水层中无机纳米粒子的微观形貌是影响其稳定性的重要因素，然而鲜有文章对此进行系统探讨。本文以纳米球、纳米棒及纳米线三种形貌的羟基磷灰石为原料，通过与聚二甲基硅氧烷复合并喷涂到木材表面的方法对木材表面进行超疏水改性，通过砂纸磨损、胶带剥离及化学腐蚀等破坏涂层的方法来探究羟基磷灰石的形貌对木材表面超疏水层稳定性的影响规律。结果表明，由于羟基磷灰石纳米球有着更小的长径比及尺寸，可更有效地进入到木材的细胞壁及细胞腔中，因而由羟基磷灰石纳米球制备而成的木材超疏水层具有更优异的疏水性及稳定性,在砂纸磨损和胶带剥离循环15次后，仍能保持超疏水性。这些研究结果可为高性能且长效稳定木材超疏水涂层的研制提供理论基础。Abstract: Superhydrophobic modification of wood surfaces can effectively limit the shrinkage and swelling of wood, thereby extending the service life of wood products. However, the practical application of superhydrophobic modification of wood surfaces is limited due to the poor stability of the superhydrophobic coating. The stability of the superhydrophobic coating is affected by the microscopic morphology of inorganic nanoparticles in the wood superhydrophobic layer. However, few research has systematically discussed this issue. In this paper, three types of hydroxyapatite nanomaterials (nanospheres, nanorods and nanowires), were used as raw materials for the superhydrophobic modification of wood surfaces by compounding with polydimethylsiloxane and spraying onto the wood surface. The effect of hydroxyapatite morphology on the stability of the superhydrophobic layer on wood was investigated through sandpaper wear, tape stripping, and chemical corrosion tests. The results demonstrate that hydroxyapatite nanospheres with smaller aspect ratios and sizes can efficiently penetrate the cellular walls and cavities of wood. As a result, the superhydrophobic layer prepared from these nanospheres exhibit better hydrophobicity and stability, and the obtained coatings can maintain superhydrophobicity after 15 cycles of sandpaper wearing and tape peeling. These findings provide a theoretical foundation for the development of high-performance and stable wood superhydrophobic coatings.
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Key words:
- wood /
- superhydrophobic modification /
- hydroxyapatite /
- microscopic morphology /
- stability
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图 1 木材表面超疏水层的制备示意图
Figure 1. Schematic of the preparation of superhydrophobic coating on wood surface
图 2 三种羟基磷灰石纳米材料的微观形貌：(a1和a2)羟基磷灰石纳米线；(b1和b2)羟基磷灰石纳米棒；(c1和c2)羟基磷灰石纳米球
Figure 2. Microstructure of three kinds of hydroxyapatite materials: (a1 and a2) hydroxyapatite nanowires; (b1 and b2) hydroxyapatite nanorods; (c1 and c2) hydroxyapatite nanospheres
图 3 (a)不同形貌HAP的XRD衍射图谱；(b)修饰不同疏水层后木材样品的FTIR谱图
Figure 3. (a) XRD pattern of HAP materials with different morphologies; (b) FTIR spectra of natural wood and different samples after modified with different hydrophobic coatings
图 4 (a, b)修饰不同表面涂层前后木材样品的外观及表面润湿性；(c-f)修饰不同表面涂层后木材样品的静态水接触角图像：(c) W-P-W;(d) R-P-W; (e) S-P-W; (f) P-W
Figure 4. (a, b) The appearance and wettability of wood samples before and after modified with different surface coatings; (c-f) The water contact angle pictures of different samples after modified with different surface coatings: (c) W-P-W; (d) R-P-W; (e) S-P-W; (f) P-W
图 5 表面润湿性的基本模型:(a)杨氏方程模型；(b) Wenzel状态；(c) Cassie-Baxter状态
Figure 5. Model of Surface wettability: (a) Young’s model; (b) Wenzel state; (c) Cassie-Baxter state
图 6 修饰相应涂层后木材样品表面的三维轮廓图：(a) W-P-W；(b) R-P-W；(c) S-P-W
Figure 6. 3 D outline diagram of different wood samples after modified with different coatings: (a) W-P-W; (b) R-P-W; (c) S-P-W
图 7 修饰相应涂层后木材样品表面的SEM图像：(a) P-W; (b) W-P-W; (c) R-P-W; (d) S-P-W
Figure 7. The SEM pictures of different wood samples after modified with different coatings: (a) P-W; (b) W-P-W; (c) R-P-W; (d) S-P-W
图 8 (a, b)木材表面超疏水层在砂纸磨损过程中的水接触角变化及变化率；(c-f)不同木材超疏水层在经砂纸磨损后的微观形貌：(c) W-P-W；(d) R-P-W；(e) S-P-W；(f) P-W
Figure 8. (a, b) Change and change rate of water contact angle of wood coating after sandpaper wear tests; (c-f) The morphologies of different superhydrophobic layers of wood after being worn by sandpaper: (c) W-P-W; (d) R-P-W; (e) S-P-W; (f) P-W
图 9 (a, b)木材表面超疏水层在胶带剥离过程中的水接触角变化及变化率；(c-f)不同木材超疏水层在经胶带剥离后的微观形貌：(c) W-P-W；(d) R-P-W；(e) S-P-W；(f) P-W
Figure 9. (a, b) Change and change rate of water contact angle of wood coating after tape peeling tests; (c-f) The morphologies of different superhydrophobic layers of wood after being worn by tape peeling: (c) W-P-W; (d) R-P-W; (e) S-P-W; (f) P-W
图 10 S-P-W样品遭受不同损伤后的FTIR谱图：(a)砂纸磨损；(b)化学腐蚀
Figure 10. The FTIR spectra of S-P-W after different kinds of damage: (a) Sandpaper; (b) Chemical corrosion
图 11 腐蚀性液滴在木材涂层上的接触角随时间的变化情况及其变化率：(a, d) pH=1的盐酸溶液；(b, e) pH=13的氢氧化钠溶液；(c, f) 3.5wt%的氯化钠溶液
Figure 11. Change and change rate of contact angle of corrosive droplets on different superhydrophobic layers of wood: (a, d) HCl solution with pH value of 1; (b, e) NaOH solution with pH value of 13; (c, f) 3.5wt% NaCl solution
图 12 木材超疏水涂层的水接触角在高湿度条件下的变化情况
Figure 12. The water contact angle changes of wood with different superhydrophobic coating under high-humidity condition
表 1 不同样品的名称缩写
Table 1. Abbreviations of the names of different samples
Abbreviation Sample W-P-W Hydroxyapatite nanowire R-P-W Hydroxyapatite nanorod S-P-W Hydroxyapatite nanosphere P-W Without hydroxyapatite N-W Natural wood 
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