Research progress on the design principle and preparation of low ice adhesion surface
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摘要: 表面結冰給通訊、電力等工業領域帶來巨大損失，電加熱和噴灑乙二醇等主動除冰方法雖然在一定程度上可以解決上述問題，但在能源、人力、環境方面需付出較高代價。為解決這一問題，低成本、低能耗的被動式防/除冰表面被寄予厚望。防/除冰表面主要分為延長結冰時間的防冰表面和低冰粘附強度的除冰表面。由于實際工況的復雜性，除冰表面比防冰表面更具有可實現性。除冰表面主要與低表面能、界面滑動和裂紋產生相關，低冰粘附強度表面按實現機理可分為化學改性低表面能表面、潤滑表面、界面滑動表面和裂紋源表面。本文對不同類型低冰粘附表面的低冰粘附強度產生的原因和表面的制備方法進行總結。同時，對冰粘附強度的測量標準進行了說明和討論，以解釋不同的測試方法對防/除冰性能測試結果造成的差異。Abstract: Ice accretion on a bare surface causes a serious problem in industries and daily life such as communication, electricity, and transportation. At present, the main de-icing method is active de-icing, which includes mechanical de-icing or electric-thermal de-icing and spraying glycol anti-icing agents. These methods have a high cost of manpower, energy, and environment. In addition, active de-icing is not applicable in many scenarios. To solve this problem, icephobic surfaces are expected to be widely used. Icephobic surfaces can be divided into surfaces that prolong the freezing time and surfaces with low ice adhesion. Anti-icing surfaces, represented by superhydrophobic surfaces, can inhibit a stable formation of ice nucleation from delaying ice formation, which enables the supercooled droplets to rebound from the surface to prevent ice formation. However, under high humidity and high atmospheric pressure, the superhydrophobic surface may lose efficiency due to frosting and other reasons. Compared with anti-icing surfaces, de-icing surfaces are more achievable. Thus, this article mainly explores surfaces with low ice adhesion. Passive de-icing mainly refers to the construction of the ice sparing surface on a bare substrate to reduce the adhesion strength of icing. Compared with active de-icing methods, the passive method has advantages of low energy consumption, low cost, and environmental friendliness. The realization of low ice adhesion is mainly related to low surface energy, interface slippage, and crack initiation. According to the realization mechanism, low ice adhesion surfaces can be divided into low surface energy surfaces, lubricated surfaces, interfacial slippage and low shear modulus surfaces, and crack initiators surfaces. The design principles and mechanism of the de-icing surface are explored and summarized in this article. In addition, to eliminate the doubts about the large variations in the reported ice adhesion strength caused by different measurement methods, the measurement standards of ice adhesion are also analyzed and discussed.
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Key words:
- de-icing /
- ice adhesion /
- test standard /
- surface design /
- superwetting
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圖 2 化學改性低表面能表面形貌及其制備流程示意圖。（a）自組裝單分子層示意圖[19]；（b）自組裝單層膜表面SEM圖像[21]；（c）CVD沉積聚四氟乙烯表面SEM圖像[22]；（d）iCVD法沉積氟化聚合物表面過程示意圖，其中TBPO為過氧化丁基（tert-butyl peroxide）[24]
Figure 2. Morphology and preparation flow diagram of the chemical-modified low surface energy surface: (a) schematic diagram of the self-assembled monolayer[19]; (b) SEM image of the surface of the self-assembled monolayer[21]; (c) SEM image of the surface of the deposited PTFE[22]; (d) fluorinated polymer surface deposition process by iCVD, TBPO is tert-butyl peroxide[24]
圖 4 SLIPs表面形貌及其示意圖。（a）閉孔結構SEM圖像[28]；（b）未經處理的鋁區域和PPy涂層區域的SEM圖像[29]；（c）在鎂合金上制備的多層SLIPs涂層的示意圖[30]；（d）聚硅氧烷和氟化POSS自組裝涂層的示意圖[31]
Figure 4. Topography and schematic diagram of SLIPs: (a) SEM image of the nanohole array[28]; (b) SEM images of the untreated aluminum area and the PPy coated area[29]; (c) schematic diagram of various barriers proposed in the prepared SLIPs coating on the magnesium alloy[30]; (d) schematic diagram of the self-assembled coating of polysiloxane and fluorinated POSS[31]
圖 5 自潤滑除冰表面的設計策略。（a）LLG的制備示意圖[36]；（b）多功能防冰水凝膠表面具備的三種防除冰手段[37]；（c）離子擴散產生潤滑層的示意圖[38]
Figure 5. Design strategy of the self-lubricating de-icing surface: (a) schematic diagram of the preparation of ice-repellent LLG[36]; (b) three ways to prevent and eliminate ice on the surface of multifunctional anti-icing hydrogel[37]; (c) schematic diagram of a lubricant layer produced by ion diffusion[38]
圖 6 界面滑動表面冰動態黏滑過程的示意圖
Figure 6. Schematic diagrams of the dynamic stick-slip process of ice on the interface sliding surface
圖 8 超過臨界尺寸后，界面滑動表面與冰的界面斷裂由自發斷裂模式向裂紋擴展斷裂模式轉變的示意圖
Figure 8. After the critical size is exceeded, the interface fracture between the sliding surface of the interface and the ice changes from a spontaneous fracture mode to a crack propagation fracture mode
圖 9 裂紋源表面除冰機理及該表面典型形式。（a）裂紋源表面機理示意圖；（b）亞微米級泡沫的橫截面SEM圖像和相應的變形性能示意圖[49]
Figure 9. De-icing mechanism and typical form of crack source surface: (a) schematic diagram of the surface mechanism of the crack source; (b) SEM image of the cross-section of the submicron foam and the schematic diagram of the deformation performance[49]
圖 10 裂紋源表面設計的策略。（a）包含亞結構的PDMS表面剪切加載前后的變形的示意圖[13]；（b）兩圖分別為樣式1的硅模板及其得到的表面[50]；（c）局部應力集中除冰表面結構示意圖[51]；（d）第II相位置形成裂紋示意圖[51]
Figure 10. Strategy of the crack source surface design: (a) schematic diagram of the deformation before and after shear loading on the PDMS surface with substructure[13]; (b) the two figures show the silicon template of style 1 and its surface[50]; (c) schematic diagram of the de-icing surface with the local stress[51]; (d) cracks are formed under the coordinates of phase II[51]
a—the length of the structure; b—the pitch of the structure in the x direction; c—the pitch of the structure in the y direction; h—the height of the structure
圖 12 探針高度對脫粘附方式的影響（（Ⅰ）純剪切，（Ⅱ）彎矩增加，（Ⅲ）剪切和拉伸疊加）
Figure 12. Influence of probe height on the mode of deadhesion((Ⅰ) pure shear, (Ⅱ) bending moment increase, and (Ⅲ) shear and stretch superimposition)
表 1 不同表面冰粘附強度大小以及相應的測試方法和測試參數
Table 1. Different surface ice adhesion strengths and corresponding test methods and test parameters
Reference Adhesion strengh/kPa Method Test
temperature/°CArea
square/mm2Probe
speed/(mm·s?1)Probe
height/mmfreezing
time/hfreezing
temperature/°C[28] 10±7 Horizontal shear ?10 24 0.1 <1 ?20 [29] 15.6±3.6 Horizontal shear ?10 24 0.1 <1 ?20 [31] 2.5±0.3 Horizontal shear ?15 0.5 2 ?18 [32] 4.27±0.92 Horizontal shear ?20 100 0.5 2 [35] 27.0±6.2 Horizontal shear ?15 5 ?15 [36] 55±15 Horizontal shear ?18 and ?60 314 0.01 <1 [41] 5.2±0.4 Horizontal shear ?18 595 0.01 <1 2 ?18 [42] 13.0±1.3 Horizontal shear ?18 595 0.01 <1 2 ?18 [44] 6.0±0.9 Horizontal shear ?18 595 0.01 <1 2 ?18 [45] 38.3 ± 0.5 Horizontal shear ?18 595 0.01 <1 2 ?18 [46] Horizontal shear ?10 or ?20 0.074 [50] Horizontal shear ?25 225 0.1 3 ?25 [53] 4.8±2.0 Horizontal shear ?15 176 0.05 0.5 1 [24] 185.3±83.7 Horizontal shear ?15 100 1.3 2 ?15 [30] 40±3 Vertical shear ?20 68 [38] 5.7 Vertical shear ?30 176 0.01 <2 0.5 ?30 [40] 0.2 Vertical shear ?10 [49] 0.9 Vertical shear ?18 14 0.002 <1 24 ?18 [21] 86.2±29 Centrifugal test ?10 96 [22] 72±12 Centrifugal test ?10 
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