生物醫(yī)用鎂合金表面電沉積硅烷改性研究
發(fā)布時(shí)間：2019-04-21 09:42
【摘要】：鎂合金具有優(yōu)異的力學(xué)相容性、生物相容性和可降解性,在臨床醫(yī)學(xué)領(lǐng)域中有廣闊的應(yīng)用前景,但過快的腐蝕速度嚴(yán)重制約了其醫(yī)學(xué)應(yīng)用。金屬表面硅烷化是近年來迅速發(fā)展起來的一種綠色環(huán)保型腐蝕防護(hù)技術(shù),在不銹鋼、鋁合金及鎂合金等多種金屬材料表面已成功應(yīng)用。本文采用電化學(xué)輔助沉積(電沉積)方法對(duì)AZ31B鎂合金進(jìn)行硅烷化處理,通過電化學(xué)工作站、掃描電子顯微鏡、能譜儀等儀器設(shè)備及體外模擬降解實(shí)驗(yàn),研究了KH-560、KH-570和BTSE三種硅烷在沉積過程中的最佳添加量,并橫向比較了相同電沉積工藝下三種硅烷膜對(duì)鎂合金耐蝕性能的影響；在三種硅烷各自最佳添加量的基礎(chǔ)上,分別添加納米二氧化硅顆粒和鈰鹽離子對(duì)三種硅烷膜進(jìn)行改性,研究了改性前后硅烷膜耐蝕性能的變化。經(jīng)研究發(fā)現(xiàn)：采用電沉積方法在AZ31B鎂合金表面成功制備出了KH-560、KH-570和BTSE三種硅烷膜。48h體外模擬體液浸泡降解實(shí)驗(yàn)表明,三種硅烷膜均能有效延緩鎂合金的降解速率,硅烷膜優(yōu)先發(fā)生點(diǎn)腐蝕,其中KH-570硅烷膜厚度最大、結(jié)構(gòu)致密且較為均勻,其耐蝕性能最佳。動(dòng)電位極化曲線測(cè)試表明,鎂合金表面電沉積三種硅烷膜后,自腐蝕電位提高,自腐蝕電流密度大幅度下降。KH-560、KH-570和BTSE三種硅烷在鎂合金表面電沉積處理過程中存在最佳添加量,分別為6ml、8ml、4ml。鎂合金經(jīng)KH-560、 KH-570和BTSE三種硅烷電沉積處理后具有相似阻抗譜特征：在Nyquist圖中,高頻區(qū)和中低頻區(qū)各有一個(gè)容抗弧,前者半徑更大,而最低頻段裸鎂合金所具有的感抗弧消失；在阻抗-頻率Bode圖中,硅烷化處理后低頻阻抗值大幅增大,耐蝕性能有效提升；在相位角-頻率Bode圖中,三種硅烷在各自最佳添加量下低頻相位角值較大,峰值趨向于低頻范圍,而在中頻區(qū)和高頻區(qū),硅烷化使得相位角值穩(wěn)定提升,表明膜層中Si-O-Si鍵和Mg-O-Si鍵結(jié)合緊密。采用ZSimpWin電化學(xué)分析軟件建立了表面硅烷化鎂合金的等效電路模型(ECM),發(fā)現(xiàn)最佳添加量下,KH-570硅烷膜層C。值穩(wěn)定在10-7 F.cm-2量級(jí),硅烷膜層厚度最大,耐蝕性能最佳。添加納米二氧化硅顆粒或鈰鹽離子改性物質(zhì),能夠進(jìn)一步提升KH-560、KH-570和BTSE三種硅烷膜對(duì)AZ31B鎂合金耐腐蝕性能的改進(jìn)效果。與納米二氧化硅顆粒相比,鈰鹽離子具有更顯著的改性作用,其可以通過電化學(xué)輔助沉積與硅烷膜起到協(xié)同作用,使硅烷膜層具有一定的自修復(fù)能力,有效增加膜層厚度、降低膜層孔隙率。
[Abstract]:Magnesium alloys have excellent mechanical compatibility, biocompatibility and biodegradability, and have broad application prospects in the field of clinical medicine. However, the rapid corrosion rate seriously restricts its medical application. Silanization is a green and environmentally friendly corrosion protection technology which has been developed rapidly in recent years. It has been successfully applied on stainless steel, aluminum alloy and magnesium alloy and so on. In this paper, AZ31B magnesium alloy was silanized by electrochemical assisted deposition (ECD) method. KH-560, was studied by electrochemical workstation, scanning electron microscope, energy spectrometer and other instruments, and simulated degradation experiments in vitro. The optimum addition of KH-570 and BTSE in the deposition process were compared. The effects of three silanes films on the corrosion resistance of magnesium alloy were compared in the same electrodeposition process. On the basis of adding nano-silica particles and cerium ions, three kinds of silane membranes were modified by adding nano-silica particles and cerium ions respectively, and the changes of corrosion resistance of silane films before and after modification were studied. It was found that three kinds of KH-560,KH-570 and BTSE silicane films were successfully prepared on the surface of AZ31B magnesium alloy by electrodeposition. 48 h simulated humoral immersion degradation experiments showed that all of them could effectively delay the degradation rate of magnesium alloys. Among them, the thickness of KH-570 silicone film is the largest, its structure is dense and uniform, and its corrosion resistance is the best. The potentiodynamic polarization curves show that the corrosion potential increases and the corrosion current density decreases greatly after electrodeposition of three kinds of silanes on the surface of magnesium alloy. KH-560, The best addition amount of KH-570 and BTSE is 6ml, 8ml and 4ml respectively in the electrodeposition process of magnesium alloy surface. Magnesium alloys have similar impedance spectra after electrodeposition of KH-560, KH-570 and BTSE. In the Nyquist diagram, there is a capacitive arc in the high frequency region and the low frequency region, and the radius of the former is larger than that in the low frequency region. However, the induction arc of bare magnesium alloy in the lowest frequency band disappears. In the impedance-frequency Bode diagram, the low-frequency impedance value increases greatly after silylation treatment, and the corrosion resistance is improved effectively. In the phase angle-frequency Bode diagram, the low-frequency phase angle of the three silanes is larger and the peak value tends to the low-frequency range, but in the medium-frequency region and the high-frequency region, the phase angle is steadily increased by silanization, and the phase angle is increased steadily by silanization in the medium-frequency region and high-frequency region. The results show that the Si-O-Si bond and the Mg-O-Si bond are closely bound in the film. The equivalent circuit model of magnesium silanide alloy surface was established by means of ZSimpWin electrochemical analysis software. It was found that under the optimal addition of KH-570 silane film C. The value is stable in the order of 10 ~ 7 F.cm-2, the thickness of silane film is the largest, and the corrosion resistance is the best. The addition of nano-silica particles or cerium ions can further improve the corrosion resistance of AZ31B magnesium alloy with KH-560,KH-570 and BTSE silicone films. The results show that the corrosion resistance of AZ31B magnesium alloy can be improved by adding nano-Sio _ 2 particles or cerium ions. Compared with nano-silica particles, cerium ion has more obvious modification effect. It can cooperate with silane film by electrochemistry-assisted deposition, so that the silicone film layer has certain self-repairing ability, and the thickness of the film can be increased effectively. The porosity of the film was decreased.
【學(xué)位授予單位】：東南大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類號(hào)】：TG174.4;R318.08
本文編號(hào)：2462072
[Abstract]:Magnesium alloys have excellent mechanical compatibility, biocompatibility and biodegradability, and have broad application prospects in the field of clinical medicine. However, the rapid corrosion rate seriously restricts its medical application. Silanization is a green and environmentally friendly corrosion protection technology which has been developed rapidly in recent years. It has been successfully applied on stainless steel, aluminum alloy and magnesium alloy and so on. In this paper, AZ31B magnesium alloy was silanized by electrochemical assisted deposition (ECD) method. KH-560, was studied by electrochemical workstation, scanning electron microscope, energy spectrometer and other instruments, and simulated degradation experiments in vitro. The optimum addition of KH-570 and BTSE in the deposition process were compared. The effects of three silanes films on the corrosion resistance of magnesium alloy were compared in the same electrodeposition process. On the basis of adding nano-silica particles and cerium ions, three kinds of silane membranes were modified by adding nano-silica particles and cerium ions respectively, and the changes of corrosion resistance of silane films before and after modification were studied. It was found that three kinds of KH-560,KH-570 and BTSE silicane films were successfully prepared on the surface of AZ31B magnesium alloy by electrodeposition. 48 h simulated humoral immersion degradation experiments showed that all of them could effectively delay the degradation rate of magnesium alloys. Among them, the thickness of KH-570 silicone film is the largest, its structure is dense and uniform, and its corrosion resistance is the best. The potentiodynamic polarization curves show that the corrosion potential increases and the corrosion current density decreases greatly after electrodeposition of three kinds of silanes on the surface of magnesium alloy. KH-560, The best addition amount of KH-570 and BTSE is 6ml, 8ml and 4ml respectively in the electrodeposition process of magnesium alloy surface. Magnesium alloys have similar impedance spectra after electrodeposition of KH-560, KH-570 and BTSE. In the Nyquist diagram, there is a capacitive arc in the high frequency region and the low frequency region, and the radius of the former is larger than that in the low frequency region. However, the induction arc of bare magnesium alloy in the lowest frequency band disappears. In the impedance-frequency Bode diagram, the low-frequency impedance value increases greatly after silylation treatment, and the corrosion resistance is improved effectively. In the phase angle-frequency Bode diagram, the low-frequency phase angle of the three silanes is larger and the peak value tends to the low-frequency range, but in the medium-frequency region and the high-frequency region, the phase angle is steadily increased by silanization, and the phase angle is increased steadily by silanization in the medium-frequency region and high-frequency region. The results show that the Si-O-Si bond and the Mg-O-Si bond are closely bound in the film. The equivalent circuit model of magnesium silanide alloy surface was established by means of ZSimpWin electrochemical analysis software. It was found that under the optimal addition of KH-570 silane film C. The value is stable in the order of 10 ~ 7 F.cm-2, the thickness of silane film is the largest, and the corrosion resistance is the best. The addition of nano-silica particles or cerium ions can further improve the corrosion resistance of AZ31B magnesium alloy with KH-560,KH-570 and BTSE silicone films. The results show that the corrosion resistance of AZ31B magnesium alloy can be improved by adding nano-Sio _ 2 particles or cerium ions. Compared with nano-silica particles, cerium ion has more obvious modification effect. It can cooperate with silane film by electrochemistry-assisted deposition, so that the silicone film layer has certain self-repairing ability, and the thickness of the film can be increased effectively. The porosity of the film was decreased.
【學(xué)位授予單位】：東南大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類號(hào)】：TG174.4;R318.08
【參考文獻(xiàn)】
相關(guān)期刊論文 前10條
1 李傳福;李艷芳;;生物醫(yī)用鎂合金材料的應(yīng)用及抗腐蝕性研究進(jìn)展[J];輕工科技;2015年04期
2 吳海江;徐國榮;許劍光;徐紅梅;吳玉蓉;顏煥元;;AZ91D壓鑄鎂合金表面最佳硅烷成膜工藝及其耐蝕性能[J];材料保護(hù);2013年09期
3 喬麗英;何聰;談安強(qiáng);況新亮;高家誠;;硅烷化處理在鎂合金表面防腐中的應(yīng)用[J];功能材料;2013年09期
4 鄭玉峰;顧雪楠;李楠;周維瑞;;生物可降解鎂合金的發(fā)展現(xiàn)狀與展望[J];中國材料進(jìn)展;2011年04期
5 王增輝;衛(wèi)中領(lǐng);李春梅;陳秋榮;;鎂合金表面處理技術(shù)進(jìn)展[J];電鍍與涂飾;2010年08期
6 張微;龍軍峰;張津;丁婷;余永梅;張紅霞;馬培培;;硅烷增強(qiáng)鎂合金防腐有機(jī)涂層的研究[J];表面技術(shù);2009年06期
7 穆玉慧;孫翠艷;王健;王健一;謝鯤;;鎂合金表面處理研究進(jìn)展[J];新材料產(chǎn)業(yè);2009年02期
8 胡吉明;王曉梅;季衛(wèi)剛;張鑒清;曹楚南;;防護(hù)性硅烷膜的摻雜改性研究進(jìn)展[J];材料科學(xué)與工程學(xué)報(bào);2008年05期
9 張津;吳超云;黃福祥;張微;;AZ31B鎂合金表面硅烷處理研究[J];中國腐蝕與防護(hù)學(xué)報(bào);2008年03期
10 胡吉明;劉P ;張鑒清;曹楚南;;LY12鋁合金表面電化學(xué)沉積制備DTMS硅烷膜及其耐蝕性研究[J];高等學(xué)�；瘜W(xué)學(xué)報(bào);2006年06期
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