發(fā)布時間：2018-03-26 17:43

  本文選題：無機基體　切入點：鋁片　出處：《湖南大學(xué)》2016年碩士論文

【摘要】：超疏水表面的應(yīng)用價值是不可限量的,但是目前制備高機械性能、耐腐蝕性表面還存在很大的難度。本論文參考了大量的文獻工作,以無機金屬材料為基體,進行了表面疏水材料的制備。主要開展了電沉積法制備硬脂酸表面、電沉積法制備氧化鈰疏水表面、水熱法制備片狀Co3O4/Al疏水表面和水熱法制備C0304/泡沫鎳疏水表面等工作的研究,通過改變實驗條件,考察了表面形貌對疏水性、機械性能和腐蝕性的影響。主要結(jié)論如下：(1)采用電沉積方法在鋁板表面構(gòu)筑了Ce02-硬脂酸/Al疏水表面。FT-IR分析結(jié)果表明經(jīng)過電沉積處理,在鋁板表面成功沉積得到了硬脂酸涂層；SEM分析表明沉積表面主要存在著兩種形貌：定向生長的乳狀凸起和“中間凹,周邊凸”的片狀結(jié)構(gòu)；EDS分析表明沉積表面不同形貌對應(yīng)元素含量存在較大的差異,說明在沉積過程中,電解質(zhì)中的不同組分存在選擇性的生長；建立了四因素、三水平(L934)的正交試驗,考察了電沉積過程中硝酸鈰濃度、硬脂酸濃度、電沉積電壓以及電沉積時間等因素,并對實驗結(jié)果進行了SEM測試和WCA測試,研究了電沉積表面的形貌與接觸角之間的關(guān)系。SEM測試結(jié)果表明電沉積過程中鋁板表面會形成了不同的形貌,主要以針狀結(jié)構(gòu)和乳狀凸起為主。根據(jù)不同樣品的原料配比可知,硝酸鈰濃度越高,越有利于形成針狀結(jié)構(gòu)；硬脂酸濃度越高,表面越有利于形成乳狀凸起結(jié)構(gòu)；當(dāng)這兩種原料的濃度均較高時,表面趨向平整,并伴隨有一些裂紋存在；通過正交試驗研究了各實驗因素對實驗結(jié)果的影響,由極差分析可知,各影響因素對接觸角的影響如下：硝酸鈰濃度電沉積電壓電沉積時間硬脂酸濃度。最佳制備條件為：0.02 mol/L硝酸鈰,0.15 mol/L硬脂酸,沉積電壓10 V,沉積時間40 min。在最佳制備條件下,接觸角可達131°。(2)通過電沉積方法制備了氧化鈰/Ni疏水表面,對疏水表面的組成、形貌以及機械性能進行了考察。XRD測試表明電沉積后載體表面有氧化鈰的沉積；通過SEM發(fā)現(xiàn)沉積后表面存在著很多的缺陷,在超聲處理5 min后表面負(fù)載物大量脫落,這也說明材料的機械性能有待進一步的提升；采用三種不同的載體進行了氧化鈰的電沉積,簡單考察了載體對表面疏水性的影響。其中,泡沫鎳的疏水性最好(接近140°),金屬Ni-A1合金網(wǎng)的疏水性其次(約為120°),壓平泡沫鎳的疏水性最差(僅為115°)。這些結(jié)果說明了網(wǎng)絡(luò)結(jié)構(gòu)載體對疏水性的構(gòu)筑是有利的,這與Cassie模型是吻合的。同時,這些結(jié)果也表明單純無機物改性可以獲得疏水表面,但仍未達到超疏水的水平。采用了硅膠浸漬法和磷酸鋅浸漬法來提升負(fù)載物與載體間的結(jié)合力,對處理后的機械性能進行了考察。實驗結(jié)果表明,硅膠浸漬處理不儀可以提高負(fù)載物與載體間的結(jié)合力,還不影響載體的疏水性；而硫酸鋅處理雖然也可以提升負(fù)載物與載體間的結(jié)合力,但是會極大的影響載體的疏水性,其中壓平泡沫鎳經(jīng)過處理后轉(zhuǎn)變?yōu)槌H水,這也說明硅膠浸漬處理為更好的載體處理方式。(3)采用水熱法合成了Co3O4/Al復(fù)合物,并對該復(fù)合物的組分、形貌進行了XRD和SEM表征。XRD測試表明經(jīng)過水熱處理,鋁板表面生成了α-Co(OH)2,且經(jīng)過在500℃空氣中煅燒3 h后,鋁板表面的α-Co(OH)2轉(zhuǎn)化成為了Co3O4; SEM測試表明較低的CTAB、較長的合成時間或較高的合成溫度均不利于合成規(guī)整形貌的片狀結(jié)構(gòu)；而當(dāng)這些因素處于比較合適的范圍時,才能合成規(guī)整形貌的片狀結(jié)構(gòu)；當(dāng)合成時間過長且原料濃度較高時,材料表面的大顆粒會大量堆積,導(dǎo)致材料表面的形貌十分粗糙,呈現(xiàn)不規(guī)整性；因此,各因素的合理調(diào)控對于表面形貌具有很大的影響；設(shè)計了四因素、三水平(L934)的正交試驗,考察了硝酸鈷濃度、CTAB濃度、合成時間和合成溫度對材料表面形貌的影響。對制備得到的CoO4/Al復(fù)合物進行PFAS疏水改性,并進行了接觸角測試,探討了表面形貌與材料疏水性之間的關(guān)系；通過極差分析,各因素對疏水性的影響程度如下：合成溫度CTAB濃度硝酸鉆濃度合成時間；最佳制備條件為：硝酸鈷質(zhì)量為1.2 g,CTAB質(zhì)量為0.15 g,水熱合成時間為18 h,水熱合成溫度為100℃；最佳條件下接觸角為158°。對PFAS疏水改性后的載體進行了機械性能測試。通過機械性能的測試發(fā)現(xiàn),C0304與鋁板間的結(jié)合力較差,這可能是因為鋁板表面過于光滑,粗糙度不夠,不能為C0304提供牢固的生長位點而引起的。(4)采用水熱法合成了C0304/泡沫鎳復(fù)合物,并對該復(fù)合物的形貌、組分進行了XRD和FT-IR表征。XRD譜圖表明燒制后α-Co(OH)2轉(zhuǎn)變?yōu)榱薈o3O4, FT-IR譜圖進一步證實了這個結(jié)論;設(shè)計了單因素試驗,考察了水熱合成時間和水熱合成溫度對材料表面形貌的影響。在合成時間的考察中,隨著合成時間的增長,材料的接觸角逐漸增大,說明合成時間對接觸角有著很大的影響。從形貌上說,合成時間的延長有利于在平泡沫鎳表面形成良好的規(guī)整形貌。隨著合成時間進一步的延長,泡沫鎳表面生長的C0304生長為半花狀結(jié)構(gòu),表面規(guī)整度提高,接觸角也明顯增大,變?yōu)?44°。當(dāng)時間增大到18h后,接觸角得到了進一步的提升,變?yōu)?56°,處于超疏水的范圍；繼續(xù)延長時間,花狀結(jié)構(gòu)變?yōu)槠瑺罱Y(jié)構(gòu),接觸角雖然略有下降,但仍處于超疏水；合成溫度對接觸角的影響也比較大。適宜的溫度范圍內(nèi),接觸角處于超疏水的范圍,溫度過高或偏低,接觸角都會明顯降低。對PFAS疏水改性后的載體進行了耐腐蝕性能測試,測試了耐腐蝕性能�？瞻着菽囋诮�(jīng)過浸漬處理后,表面形貌破壞十分嚴(yán)重。接觸角也由最初的76°下降為33°、67°、58°。說明未經(jīng)負(fù)載和改性的泡沫鎳,耐腐蝕性能較差；與空白泡沫鎳相比,PFAS改性處理后,泡沫鎳的疏水性有了明顯的提升,但相比于未腐蝕前的102°,仍有了很大程度的下降,均轉(zhuǎn)變?yōu)橛H水狀態(tài)。說明單一PFAS改性對泡沫鎳耐腐蝕性是不夠的。負(fù)載不同形貌C0304的泡沫鎳在PFAS改性后具有很好的抗腐蝕能力,在經(jīng)過酸堿鹽處理后仍然可以維持良好的疏水性。而且,可以發(fā)現(xiàn)花狀和片狀結(jié)構(gòu)與不完整花狀結(jié)構(gòu)相比,疏水性更為良好,經(jīng)過耐腐蝕測試后接觸角分別為152°和155°。這說明表面負(fù)載Co3O4對疏水性起著更為重要的影響。
[Abstract]:The application value of super - hydrophobic surface is not limited , but it is difficult to prepare high mechanical and corrosion - resistant surface at present . This paper makes a study on the preparation of surface hydrophobic material by using inorganic metal material as matrix . The main conclusions are as follows : ( 1 ) The surface morphology has been prepared on the surface of aluminum plate by electrodeposition method . The results of FT - IR analysis show that Ce02 - stearic acid / Al hydrophobic surface has been constructed on the surface of aluminum plate .
The SEM analysis showed that the deposition surface mainly existed two kinds of morphology : the shape - like bulge with directional growth and the lamellar structure of " middle concave and peripheral convex " ;
EDS analysis shows that there is a large difference in the content of the corresponding elements in the deposited surface , and the selective growth of different components in the electrolyte during the deposition process is explained .
A four - factor , three - level ( L934 ) orthogonal test was established to investigate the factors such as concentration of cerium nitrate , concentration of stearic acid , electrodeposition voltage and electrodeposition time during electrodeposition .
The higher the concentration of stearic acid , the more favorable the surface is , the more favorable the structure is formed .
When the concentration of the two kinds of raw materials is higher , the surface tends to be flat and accompanied by some cracks .
The effects of various experimental factors on the experimental results were studied by orthogonal experiments . The influence factors on the contact angle were determined by the polarization analysis . The optimum conditions were : 0.02 mol / L cerium nitrate , 0.15 mol / L stearic acid , 10 V deposition voltage and 40 min deposition time . The composition , morphology and mechanical properties of the hydrophobic surface were investigated by electrodeposition .
It was found that there were a lot of defects on the surface after 5 min of ultrasonic treatment , and the mechanical properties of the materials needed to be further improved .
The electrodeposition of cerium oxide was carried out by three different carriers , and the influence of the carrier on the surface hydrophobicity was investigated . The hydrophobic property of Ni - Al alloy was better than that of Cassie model .
XRD and SEM characterization of 偽 - Co ( OH ) 2 on the surface of aluminum plate have been carried out by hydrothermal method .
When these factors are in the appropriate range , the sheet - like structure with regular topography can be synthesized .
When the synthesis time is too long and the concentration of the raw materials is high , large particles on the surface of the material can be accumulated in a large amount , so that the appearance of the surface of the material is very rough , and the irregularity is presented ;
Therefore , the reasonable regulation of each factor has great influence on the surface topography ;
A four - factor and three - level ( L934 ) orthogonal test was designed to investigate the effects of cobalt concentration , CTAB concentration , synthesis time and synthesis temperature on the surface morphology of the material .
The influence degree of each factor on hydrophobicity is as follows : synthesis temperature ( CTAB ) concentration nitric acid drilling concentration synthesis time ;
The optimum conditions were as follows : the mass of cobalt nitrate was 1.2 g , the mass of CTAB was 0.15 g , the hydrothermal synthesis time was 18 h , and the hydrothermal synthesis temperature was 100 鈩，

本文編號：1668890