目的 开发一种具备超疏水/超亲油特性的改性珍珠岩材料,并实现含油污水的快速检测,以满足海洋溢油、工业含油污水等污染场景高效检测与污染防控的迫切需求。方法 采用化学改性工艺对天然珍珠岩进行低表面能处理,经研磨、硬脂酸改性、烘干、再次研磨等工艺后,得到具有超疏水性和超亲油性的珍珠岩粉末。系统评估了改性后超疏水珍珠岩粉末的润湿性。进一步采用改性后珍珠岩粉末制备了超疏水液体弹珠,评估了超疏水液体弹珠的稳定性,测试了其对含油污水的灵敏度。最终设计并开发出一种含油污水检测器。结果 超疏水珍珠岩粉末表面不含氟元素,并具有良好的超疏水性能和超亲油性。采用各种水基液体（水、可乐、咖啡、牛奶等）均可制备出液体弹珠。液体弹珠经注水、吸水、切割、跌落、挤压、远距离运输后仍保持良好的稳定性。此外,液体弹珠接触到含油污水后在几十毫米内即可破裂,展现出良好的灵敏度。结论 制备的珍珠岩具有良好的超疏水性、超亲油性,制备的液体弹珠对含油污水展现出良好的灵敏度,该方法所能测试的油膜厚度的极限值为0.17 μm,开发的含油污水检测盒可实现含油污水的快速检测。上述含油污水检测方法无需使用大量的化学试剂,减少了对环境的影响。同时,它对海洋溢油、工业废水等不同来源、类型的废水均适用,在污染防治、废水处理等方面具有广阔的应用前景。
Abstract
The work aims to address the urgent need for efficient detection of oily wastewater by developing a kind of environmentally friendly superhydrophobic/superoleophilic perlite powder through a fluorine-free chemical modification process. The preparation method involved sequential grinding of natural perlite, surface modification with stearic acid, controlled drying, and final micronization to obtain functionalized powder. The rough structures and the low surface energy functional groups endowed the perlite powder with superhydrophobicity. Comprehensive characterization confirmed the successful acquisition of required wettability properties, with the modified perlite powder exhibiting exceptional water repellency (contact angle exceeding 150°) and oil affinity without incorporating fluorinated compounds. In addition, based on the developed superhydrophobic perlite powder, stable superhydrophobic liquid marbles were prepared with various aqueous media such as water, cola, coffee, and milk. The comprehensive performance of superhydrophobic liquid marbles was systematically evaluated, and the results showed that the prepared superhydrophobic liquid marbles had good stability. The superhydrophobic liquid marbles maintained structural integrity during water injection and water suction experiments. Superhydrophobic liquid marbles were also cut at random without damage. After the PET sheet was placed on the liquid marbles and then removed, the superhydrophobic liquid marbles could return to their original shape, indicating that they had good load-bearing capacity. Furthermore, superhydrophobic liquid marbles remained unbroken after falling from a certain height. In addition, the evaporation time of the superhydrophobic liquid marbles was significantly longer than that of water droplets at different temperatures, which indicated that the liquid marbles had a longer service life when used. Under the effect of gravity, the superhydrophobic liquid marbles maintained a stable state, and rolled along the straight-line track and S-shaped track directionally, and there was no orbital deviation or rupture in the whole process. The superhydrophobic liquid marbles broke up rapidly within tens of milliseconds upon contact with oily wastewater such as water/diesel oil, water/peanut oil, and water/hexane, indicating that the prepared superhydrophobic liquid marbles exhibited good sensitivity to water/oil mixtures. This observable rupture phenomenon provided the fundamental detection mechanism. The mechanism by which superhydrophobic liquid marbles were highly sensitive to water/oil mixtures was revealed. When a superhydrophobic liquid marble was placed on the surface of the water/oil mixture, the superhydrophobic perlite powder was wetted immediately upon contact with the oil, and the superhydrophobicity was lost, leading to the rapid rupture of the superhydrophobic liquid marble. Further, an oily wastewater detector was prepared based on the mechanism that superhydrophobic liquid marbles had high sensitivity to oily wastewater. When the test liquid was relatively clean water, the water was infiltrated along the bottom non-woven fabric to the liquid marbles, and the liquid marbles did not rupture. When the water/diesel mixture was tested, the liquid marbles ruptured immediately after coming into contact with the test liquid, and the minimum oil film thickness measured by this method was about 0.17 μm. Thus, the oily wastewater detector can detect the presence of oily contaminants in water. In summary, the developed oily wastewater detector demonstrates particular promise for on-site pollution screening in marine ecosystems and industrial settings, where its reagent-free operation reduces ecological impact while providing timely contamination alerts.
关键词
海洋防污 /
超疏水表面 /
微/纳结构 /
低表面能 /
含油污水
Key words
marine antifouling /
superhydrophobic surfaces /
micro- and nano- structures /
low surface energy /
oily wastewater
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基金
山东省自然科学基金（ZR2025QC1172,ZR2024QE379）
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