TWI516370B - 光觸媒膜層結構 - Google Patents
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- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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Description
本揭露係有關一種塗層結構,尤指一種光觸媒膜層結構。
光觸媒材料是一種具有自清潔功能之仿生材料,因此現已廣泛運用於日常生活科技之中。近年,隨著科技的發展及生活水平的提升,除了光觸媒要求生活用品(如,自清潔、抗菌)的效能外,對於安全重視程度也日益增加。
傳統上,結合有高分子樹脂之光觸媒塗料,礙於光觸媒塗料中含有高分子樹脂常導致塗層塗佈於戶外,有日照老化之疑慮,因此無法利用來自陽光中紫外線光譜,啟動光觸媒作用達到除污或除臭之作用。
另一方面,光觸媒塗層越粗糙、表面積越大之情況下光觸媒作用的效果則越佳。然而,利用燒結製得的光觸媒陶瓷,在燒結過程中,使得顆粒表面原子傾向自身中心擴散,因此,使所製得之光觸媒塗層表面趨於平滑,遂導致所製得之光觸媒效能不彰。
通常,用於將光觸媒材料固定於基材上之法包括:溶膠凝膠法、電化學沉積法、化學氣相沉積法、水熱法、反應蒸鍍法、噴霧法、浸沾、旋轉噴覆法或網印法等。例如,以反應蒸鍍法製備TiO2光觸媒材料,該方法中為了增加材料本身彼此間或材料與基
板間的黏著力,均會添加黏著劑等高分子藥液,且為了處理掉揮發劑,有時還須搭配加熱或燒結煅燒方式趕走剩餘揮發劑,並加速黏著劑固化,藉以強化與基板之黏合性,以形成光觸媒膜層。
然而,使用反應蒸鍍法常會有殘留酸或鹼液等,長期碰觸有造成身體傷害、污染食物或環境危害之疑慮。此外,TiO2光觸媒膜之製備大多是利用浸鍍、噴鍍、淋鍍、刷鍍、旋鍍等製程固定於基板上,該些方法使該TiO2光觸媒對於基材之附著效果差,容易因外力作用產生剝落現象。
而以物理氣相或化學氣相沉積法,所製得之光觸媒膜層較薄,約小於等於1微米,但可能造成紫外光線直接穿透,無法均勻地進行散射與吸收,且總體表面積小更使的光觸媒處理外界有機汙染物之效果較差。此外,又由於該光觸媒膜層之厚度過薄,並不足以應付長期的有磨耗傷害膜層之戶外環境(例如,戶外牆壁或橋樑外表等處),因此常導致該些地方之光觸媒膜層易快速的損耗消失,而失去原有光觸媒特性。
一種光觸媒膜層結構,係包括:複數微米顆粒;複數奈米顆粒;以及複數塊體,且各該塊體之體積大於各該奈米顆粒之體積,且各該微米顆粒、奈米顆粒及塊體係含有氧化鋅及摻雜金屬,其中,該摻雜金屬的含量係佔該光觸媒膜層結構之1至5wt%,且該複數微米顆粒及奈米顆粒係佔該光觸媒膜層結構體積的10至50%。
第1及1'圖係顯示實施例1製得之光觸媒膜層結構以掃描式
電子顯微鏡放大2000倍觀察之外觀,且第1圖中,黑色箭頭所示處係複數微米顆粒,白色箭頭所示處係複數奈米顆粒;第1’圖係顯示光觸媒膜層結構之顆粒局部放大圖,且如圖中箭頭所示,該顆粒之殼體係內部中空;第2A至2C圖係顯示本揭露不同厚度之光觸媒膜層結構之截面光學顯微鏡照片;第3圖係顯示本揭露之光觸媒膜層結構之X光繞射分析圖譜;第4圖係顯示本揭露之光觸媒膜層結構之截面電子顯微鏡照片;第5圖係顯示本揭露之光觸媒膜層結構之能量散佈分析圖譜;以及第6圖係顯示光照實驗之各時間點的吸收光譜。
以下藉由特定的具體實施例說明實施方式,熟悉此技藝之人士可由本說明書所揭示之內容輕易地瞭解本揭露之其他優點及功效。
本揭露藉由熱噴塗方式,使光觸媒原料於熔融或部份熔融之狀態下,以高壓噴濺至基材上,先噴塗至基材表面之光觸媒原料炸裂為不規則之球形或非球形顆粒,使後噴塗至基材表面之光觸媒原料可藉由熔融或部分熔融之方式與先噴塗至基材表面之光觸媒原料有效地結合,以增加光觸媒原料附著至基材表面之效率。
具體而言,本揭露之光觸媒膜層結構係藉由噴濺形成,在噴濺之飛行過程中及接觸基板時,由於光觸媒原料炸裂而產生微米
顆粒及奈米顆粒,在後續噴塗之光觸媒原料至基材表面時,該光觸媒原料所碎裂之微米顆粒及奈米顆粒透過熔融彼此間相互黏結而形成粒徑較大的塊體。這些微米顆粒及扁平化塊體具有擔負黏合基材與奈米顆粒之角色,在與基材接合面上更能比傳統塗刷法或黏合一光觸媒紙板、塑膠板或金屬板之鍵結強度更高。
本揭露使用之光觸媒原料係具有中空結構,於熱噴塗製程中,該光觸媒原料可因熱噴塗製程加熱膨脹而在後續噴塗至基材之飛行過程中以炸開或崩開方式分裂為複數奈米及微米顆粒,且該些奈米及微米顆粒之形狀可為非球形或球形。
本揭露提供之光觸媒膜層結構,係包括:複數微米顆粒;複數奈米顆粒;以及複數塊體,且各該塊體之體積大於各該奈米顆粒之體積,其中,各該微米顆粒、奈米顆粒及塊體係含有氧化鋅及摻雜金屬,該摻雜金屬的含量係佔該光觸媒膜層結構之1至5wt%,且該複數微米顆粒及奈米顆粒係佔該光觸媒膜層結構體積的10至50%。
於一具體實例中,該複數微米顆粒之粒徑範圍係介於5至45μm。該複數奈米顆粒之粒徑範圍係介於95至195nm。
於另一具體實例中,該部分塊體在平行於該基材表面之方向上的尺寸係大於垂直於該基材表面之方向上的尺寸。
於本揭露中,該微米顆粒、奈米顆粒及塊體彼此間係相互黏結。具體而言,各該微米顆粒、奈米顆粒及塊體係經熔融或部分熔融而相互黏結。
本揭露提供的光觸媒膜層結構之厚度係介於20至70μm。
本揭露提供的光觸媒膜層結構之孔隙率係介於1至20%。
於一具體實施例中,該摻雜金屬係選自Al及Ag所組成群組之至少一種元素。
此外,該氧化鋅係佔該光觸媒膜層結構之95至99wt%,且該摻雜金屬係位於氧化鋅之晶格結構中。
於一具體實施例中,該光觸媒膜層結構係形成於一基材上,其中,該基材可為金屬、合金、陶瓷或玻璃。
於另一具體實施例中,該基材為玻璃,且該玻璃基材表面係部分熔融,以黏結該光觸媒膜層結構。
首先,於本實施例中之基材分別為不銹鋼(SS304)、鋁和玻璃,尺寸L120×W25×t3mm3,並使用熱熔射噴塗裝置(A3000,F4 gun),並通以由每分鐘41升之氬氣與每分鐘8至14升之氫氣所組成之混合氣體之環境下,以口徑為6mm之電漿熔射槍,於電流530至620安培,於110至140毫米之噴塗距離,以每分鐘3.5升之氬氣做為載流氣體,輸送每分鐘10至12克之光觸媒原料(購自永朕材料科技公司,QF-ZNA-97),來回噴塗在試片面積L120×W25mm2上20趟,以得到本揭露之光觸媒膜層結構,並發現光觸媒膜層結構可完整牢固地形成在不銹鋼(SS304)、鋁和玻璃上。
此外,以掃描式電子顯微鏡(scanning electron microscope,SEM)放大2000倍觀察實施例1製得之光觸媒膜層結構之外觀,如第1圖所示,其中,黑色箭頭所示處係複數微米顆粒,白色箭頭所示處係複數奈米顆粒。據此可知,複數奈米顆粒係因炸開或崩開方式形成,且奈米顆粒黏結在微米顆粒上。
請參閱第1’圖,係顯示光觸媒膜層結構之顆粒局部放大圖。如圖之箭頭所示,該顆粒之殼體係內部中空。並且根據第1及1’圖所示,本領域具有通常知識者可看出原始輸送之光觸媒原料粉末僅為微米尺度範圍之粉末,本實施例並非傳統為了特別製作具奈米尺度之光觸媒膜層,改以輸送微米混合奈米、次微米混合奈米,或者輸送僅奈米尺度等範圍之粉末,而係經熱熔射方式得到具有複數微米顆粒、複數奈米顆粒、以及複數塊體之光觸媒膜層結構。
請參閱第2A至2C圖,係本揭露不同厚度之光觸媒膜層結構之截面光學顯微鏡照片,各該圖示之光觸媒膜層結構係使用實施例1之方法將光觸媒原料噴塗至玻璃基板上製得。此外,當光觸媒膜層結構之厚度為20至70μm時,針對甲基藍降解,方有特定光觸媒效率,厚度為20μm附近,例如厚度為19.5μm時,具有近70%之功效,而厚度為70μm附近則低於60%之功效,而當光觸媒膜層結構厚度為40~60μm時,有最高效率,即高於70%之功效。另一方面,光觸媒膜層結構厚度過薄,將不利於磨耗大之使用環境,厚度越厚,除了效率不高外,製膜成本相對高。
此外,請參閱第3圖,經X光繞射分析(XRD)結果顯示,本揭露之光觸媒膜層結構仍屬於氧化鋅(ZnO)之標準陶瓷金相(PDF36-1451)。由前可知,本揭露使用熱噴塗法形成鍍膜,並不會影響或改變光觸媒原料原有之金相。
首先,於本實施例中之基材為不銹鋼(SS304),尺寸L120×W25×t3mm3,並使用熱熔射噴塗裝置(Model J-3 spraywelder),
並以20至25Psi的壓力輸送冷空氣;以17Psi的壓力輸送氧氣(43% Flow)與以15Psi的壓力輸送乙炔(C2H2)(34% Flow)所組成之混合氣體之環境下,以口徑為6mm之熔射槍,於220至230毫米之噴塗距離,來回噴塗在試片面積L120×W25mm2上,10至12趟,以得到本揭露之光觸媒膜層結構。同樣地,該光觸媒膜層結構可完整牢固地形成在不銹鋼上。
於本揭露中,對於用以輸送該光觸媒原料之載流氣體並未有特殊的限制,亦可使用包括,但不限於N2、CO2或CH4等氣體做為載流氣體,以增加C、H或N等非金屬元素的含量。此外,當本揭露所使用之基材為玻璃時,該玻璃基材表面係部分熔融,以黏結該光觸媒膜層結構。
相較於習知AZO以細長纖維狀成長或多角型態存在,並不適用於熱熔射機台粉末輸送機制,但本揭露光觸媒膜層結構所使用之光觸媒原料係5至45微米較大球狀顆粒,可以形成如熔融或半熔融而得扁平化顆粒(Flattencd particles),這些扁平化顆粒係微米級,且具有擔負黏合基材與奈米顆粒之角色,在與基材接合面上更能比傳統塗刷法或黏合一光觸媒紙板、塑膠板或金屬板之鍵結強度更高。此外,後續撞擊至基材之奈米及微米顆粒亦因相互熔融產生尺寸較大之塊體,使本揭露之光觸媒膜層結構得同時具有奈米顆粒、微米顆粒與塊體。
第4圖為本揭露之光觸媒膜層結構之電子顯微鏡截面金相,由此照片中,可以進一步說明光觸媒膜層結構特徵。扁平化塊體(如圖中大片之灰色塊體所示)擔負黏合彼此,且一直串接至與基材之界面;而奈米顆粒群(如白色箭頭所示)分佈於塗層孔洞中,
當光觸媒膜層表面被磨耗掉後,仍會有新的高表面積光觸媒奈米顆粒露出,可以再發揮對有機污染物之分解作用。
再者,傳統塗刷法有配合燒結法之方式,以增加光觸媒材料與基板黏合程度,然而,燒結法相較本製程溫度高且時間長,會破壞奈米結構,使得奈米顆粒長大成為微米顆粒,無法達到本揭露之熱噴塗方式所產生之光觸媒膜層結構。本揭露之光觸媒膜層結構具有噴濺顆粒(splat particles),且以該噴濺顆粒陸續堆疊形成扁平化顆粒,並伴隨奈米批覆微米顆粒的混合結構。
首先,使用電弧離子鍍膜(Arc ion plating,AIP)鍍覆厚度為<1μm之摻鋁氧化鋅(AZO)薄膜。
係使用能量散佈分析儀(JEOL;JSM-6500F)進行測量,並將量測結果記錄於表1,測試圖譜如第5圖所示。
請參閱表1及第5圖,根據表1的能量散佈分析結果可知,本揭露之光觸媒膜層結構中的元素含量比例相當接近理想光觸媒組成的配比Zn、O、Al之重量百分比為77.93wt%、20.48wt%、1.59wt%。換言之,本揭露之光觸媒膜層結構仍保有氧化鋅(ZnO)
原有之金相,且本揭露之光觸媒膜層結構並未在熱噴塗的過程中改變或受到破壞。
依據期刊(Journal of The Electrochemical Society,153,10,F237-F243,2006.)中採用之檢測方法進行光照實驗並測量其吸收率的變化。
將光觸媒原料以實施例1之方法形成於2.5×2.5cm2玻璃上,並將製得之光觸媒膜層結構試片放入一玻璃皿中,該玻璃皿內再浸入1×10-5M濃度的甲基藍藥液,並由一封閉式可隔離外部光線之箱內,提供照度1045±40μW/cm2、波長為365nm之紫外光光源,用以照射玻璃皿中之光觸媒膜層結構試片,分別於第1、2、3、4、5、6、10、14、16、18、22及24小時以UV-Vis光譜儀分析其反應後之甲基藍藥液之吸光值,並將結果顯示於第6圖。另外,光觸媒膜層結構在照光24小時後,甲基藍藥液的顏色已退色至如RO水般透明,且在600至700nm之波長範圍之吸收值顯著降低,表示確具有光觸媒效果。
此外,以換算甲基藍藥液之濃度做說明。當以比較例1之光觸媒膜層紀錄12小時後之甲基藍藥液之濃度,發現並無明顯變化。但以實施例1形成的本揭露光觸媒膜層結構及市售二氧化鈦薄膜進行測試,甲基藍藥液之濃度可降至0.40×10-5M,當記錄時間延長至45小時,以市售二氧化鈦薄膜測得之甲基藍藥液之濃度降至約0.12×10-5M,但以本揭露光觸媒膜層結構測得之甲基藍藥液之濃度則降至約0.04×10-5M,顯示本揭露光觸媒膜層結構具有優異且長時效之光觸媒效果。
再者,於進行光觸媒效果之測試前分別以三用電錶確認比較例1及實施例1皆具有導電特性。然而,經過12小時光觸媒反應後,比較例1之膜層部份剝落,且經三用電錶簡易量測,已經不具有導電特性的。有別於比較例1,本揭露之光觸媒膜層結構12小時光觸媒反應後,仍然保持完整且保有導電特性。
依據規範CNS15353所做之抗菌實驗,以光波長543nm及照度1500lux照光條件,進行照光及避光培養24小時後,於該光觸媒薄膜結構試片金黃色葡萄球菌液(BCRC 10451),並計算金黃色葡萄球菌的菌落數,並將結果記錄於表2。
根據表2之數據可知,實施例1之光觸媒膜層對於菌株的貼附,並有效防止菌落的生成,具有絕佳之抗菌效果。
根據ASTM C633標準測試拉伸破斷實驗(PAT adhesion tester,GM01,DFD儀器公司),於直徑為8.16mm的鋼製鍛模(dolly)面以Sulzer Metco公司出品的黏合劑(Plasma tex KLEBBI)黏合測試試片,試片係以實施例2之方法分別使用光觸媒原料及一般氧化鋁粉末形成光觸媒膜層結構,每一類試片進行3次測量,並取得平均值,當作該拉伸破斷實驗值。
結果顯示,氧化鋁光觸媒膜層結構的強度值僅有21.2MPa,但本揭露之光觸媒膜層結構的強度值高達50.8MPa,確實具有良好附著力。
綜上所述,由於本揭露係藉由熱熔射法將光觸媒原料以熔融或半熔融之狀態噴塗至基材上,且在加熱環境下該光觸媒原料能以炸開或崩開方式分裂出許多近球形或球形的奈米及微米顆粒,且該奈米顆粒會黏附於近球形或球形的微米顆粒上,藉由載流氣體輸送這些熔融或半熔融飛行顆粒,並陸續堆疊成形於基材上,並透過重複噴塗熔射之趟數,來使調整塗層所欲之厚度,得到本揭露具有奈米顆粒披覆微米顆粒之混合結構的光觸媒膜層結構。
於本揭露中,由於在噴塗過程中,先撞擊至基材之光觸媒原料中的微米顆粒已經成為熔融或半熔融產生扁平化顆粒(Flattened particles),這些扁平化顆粒係微米級,且具有擔負黏合基材與奈米顆粒之角色,在與基材接合面上更能比傳統塗刷法或黏合一光觸媒紙板、塑膠板或金屬板之鍵結強度更高,此外,後續撞擊至基材之奈米及微米顆粒亦因相互熔融產生尺寸較大之塊體,使本揭露之光觸媒膜層結構得同時具有奈米顆粒、微米顆粒與塊體。具體而言,本揭露係將該光觸媒原料透過熱熔射製程,而產生熱熔融之狀態下材料,由高壓空氣之推力,將熔融材料噴覆到工件表面,增強膜層附著力。
上述實施例係用以例示性說明本揭露之原理及其功效,而非用於限制本揭露。任何熟習此項技藝之人士均可在不違背本揭露之精神及範疇下,對上述實施例進行修改。因此本揭露之權利保護範圍,應如後述之申請專利範圍所列。
Claims (10)
- 一種光觸媒膜層結構,包括:複數微米顆粒;複數奈米顆粒;以及複數塊體,且各該塊體之體積大於各該奈米顆粒之體積,其中,各該微米顆粒、奈米顆粒及塊體係含有氧化鋅及摻雜金屬,該摻雜金屬的含量係佔該光觸媒膜層結構之1至5wt%,且該複數微米顆粒及奈米顆粒係佔該光觸媒膜層結構體積的10至50%。
- 如申請專利範圍第1項之光觸媒膜層結構,其中,該複數微米顆粒之粒徑範圍係介於5至45μm。
- 如申請專利範圍第1項之光觸媒膜層結構,其中,該複數奈米顆粒之粒徑範圍係介於95至195nm。
- 如申請專利範圍第1項之光觸媒膜層結構,其厚度係介於20至70μm。
- 如申請專利範圍第1項之光觸媒膜層結構,其孔隙率係介於1至20%。
- 如申請專利範圍第1項之光觸媒膜層結構,其中,該摻雜金屬係選自Al及Ag所組成群組之至少一種元素。
- 如申請專利範圍第1項之光觸媒膜層結構,其中,該氧化鋅係佔該光觸媒膜層結構之95至99wt%。
- 如申請專利範圍第1項之光觸媒膜層結構,其係形成於一基材上。
- 如申請專利範圍第8項之光觸媒膜層結構,其中,該基材為金 屬、合金、陶瓷或玻璃。
- 如申請專利範圍第8項之光觸媒膜層結構,其中,該部分塊體在平行於該基材表面之方向上的尺寸係大於垂直於該基材表面之方向上的尺寸。
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