基于聚多巴胺的超疏水棉织物的一锅法制备及其油水分离性能

doi:10.11901/1005.3093.2021.103

基于聚多巴胺的超疏水棉织物的一锅法制备及其油水分离性能

张红亮, 赵国庆, 欧军飞^,, Amirfazli Alidad

江苏理工学院材料工程学院常州 213000

Superhydrophobic Cotton Fabric Based on Polydopamine via Simple One-Pot Immersion for Oil Water Separation

ZHANG Hongliang, ZHAO Guoqing, OU Junfei^,, Amirfazli Alidad

School of Materials Engineering, Jiangsu University of Technology, Changzhou 213000, China

通讯作者: 欧军飞，教授，oujunfei_1982@163.com，研究方向为表面功能材料

收稿日期: 2021-01-19 修回日期: 2021-05-14

基金资助:

国家自然科学基金. 52073127
常州市科技计划. CM20-193004. CZ20190020

Corresponding authors: OU Junfei, Tel:(0519)86953280, E-mail:oujunfei_1982@163.com

Received: 2021-01-19 Revised: 2021-05-14

作者简介 About authors

张红亮，男，1996年，硕士生

摘要

将棉织物浸入多巴胺、硝酸银、十六烷基三甲氧基硅烷的乙醇溶液中，取出烘干制备出超疏水棉织物。用扫描电子显微镜和X射线光电子能谱表征其表面形貌和元素，用接触角测量仪测量其接触角并进行摩擦或液体浸泡(如酸、碱、沸水)实验检测其耐用性。结果表明，聚多巴胺的强附着性使原位生成的银纳米粒子能经受摩擦或不同液体的浸泡，从而使超疏水织物具有良好的耐用性。超疏水棉织物还具有良好的油水分离性能，其油水分离效率高达97%，油流量最高可达15.93 m³·m^-2·h^-1。

关键词： 材料表面与界面 ; 荷叶效应 ; 贻贝效应 ; 耐用性 ; 废水处理

Abstract

Superhydrophobic fabric was fabricated by dipping the cotton fabric into ethanol solution of dopamine, silver nitrate and hexdecyltrimethoxysilane followed by bakingdry, and of which the surface morphology and chemical composition were characterized by scanning electron microscope and x-ray photoelectron spectroscope, respectively. Surface wettability was measured by contact angle meter. Durability was assessed by abrasion or immersion in different aqueous solutions of acid, alkali, or boiling water. Results show that the in-situ-generated Ag particles were retained after abrasion or immersion test due to the high adhesion of polydopamine; thus, the so-obtained superhydrophobic fabric possessed good durability. Moreover, the superhydrophobic fabric showed good oil-water separation performance with oil-water separation efficiency up to 97% and oil flow up to 15.93 m³·m^-2·h^-1.

Keywords： surface and interface in the materials ; lotus effect ; mussel effect ; durability ; wastewater treatment

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张红亮, 赵国庆, 欧军飞, Amirfazli Alidad. 基于聚多巴胺的超疏水棉织物的一锅法制备及其油水分离性能. 材料研究学报[J], 2022, 36(2): 114-122 DOI:10.11901/1005.3093.2021.103

ZHANG Hongliang, ZHAO Guoqing, OU Junfei, Amirfazli Alidad. Superhydrophobic Cotton Fabric Based on Polydopamine via Simple One-Pot Immersion for Oil Water Separation. Chinese Journal of Materials Research[J], 2022, 36(2): 114-122 DOI:10.11901/1005.3093.2021.103

海上泄露的石油和工业排放的含油废水，使环境严重污染^[1]。传统的油水分离方法，如重力分离^[2]、絮凝^[3]、浮选^[4]、吸收剂^[5]和气浮分离法等，成本高、分离效率低且不可回收而造成二次污染。因此，急需简单、低成本和高效率的油水分离方法。

超疏水材料是受荷叶启发而发展起来的一类表面功能材料，可应用在自清洁、防雾、防冰、防腐蚀和油水分离等领域。可制备超疏水油水分离材料基材的多孔材料，有金属网格、海绵和棉织物等^[6~12]。Cao等^[9]用电沉积和浸渍方法制备的层状结构超疏水超亲油铜网，其油水分离效率高于90%。Liu等^[10]用简单浸泡和硬脂酸改性制备的超疏水钢网，对油水混合物的分离效果良好。Wang等^[11]沉积被十六烷基三甲氧基硅烷包覆的二氧化硅颗粒制备的超疏水钢网，能高效分离油水且可重复使用。Mi等^[12]用自组装静电纺丝和煅烧法制备的超疏水二氧化硅纤维海绵，对各种油品的吸附率高达其重量的122倍，在恶劣环境下具有良好的稳定性且可重复使用。

虽然以金属网格和海绵为基底制备的超疏水材料分离油水的效率高，但是被油污损后难以清洗易造成二次污染。与金属网格和海绵相比，棉织物质地柔软、重量轻、成本低且可生物降解。Jiang等^[13]用交联聚合法在棉织物上制备的超疏水涂层，对各种油水混合物的分离效率高达99%以上。虽然超疏水棉织物的油水分离效率高，但是其耐久性还有待提高。贻贝具有极强的附着力。Lee等^[14]发现聚多巴胺具有类似贻贝分泌的蛋白结构和极强的粘附性，可粘附在各种有机无机表面。聚多巴胺结构中含有大量的羟基和氨基官能团，既可作为结合位点共价固定目标分子，也能通过氧化-还原反应或螯合作用与过渡金属离子结合制备出功能复合材料。因此，聚多巴胺可作为中间层在基材表面结合功能分子^[15,16]。基于这种特性，研究人员制备出一系列超疏水表面。Wang等^[17]将十六烷基三甲氧基硅烷分散在多巴胺水溶液中，制备出全水性涂料溶液。Yan等^[18]使用氧化剂(NaBO₃)使多巴胺快速聚合沉积到织物上，然后将十八胺经席夫碱反应接枝到织物上，制备出的超疏水织物在恶劣环境下具有良好的耐久性和稳定性，可重复用于油水分离。本文用一种更为简便的一锅法在织物表面自组装沉积多巴胺、纳米银和十六烷基三甲氧基硅烷，制备超疏水织物并研究其油水分离性能。

1 实验方法

1.1 实验用材料

棉织物(平均厚度0.54 mm，单位面积质量367.83 g/m²)。多巴胺盐酸盐(DA，98.5%)和三羟甲基氨基甲烷(TRIS，99.8%)。十六烷基三甲氧基硅烷(HDTMS，≥85%)。无水乙醇和硝酸银(AgNO₃，≥99.8%)。

1.2 超疏水棉织物制备

将棉织物(3 cm×3 cm)依次用无水乙醇、丙酮、去离子水超声清洗5 min，烘干后备用。将一定量的DA、AgNO₃装到50 mL无水乙醇中使其浓度分别为2n mg/mL和1.6n mg/mL(n=1~5，如表1所示)；用Tris-HCl将溶液的pH值调到8.5后加入HDTMS(100 μL)，超声振荡得到混合溶液。将预处理后的棉织物浸入混合溶液中5 min，取出后在100℃烘箱中烘干。将上述“浸泡-烘干”过程循环m次，最后在乙醇中超声清洗5 min。经上述样品记为TF-nC-mC(TF代表Treated fabric；第一个C代表Concentration；第二个C代表Cycles)，详见表1。

表1 用于制备TF-nC-mC样品的多巴胺和硝酸银的浓度

Table 1 Concentration of dopamine (DA) and AgNO₃ for the TF-nC-mC sample (mg·mL^-1)

Solute	n=1	n=2	n=3	n=4	n=5
DA	2.0	4.0	6.0	8.0	10.0
AgNO₃	1.6	3.2	4.8	6.4	8.0

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1.3 性能表征

用接触角测量仪(Krüss，DSA30)测量样品的润湿性，液滴的体积为10 μL；滚动角测量参考文献[19]；用场发射扫描电子显微镜(Regulus8100型，FE-SEM，Nova Nano SEM，FEI)观察样品的表面形貌；用X射线光电子能谱仪(PHI-5702型，XPS)分析样品的表面组成，以空气中的污染碳(C 1s：284.8 eV)为基准，校准结合能。

耐用性测量：将样品浸入不同的液体(如pH=1的HCl水溶液、pH=12的NaOH水溶液、恒温沸水)中，测试超疏水织物的耐化学稳定性。将超疏水织物样品浸入乙醇中进行超声清洗(180 W，40 kHz)，测试其机械稳定性；用摩擦色牢度仪(Y571M)进行摩擦测试，摩擦对偶为未处理的棉织物，载荷为45 kPa，往复行程为104 mm(1个循环)，频率为每分钟60个循环。用加速水洗机(GSX-8)测试耐水洗性能，测试标准为AATCC试验方法61-2007标准，实验条件为1B(洗涤温度32℃，10个标准不锈钢钢球，0.37%洗衣粉，每个循环20 min)，一次加速洗涤相当于5次商业或家庭洗涤。

油水分离测试：将油水混合物倒入油水分离装置在重力作用下分离，分离膜为超疏水织物。油水分离效率为

e = \frac{v (m L)}{50 (m L)} \times 100 %

(1)

油流量为

j = \frac{v}{A \times t}

(2)

其中v、A和t分别为收集油的体积、超疏水织物的有效面积和油水分离时间。

2 结果和讨论

2.1 表面湿润性、表面形貌和表面成分

未处理的原始棉织物亲水性极强，水滴一接触立刻被吸收。棉织物的这种超亲水性，与其化学成分和粗糙结构等因素密切相关。棉纤维是由D-葡萄糖(β型)单元经过1-4苷键互相连接聚合而成的直链天然高分子化合物，分子链中含有大量的羟基。棉纤维表面的亲水羟基(图1a)使其本征接触角小于90°。另一方面，由棉纤维加工成的棉织物具有纺织粗糙结构。根据Wenzel润湿公式 $c o s θ_{W} = r c o s θ_{Y}$ ^[20](其中θ_Y为棉纤维的本征接触角，r为大于1的粗糙度因子，θ_W为表观接触角)，粗糙的本征亲水表面使表观接触角降低。同时，纤维间的疏松多孔结构(图1a)产生的毛细作用使织物的亲水性进一步提高。总之，棉织物的超亲水性是表面亲水羟基、纺织粗糙结构和纤维间疏松多孔的结构所致。

图1

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图1 TF-nC-mC的制备原理图、原始棉织物的微观形貌图、TF-nC-mC样品的微观形貌随着浓度系数n和沉积循环次数m的变化

Fig.1 Preparation schematic (a), SEM images for original cotton fabric (b) and (c) change of the TF-nC-mC samples with different values of concentration parameter n (m=5) and (d) immersion cycle m (n=3)

处理后，TF-nC-mC样品的疏水性增强(表2)，其浓度系数n和沉积循环次数m对样品的润湿性影响较大。当n=3，即溶液的浓度提高到基准浓度(DA：2 mg/mL、AgNO₃：1.6 mg/mL)的3倍时接触角滚动角均达到峰值。在表面疏水性方面，DA、AgNO₃的最佳溶液浓度分别为6 mg/mL、4.8 mg/mL。除了溶液的浓度，循环次数m对样品表面的润湿性也有主要的影响。循环次数m=1时TF-3C-1C样品就具有一定的吸水性，m增大到2使样品的接触角急剧增大到144.8°，当m增大到3时接触角约为160°，但是当m进一步增大到4、5时接触角不再增大。

表2 TF-nC-mC样品表面润湿性与浓度倍数n和沉积循环次数m的关系

Table 2 Surface wettability for the TF-nC-mC sample with different concentration parameter n and immersion cycle m

	TF-nC-5C		TF-3C-mC
	Contact angle/(°)	Sliding angle/(°)	Contact angle/(°)	Sliding angle/(°)
n=1	153.8±1.7	15±1.6	-	-
n=2	159.2±1.8	9±1.1	-	-
n=3	161.3±1.9	5±1.8	-	-
n=4	159.7±1.6	8±1.2	-	-
n=5	150.1±1.8	12±1.3	-	-
m=1	-	-	0	-
m=2	-	-	144.8±1.5	23±1.6
m=3	-	-	160.3±1.9	6±1.8
m=4	-	-	160.8±1.4	6±1.3
m=5	-	-	161.2±1.3	5±1.4

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影响表面润湿性的一个重要因素，是表面形貌。为了解释不同TF-nC-mC样品的表面润湿性，图1总结了不同样品的微观形貌。可以看出，原棉纤维的表面光洁、平滑且无明显颗粒物，只有一些天然纹理(图1b3)。TF-nC-5C样品的沉积浓度系数n对表面形貌的影响较大。n=1的样品，其表面有零星的沉积物；n=3的样品，表面的沉积物增多，并与棉纤维的微米结构构筑出多级粗糙结构；n=5的样品，表面的沉积物进一步增多，织物的纤维结构被覆盖使结构的粗糙度降低。这表明，n=3是最佳的沉积浓度参数，n=3的样品表面的粗糙结构最有利于产生超疏水性。对于TF-3C-mC样品，沉积循环m是影响表面形貌的主要因素。与图1d2相比，图1d1中样品的表面只有少许沉积物，大部分表面呈现出棉织物原本的微观形貌，这正是循环一次样品亲水的原因。随着循环次数的增加其表面粗糙度所致提高，使接触角增大。

为了明确沉积物的化学成分，对处理前后的棉织物进行了XPS分析，结果如图2所示。可以看出，原始棉织物的XPS全谱(图2a)中有明显的C、O峰，TF-3C-5C样品多出了N、Ag、Si元素峰，分别源于前驱体溶液中的多巴胺、硝酸银和十六烷基三甲氧基硅烷。Ag3d的高分辨率图谱如图2b所示，可见谱线双峰中心分别对应结合能相距6 eV的367.5 eV和373.5 eV，与文献[21]中银单质的Ag3d峰吻合。多巴胺及其聚合产物聚多巴胺的邻苯二酚基团，对很多金属离子有较强的配位作用，且邻苯二酚基团氧化变成醌的同时能还原金属阳离子。因此，银离子在PDA表面原位还原并沉积于其上构成微糙结构。原始棉织物的C1s高分辨率谱，如图2c所示。根据C1s可拟合出结合能位于284.7 eV处的C-C/C-H峰(峰面积占55%)、结合能位于286.3 eV处的C-O峰(峰面积占30%)以及结合能位于287.8 eV处的C=O峰(峰面积占15%)。图2d中位于284.7 eV的峰强大大增大的原因，是HDTMS的加入使样品表面非极性碳的含量大大提高、表面极性降低和表面能降低。

图2

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图2 TF-3C-5C样品和原始棉织物的XPS全谱、Ag3d高分辨谱、原始棉织物的C1s高分辨谱以及TF-3C-5C样品的C1s高分辨谱

Fig.2 XPS spectra of different samples (a) survey spectrum of theTF-3C-5C sample, (b) Ag3d high resolution spectrum of theTF-3C-5C sample, (c) C1s high resolution spectrum of the pristine fabric and (d) C1s high resolution spectrum of the TF-3C-5C sample

2.2 耐用性

用不同方法评价超疏水织物的耐用性，测试后织物的表面形貌和化学成分，结果分列于图3和表3。测试后，织物出现不同程度的褪色；用色差仪定量分析测试前后织物的色差，可见超声清洗和加速洗涤后ΔE^*_ab值最大，样品显著褪色。其原因是，在超声清洗与加速洗涤过程中不仅存在强烈的机械作用(如超声过程中的空化作用、加速洗涤过程中的摩擦)，还存在化学作用(如乙醇、洗涤剂等对沉积物的洗脱)。同时，样品的抗碱液浸泡性不如抗酸性。其原因是，聚多巴胺是多巴胺溶液中的单体、氧化物、低聚物、高聚物通过非共价键力(电荷转移、π-π堆积和氢键)结合在一起。200次磨损测试后织物的接触角下降到130°，因为涂层发生严重的破坏，从图3f可清晰看到在织物纤维上留下的磨痕。对测试后样品的表面成分分析结果表明，测试后织物表面的N、Si、Ag元素含量均下降；N元素来源于聚多巴胺，Si元素来源于十六烷基三甲氧基硅烷，Ag元素来源于硝酸银。这表明，经物理化学冲击后织物表面的超疏水涂层被逐渐剥离。随着表面微观形貌和表面化学的改变，TF-3C-5C样品的疏水性也随着测试的进行而降低，如图4所示。通过与典型文献[20,22~28]的对比，可见其耐用性处于主流水平(表4)。

图3

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图3 超声波处理、清洗、沸水、碱、酸和磨损试验后表面形态的变化

Fig.3 Variation of surface morphology after (a) ultrasonicating, (b) laundering, (c) water boiling, (d) alkali, (e) acid, (f) abrading testing

表3 耐用性测试后样品的表面形貌、表面润湿性以及表面化学的变化

Table 3 Variation of surface morphology, surface wettability, and surface chemistry after testing

Testing	CA/(°)	ΔE^*_ab	N% (4.56)^&	Ag% (1.12)^&	Si% (5.35)^&
Ultrasonicating for 5 h	151.2±1.5	17.8	3.51	0.98	3.62
Laundering for 30 cycles	149.1±1.1	17.4	3.81	0.43	4.96
Water boiling for 72 h	149.8±1.3	15.4	4.28	0.84	4.41
Alkali soaking for 72 h	150.9±0.9	17.6	3.95	1.06	4.28
Acid soaking for 168 h	148.7±1.2	15.3	4.36	1.03	4.82
Abrading for 200 cycles	132.6±1.2	14.7	4.04	0.82	3.62

^&the data in the brackets are content of serface elements of the sample before treated measured by XPS

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图4

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图4 超疏水织物TF-3C-C的表面湿润性与超声清洗时间、加速洗涤次数、沸水处理时间碱液浸泡时间、酸液浸泡时间以及摩擦次数的关系

Fig.4 Variation of surface wettability for theTF-3C-5C sample against ultrasonication time (a), laundering cycles (b), water boiling time (c), alkali treating time (d), acid treating time (e), abrading cycles (f)

表4 TF-3C-5C超疏水织物的耐用性与文献值的对比

Table 4 Wettability variation for the TF-3C-5C sample and control samples in references

	SF-3C-5C	Comparison	Samples in reference	Ref.
Ultrasonic cleaning	CA=157.2° and SA=9° after 1 h in ethanol	>	CA varied from 159° to 150° after 1 h in ethanol	[22]
Ultrasonic cleaning	CA=157.2° and SA=9° after 1 h in ethanol	<	CA varied from 154° to 152° after 24 h in acetone	[23]

Laundering	CA=152° and SA=18° after 25 cycles	>	CA varied from 157° to 147° after 20 cycles	[20]
Laundering	CA=152° and SA=18° after 25 cycles	<	CA varied from 152° to ca. 150° after 100 cycles	[24]

Water Boiling	CA=152.2° and SA=18° after 48 h	>	CA varied to ca. 150° and SA increased to 15° after 35 min	[25]

Alkali Soaking	CA=153.2° and SA=14° after 48 h	>	CA varied from 156.3° to 152.2° after 48 h	[20]
Alkali Soaking	CA=153.2° and SA=14° after 48 h	>	CA varied from 156.9° to 151.6° after 48 h	[26]

Acid Soaking	CA>157.7° and SA=6° after 48 h	>	CA varied from 154.7° to 150.6° after 12 h CA varied from 156.9° to 142.3° after 24 h CA varied from 156.3° to 152.5° after 48 h	[27] [26] [20]

Abrading	CA=132.6° and SA<30° after 200 cycles	<	CA and SA remained almost unchanged after 200 cycles	[28]

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2.3 分离油水的性能

原始棉织物具有亲水亲油性，容易被油和水浸润，改性后的棉织物具有超疏水和超亲油特性。特殊的润湿性，使改性后的棉织物能吸附水中的油。如图5a所示，改性后的棉织物与油水混合物接触后能立即吸附漂浮在水面用红色染料染色的正己烷。吸附后，水面上没有残留的油渍。同时，还用密度高于水的氯仿测定了超疏水性织物的吸油性能。结果表明，将超疏水棉织物浸入水中后，水中的氯仿(红色染料染色)被完全吸收(图5b)。

图5

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图5 超疏水织物对正己烷(油红染色)和三氯甲烷(油红染色)的选择性吸附

Fig.5 Selective absorption of superhydrophobic cotton for cyclohexane (dyed with oil red ) in water (a) and trichloromethane (dyed with oil red ) in water (b)

用超疏水棉织物TF-3C-5C作为分离膜，将油水混合物倒入图6a所示的装置进行油水分离。使用氯仿(1.48 g/cm³)、二氯甲烷(1.33 g/cm³)、正己烷(0.66 g/cm³)、二甲苯(0.86 g/cm³)，可制成各种油水混合物。如果油的密度高于水，可将油水混合物直接倒入水中；若油的密度低于水，需将装置倾斜一定角度进行分离。用公式(1)和(2)可定量计算油水分离效率(图6b)和油通量(图6c)。结果表明，超疏水织物对上述油/水混合物的分离效率均高于96%，油通量大于13 m³·m^-2·h^-1。

图6

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图6 使用TF-3C-5C超疏水织物分离膜进行油水分离

Fig.6 Oil/water separation with the superhydrophobic filtration membrane of TF-3C-5C (a) setup, (b) separation efficiency for different oil/water mixtures, (c) flux of different oils penetrating through the superhydrophobic fabric, (d) variation of separation efficiency against separation cycle and (e) oil water emulsion separation

使用超疏水棉织物对二氯甲烷/水混合物进行20次油水分离实验，油水分离效率在96%上下波动(图6d)。Yao等^[29]合成的PC-a/SiO₂织物对由重力驱动的几种重油/水有优异的分离性能，油通量约为6.5~9.5 m³·m^-2·h^-1，分离效率均高于90%。Zheng等^[30]制备的碳纳米管导电超疏水织物，对三氯甲烷-水和正己水混合物的分离效率分别达到94.5%和94.8%；经过30次分离循环后，棉织物的分离效率仍高于90%。上述结果表明，这些超疏水织物对油水有较高的分离效率和可重复使用性。

同时，超疏水棉织物还可用于分离乳化油。将5 mL水和45 mL二氯甲烷混合后再加入乳化剂吐温，以2000 r/min的转读搅拌1 h，制备出乳白色乳化液。将乳化液倒入油水分离装置后油脂很快渗透过分离膜，水和乳化剂则留在容器上方，其分离效果如图6e所示。用微量水份测定仪GY106测定出，油/水乳液分离后的二氯甲烷的含水量为0.15 μg/mL。这表明，乳化油分离后油中只残存微量的水。

3 结论

用一锅浸渍法制备的超疏水棉织物疏水亲油，具有良好的机械性能、化学性能和稳定性，其接触角可达(163.5±1.5)°，滚动角为5°。这种超疏水棉织物对二氯甲烷、氯仿等油水混合物的分离效率均高于96%，油通量大于13 m³·m^-2·h^-1。这种超疏水棉织物对乳化液也有较高的分离性能，分离后的二氯甲烷含水量为0.15 μg/mL。

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... 海上泄露的石油和工业排放的含油废水，使环境严重污染^[1].传统的油水分离方法，如重力分离^[2]、絮凝^[3]、浮选^[4]、吸收剂^[5]和气浮分离法等，成本高、分离效率低且不可回收而造成二次污染.因此，急需简单、低成本和高效率的油水分离方法. ...

Superhydrophobic meshes that can repel hot water and strong corrosive liquids used for efficient gravity-driven oil/water separation

2016

Self-supporting superhydrophobic thin polymer sheets that mimic the nature's petal effect

2012

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2016

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2007

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2013

... 超疏水材料是受荷叶启发而发展起来的一类表面功能材料，可应用在自清洁、防雾、防冰、防腐蚀和油水分离等领域.可制备超疏水油水分离材料基材的多孔材料，有金属网格、海绵和棉织物等^[6~12].Cao等^[9]用电沉积和浸渍方法制备的层状结构超疏水超亲油铜网，其油水分离效率高于90%.Liu等^[10]用简单浸泡和硬脂酸改性制备的超疏水钢网，对油水混合物的分离效果良好.Wang等^[11]沉积被十六烷基三甲氧基硅烷包覆的二氧化硅颗粒制备的超疏水钢网，能高效分离油水且可重复使用.Mi等^[12]用自组装静电纺丝和煅烧法制备的超疏水二氧化硅纤维海绵，对各种油品的吸附率高达其重量的122倍，在恶劣环境下具有良好的稳定性且可重复使用. ...

Polydimethylsiloxane-based superhydrophobic surfaces on steel substrate: fabrication, reversibly extreme wettability and oil-water separation

2017

Robust and durable superhydrophobic steel and copper meshes for separation of oil-water emulsions

2019

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2017

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2016

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2016

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2020

... [12]用自组装静电纺丝和煅烧法制备的超疏水二氧化硅纤维海绵，对各种油品的吸附率高达其重量的122倍，在恶劣环境下具有良好的稳定性且可重复使用. ...

Fabrication of superhydrophobic cotton fabrics using crosslinking polymerization method

2018

... 虽然以金属网格和海绵为基底制备的超疏水材料分离油水的效率高，但是被油污损后难以清洗易造成二次污染.与金属网格和海绵相比，棉织物质地柔软、重量轻、成本低且可生物降解.Jiang等^[13]用交联聚合法在棉织物上制备的超疏水涂层，对各种油水混合物的分离效率高达99%以上.虽然超疏水棉织物的油水分离效率高，但是其耐久性还有待提高.贻贝具有极强的附着力.Lee等^[14]发现聚多巴胺具有类似贻贝分泌的蛋白结构和极强的粘附性，可粘附在各种有机无机表面.聚多巴胺结构中含有大量的羟基和氨基官能团，既可作为结合位点共价固定目标分子，也能通过氧化-还原反应或螯合作用与过渡金属离子结合制备出功能复合材料.因此，聚多巴胺可作为中间层在基材表面结合功能分子^[15,16].基于这种特性，研究人员制备出一系列超疏水表面.Wang等^[17]将十六烷基三甲氧基硅烷分散在多巴胺水溶液中，制备出全水性涂料溶液.Yan等^[18]使用氧化剂(NaBO₃)使多巴胺快速聚合沉积到织物上，然后将十八胺经席夫碱反应接枝到织物上，制备出的超疏水织物在恶劣环境下具有良好的耐久性和稳定性，可重复用于油水分离.本文用一种更为简便的一锅法在织物表面自组装沉积多巴胺、纳米银和十六烷基三甲氧基硅烷，制备超疏水织物并研究其油水分离性能. ...

Mussel-inspired surface chemistry for multifunctional coatings

2007

Interactions of dopamine and dopamine hydrochloride with ethanol

2016

Copper ions chelated mesoporous silica nanoparticles via dopamine chemistry for controlled pesticide release regulated by coordination bonding

2020

Durable, self-healing, superhydrophobic fabrics from fluorine-free, waterborne, polydopamine/alkyl silane coatings

2017

Biomimetic, dopamine-modified superhydrophobic cotton fabric for oil–water separation

2020

Water shedding angle: a new technique to evaluate the water-repellent properties of superhydrophobic surfaces

2009

... 用接触角测量仪(Krüss，DSA30)测量样品的润湿性，液滴的体积为10 μL；滚动角测量参考文献[19]；用场发射扫描电子显微镜(Regulus8100型，FE-SEM，Nova Nano SEM，FEI)观察样品的表面形貌；用X射线光电子能谱仪(PHI-5702型，XPS)分析样品的表面组成，以空气中的污染碳(C 1s：284.8 eV)为基准，校准结合能. ...

Resistance of solid surfaces to wetting by water

1936

... 未处理的原始棉织物亲水性极强，水滴一接触立刻被吸收.棉织物的这种超亲水性，与其化学成分和粗糙结构等因素密切相关.棉纤维是由D-葡萄糖(β型)单元经过1-4苷键互相连接聚合而成的直链天然高分子化合物，分子链中含有大量的羟基.棉纤维表面的亲水羟基(图1a)使其本征接触角小于90°.另一方面，由棉纤维加工成的棉织物具有纺织粗糙结构.根据Wenzel润湿公式

c o s θ_{W} = r c o s θ_{Y}

^[20](其中θ_Y为棉纤维的本征接触角，r为大于1的粗糙度因子，θ_W为表观接触角)，粗糙的本征亲水表面使表观接触角降低.同时，纤维间的疏松多孔结构(图1a)产生的毛细作用使织物的亲水性进一步提高.总之，棉织物的超亲水性是表面亲水羟基、纺织粗糙结构和纤维间疏松多孔的结构所致. ...

... 用不同方法评价超疏水织物的耐用性，测试后织物的表面形貌和化学成分，结果分列于图3和表3.测试后，织物出现不同程度的褪色；用色差仪定量分析测试前后织物的色差，可见超声清洗和加速洗涤后ΔE^*_ab值最大，样品显著褪色.其原因是，在超声清洗与加速洗涤过程中不仅存在强烈的机械作用(如超声过程中的空化作用、加速洗涤过程中的摩擦)，还存在化学作用(如乙醇、洗涤剂等对沉积物的洗脱).同时，样品的抗碱液浸泡性不如抗酸性.其原因是，聚多巴胺是多巴胺溶液中的单体、氧化物、低聚物、高聚物通过非共价键力(电荷转移、π-π堆积和氢键)结合在一起.200次磨损测试后织物的接触角下降到130°，因为涂层发生严重的破坏，从图3f可清晰看到在织物纤维上留下的磨痕.对测试后样品的表面成分分析结果表明，测试后织物表面的N、Si、Ag元素含量均下降；N元素来源于聚多巴胺，Si元素来源于十六烷基三甲氧基硅烷，Ag元素来源于硝酸银.这表明，经物理化学冲击后织物表面的超疏水涂层被逐渐剥离.随着表面微观形貌和表面化学的改变，TF-3C-5C样品的疏水性也随着测试的进行而降低，如图4所示.通过与典型文献[20,22~28]的对比，可见其耐用性处于主流水平(表4). ...

... Wettability variation for the TF-3C-5C sample and control samples in references

Table 4

SF-3C-5C

Comparison

Samples in reference

Ref.

Ultrasonic cleaning

CA=157.2° and SA=9° after 1 h in ethanol

CA varied from 159° to 150° after 1 h in ethanol

[22]

CA varied from 154° to 152° after 24 h in acetone

[23]

Laundering

CA=152° and SA=18° after 25 cycles

CA varied from 157° to 147° after 20 cycles

[20]

CA varied from 152° to ca. 150° after 100 cycles

[24]

Water Boiling

CA=152.2° and SA=18° after 48 h

CA varied to ca. 150° and SA increased to 15° after 35 min

[25]

Alkali Soaking

CA=153.2° and SA=14° after 48 h

CA varied from 156.3° to 152.2° after 48 h

[20]

CA varied from 156.9° to 151.6° after 48 h

[26]

Acid Soaking

CA>157.7° and SA=6° after 48 h

CA varied from 154.7° to 150.6° after 12 h ...

... [20]

CA varied from 156.9° to 151.6° after 48 h

[26]

Acid Soaking

CA>157.7° and SA=6° after 48 h

CA varied from 154.7° to 150.6° after 12 h ...

... [20] ...

Anti-galvanic reduction of thiolate-protected gold and silver nanoparticles

2012

... 为了明确沉积物的化学成分，对处理前后的棉织物进行了XPS分析，结果如图2所示.可以看出，原始棉织物的XPS全谱(图2a)中有明显的C、O峰，TF-3C-5C样品多出了N、Ag、Si元素峰，分别源于前驱体溶液中的多巴胺、硝酸银和十六烷基三甲氧基硅烷.Ag3d的高分辨率图谱如图2b所示，可见谱线双峰中心分别对应结合能相距6 eV的367.5 eV和373.5 eV，与文献[21]中银单质的Ag3d峰吻合.多巴胺及其聚合产物聚多巴胺的邻苯二酚基团，对很多金属离子有较强的配位作用，且邻苯二酚基团氧化变成醌的同时能还原金属阳离子.因此，银离子在PDA表面原位还原并沉积于其上构成微糙结构.原始棉织物的C1s高分辨率谱，如图2c所示.根据C1s可拟合出结合能位于284.7 eV处的C-C/C-H峰(峰面积占55%)、结合能位于286.3 eV处的C-O峰(峰面积占30%)以及结合能位于287.8 eV处的C=O峰(峰面积占15%).图2d中位于284.7 eV的峰强大大增大的原因，是HDTMS的加入使样品表面非极性碳的含量大大提高、表面极性降低和表面能降低. ...

Wettability of porous surfaces

1944

... Wettability variation for the TF-3C-5C sample and control samples in references

Table 4

SF-3C-5C

Comparison

Samples in reference

Ref.

Ultrasonic cleaning

CA=157.2° and SA=9° after 1 h in ethanol

CA varied from 159° to 150° after 1 h in ethanol

[22]

CA varied from 154° to 152° after 24 h in acetone

[23]

Laundering

CA=152° and SA=18° after 25 cycles

CA varied from 157° to 147° after 20 cycles

[20]

CA varied from 152° to ca. 150° after 100 cycles

[24]

Water Boiling

CA=152.2° and SA=18° after 48 h

CA varied to ca. 150° and SA increased to 15° after 35 min

[25]

Alkali Soaking

CA=153.2° and SA=14° after 48 h

CA varied from 156.3° to 152.2° after 48 h

[20]

CA varied from 156.9° to 151.6° after 48 h

[26]

Acid Soaking

CA>157.7° and SA=6° after 48 h

CA varied from 154.7° to 150.6° after 12 h ...

Fabrication of superhydrophobic surfaces by dislocation-selective chemical etching on aluminum, copper, and zinc substrates

2005

... Wettability variation for the TF-3C-5C sample and control samples in references

Table 4

SF-3C-5C

Comparison

Samples in reference

Ref.

Ultrasonic cleaning

CA=157.2° and SA=9° after 1 h in ethanol

CA varied from 159° to 150° after 1 h in ethanol

[22]

CA varied from 154° to 152° after 24 h in acetone

[23]

Laundering

CA=152° and SA=18° after 25 cycles

CA varied from 157° to 147° after 20 cycles

[20]

CA varied from 152° to ca. 150° after 100 cycles

[24]

Water Boiling

CA=152.2° and SA=18° after 48 h

CA varied to ca. 150° and SA increased to 15° after 35 min

[25]

Alkali Soaking

CA=153.2° and SA=14° after 48 h

CA varied from 156.3° to 152.2° after 48 h

[20]

CA varied from 156.9° to 151.6° after 48 h

[26]

Acid Soaking

CA>157.7° and SA=6° after 48 h

CA varied from 154.7° to 150.6° after 12 h ...

Ultrafast nano-structuring of superwetting Ti foam with robust antifouling and stability towards efficient oil-in-water emulsion separation

2019

... Wettability variation for the TF-3C-5C sample and control samples in references

Table 4

SF-3C-5C

Comparison

Samples in reference

Ref.

Ultrasonic cleaning

CA=157.2° and SA=9° after 1 h in ethanol

CA varied from 159° to 150° after 1 h in ethanol

[22]

CA varied from 154° to 152° after 24 h in acetone

[23]

Laundering

CA=152° and SA=18° after 25 cycles

CA varied from 157° to 147° after 20 cycles

[20]

CA varied from 152° to ca. 150° after 100 cycles

[24]

Water Boiling

CA=152.2° and SA=18° after 48 h

CA varied to ca. 150° and SA increased to 15° after 35 min

[25]

Alkali Soaking

CA=153.2° and SA=14° after 48 h

CA varied from 156.3° to 152.2° after 48 h

[20]

CA varied from 156.9° to 151.6° after 48 h

[26]

Acid Soaking

CA>157.7° and SA=6° after 48 h

CA varied from 154.7° to 150.6° after 12 h ...

Bioinspired self-healing superhydrophobic coatings

2010

... Wettability variation for the TF-3C-5C sample and control samples in references

Table 4

SF-3C-5C

Comparison

Samples in reference

Ref.

Ultrasonic cleaning

CA=157.2° and SA=9° after 1 h in ethanol

CA varied from 159° to 150° after 1 h in ethanol

[22]

CA varied from 154° to 152° after 24 h in acetone

[23]

Laundering

CA=152° and SA=18° after 25 cycles

CA varied from 157° to 147° after 20 cycles

[20]

CA varied from 152° to ca. 150° after 100 cycles

[24]

Water Boiling

CA=152.2° and SA=18° after 48 h

CA varied to ca. 150° and SA increased to 15° after 35 min

[25]

Alkali Soaking

CA=153.2° and SA=14° after 48 h

CA varied from 156.3° to 152.2° after 48 h

[20]

CA varied from 156.9° to 151.6° after 48 h

[26]

Acid Soaking

CA>157.7° and SA=6° after 48 h

CA varied from 154.7° to 150.6° after 12 h ...

Biomimetic polymeric superhydrophobic surfaces and nanostructures: from fabrication to applications

2017

... Wettability variation for the TF-3C-5C sample and control samples in references

Table 4

	SF-3C-5C	Comparison	Samples in reference	Ref.
Ultrasonic cleaning	CA=157.2° and SA=9° after 1 h in ethanol	>	CA varied from 159° to 150° after 1 h in ethanol	[22]
Ultrasonic cleaning	CA=157.2° and SA=9° after 1 h in ethanol	<	CA varied from 154° to 152° after 24 h in acetone	[23]

Laundering	CA=152° and SA=18° after 25 cycles	>	CA varied from 157° to 147° after 20 cycles	[20]
Laundering	CA=152° and SA=18° after 25 cycles	<	CA varied from 152° to ca. 150° after 100 cycles	[24]

Water Boiling	CA=152.2° and SA=18° after 48 h	>	CA varied to ca. 150° and SA increased to 15° after 35 min	[25]

Alkali Soaking	CA=153.2° and SA=14° after 48 h	>	CA varied from 156.3° to 152.2° after 48 h	[20]
Alkali Soaking	CA=153.2° and SA=14° after 48 h	>	CA varied from 156.9° to 151.6° after 48 h	[26]

Acid Soaking	CA>157.7° and SA=6° after 48 h	>	CA varied from 154.7° to 150.6° after 12 h ... ... [26] ... Robust fluorine-free colorful superhydrophobic PDMS/NH2-MIL-125(Ti)@cotton fabrics for improved ultraviolet resistance and efficient oil-water separation 1 2019 ... [27] ... Unexpected superhydrophobic polydopamine on cotton fabric 2 2020 ... 用不同方法评价超疏水织物的耐用性，测试后织物的表面形貌和化学成分，结果分列于图3和表3.测试后，织物出现不同程度的褪色；用色差仪定量分析测试前后织物的色差，可见超声清洗和加速洗涤后ΔE^*_ab值最大，样品显著褪色.其原因是，在超声清洗与加速洗涤过程中不仅存在强烈的机械作用(如超声过程中的空化作用、加速洗涤过程中的摩擦)，还存在化学作用(如乙醇、洗涤剂等对沉积物的洗脱).同时，样品的抗碱液浸泡性不如抗酸性.其原因是，聚多巴胺是多巴胺溶液中的单体、氧化物、低聚物、高聚物通过非共价键力(电荷转移、π-π堆积和氢键)结合在一起.200次磨损测试后织物的接触角下降到130°，因为涂层发生严重的破坏，从图3f可清晰看到在织物纤维上留下的磨痕.对测试后样品的表面成分分析结果表明，测试后织物表面的N、Si、Ag元素含量均下降；N元素来源于聚多巴胺，Si元素来源于十六烷基三甲氧基硅烷，Ag元素来源于硝酸银.这表明，经物理化学冲击后织物表面的超疏水涂层被逐渐剥离.随着表面微观形貌和表面化学的改变，TF-3C-5C样品的疏水性也随着测试的进行而降低，如图4所示.通过与典型文献[20,22~28]的对比，可见其耐用性处于主流水平(表4). ... ... [20]

Abrading	CA=132.6° and SA<30° after 200 cycles	<	CA and SA remained almost unchanged after 200 cycles	[28]

<strong>2.3</strong> 分离油水的性能

原始棉织物具有亲水亲油性，容易被油和水浸润，改性后的棉织物具有超疏水和超亲油特性.特殊的润湿性，使改性后的棉织物能吸附水中的油.如图5a所示，改性后的棉织物与油水混合物接触后能立即吸附漂浮在水面用红色染料染色的正己烷.吸附后，水面上没有残留的油渍.同时，还用密度高于水的氯仿测定了超疏水性织物的吸油性能.结果表明，将超疏水棉织物浸入水中后，水中的氯仿(红色染料染色)被完全吸收(图5b). ...

A durable bio-based polybenzoxazine/SiO₂ modified fabric with superhydrophobicity and superoleophilicity for oil/water separation

2019

... 使用超疏水棉织物对二氯甲烷/水混合物进行20次油水分离实验，油水分离效率在96%上下波动(图6d).Yao等^[29]合成的PC-a/SiO₂织物对由重力驱动的几种重油/水有优异的分离性能，油通量约为6.5~9.5 m³·m^-2·h^-1，分离效率均高于90%.Zheng等^[30]制备的碳纳米管导电超疏水织物，对三氯甲烷-水和正己水混合物的分离效率分别达到94.5%和94.8%；经过30次分离循环后，棉织物的分离效率仍高于90%.上述结果表明，这些超疏水织物对油水有较高的分离效率和可重复使用性. ...

Conductive superhydrophobic cotton fabrics via layer-by-layer assembly of carbon nanotubes for oil-water separation and human motion detection

2019

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