铝合金在海水中的腐蚀性能研究
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摘要
铝合金具有优异的耐蚀性能,在海洋开发中占有不可替代的地位,然而海水中含有大量的腐蚀性氯离子,铝合金在海水中因氧化膜的破裂而极易发生局部腐蚀,因此,研究深海环境下铝合金的腐蚀行为对海洋工程显得非常重要。本论文采用动电位扫描、电化学阻抗谱(electrochemical impedance spectroscopy,EIS)等电化学技术结合扫描电子显微镜(SEM)、三维视屏等材料研究手段对1060、5083两种铝合金在不同状态的海水中的腐蚀行为进行了研究。主要研究结果为以下几个方面：
1.研究了5083铝合金在不同温度和不同溶解氧的海水中的腐蚀行为,以及1060和5083两种铝合金在实海中连续挂样一年的月平均腐蚀速率。当溶解氧为6.5 mg/L时,随着温度的降低,5083铝合金自腐蚀电位和点蚀电位正移,维钝电流密度减小；在溶解氧浓度为2 mg/L的状态下,随着温度的降低,5083铝合金自腐蚀电位负移,点蚀电位正移,维钝电流密度增大。随着温度的降低,电化学阻抗谱中容抗弧直径逐渐增大,阻抗模值增大。低温时,阻抗谱为一容抗弧,温度升高时,低频出现Warburg阻抗。腐蚀微观形貌分析结果表明铝合金在高温高氧状态下主要以均匀腐蚀为主,而在低温低氧状态下发生了明显点蚀。在实海中,温度是影响1060和5083铝合金在海水中腐蚀速率的主要因素,两种铝合金的腐蚀规律相似,5083铝合金腐蚀速率稍高于1060。
2.研究了5083铝合金在低温低氧下不同pH的海水中的腐蚀行为。随着pH值的升高,5083铝合金自腐蚀电位负移,维钝电流密度增大,钝化区范围扩大,但点蚀电位变化不大。交流阻抗谱结果表明：随着pH值的升高,容抗弧直径逐渐减小,阻抗模值减小,这说明铝合金在碱性海水中腐蚀速度增大,当pH值为7.2、7.7、8.2时,低频出现Warburg阻抗,阴极过程受扩散控制。pH值越低,5083铝合金表面越容易发生点蚀,随着pH值的升高,5083铝合金以均匀腐蚀为主。
3.研究了5083铝合金在低温低氧环境下孔蚀发展过程,发现随着浸泡时间的延长,5083铝合金自腐蚀电位和点蚀电位正移,钝化区范围扩大,而维钝电流密度先减小,而后基本稳定,阻抗模值先增大,后减小。同时,5083铝合金电极在浸泡0-12 h后,铝合金表面氧化膜较为完整,处于点蚀诱发期,浸泡至12-48 h后,有大量的点蚀坑生成,处于点蚀发展期,浸泡至48-96 h时,蚀坑数量减少,处于腐蚀过渡期,96 h以后,试样表面生成了一层氧化膜,铝合金发生均匀腐蚀,处于腐蚀后期。
Aluminum alloys are commonly used in marine application with excellent corrosion resistance. Since seawater is recognized to be very corrosive for metals, the oxide film breaks down at specific points leading to the formation of pits on the aluminum surface. It is necessary to study the corrosion and its protection of aluminum alloy in deep-sea and-corrosion rate of aluminum alloys in different kinds of seawater is an important corrosion parameter which is widely used in marine engineering. In this paper, potentiodynamic scanning, electrochemical impedance spectroscopy(EIS) electrochemical techniques and scanning electron microscopy(SEM),3D screen materials research tools were used to study the corrosion behaviors of aluminum alloys 1060 and 5083 in different kinds of seawater. The research results of this paper are as follows:
1. The effect of temperature and dissolved oxygen on the corrosion behavior of aluminum alloy 5083 in seawater and the change of average monthly corrosion rate of aluminum alloys 1060 and 5083 in real sea were studied. When the dissolved oxygen was 6.5mg/L with decrease of the temperature, the corrosion potential of aluminum alloy 5083 and pitting potential shifted positively, passive current density decreased; when the dissolved oxygen was 2mg/L with decreased of the temperature, the corrosion potential of aluminum alloy 5083 shifted negatively, the pitting potential shifted positively, and passive current density increased. With decreasing temperature, capacitance arc diameter increased, so the impedance modulus increased. Impedance spectroscopy showed a capacitance arc in low temperature, low-frequency Warburg impedance appeared in high temperature. The morphology of the alloy 5083 showed that the alloy 5083 suffered obvious pitting corrosion in seawater at low temperature and low content of dissolved oxygen, while the oxide films were prone to form on the alloy 5083 at high temperature and dissoved oxygen. Temperature was the main factor affecting corrosion rate of aluminum alloy 1060 and 5083 in real sea, corrosion rate of the two aluminum alloys had similar a law, but the corrosion rate of aluminum alloy 5083 was higher than that of aluminum alloy 1060.
2. The effect of pH on the corrosion behavior of aluminum alloy 5083 in seawater at low temperature and dissolved oxygen was studied. The corrosion potential of aluminum alloy 5083 shifted negatively, passive current density increased and the passivation region broadened, but the pitting potential changed little with the increase of pH value. The result obtained from AC impedance test indicated that capacitance arc diameter decreased, the impedance modulus decreased with the he increase of pH value, showing the fastest corrosion rate of aluminum alloy 5083 in alkaline seawater. When the pH value was 7.2,7.7,8.2, Warburg impedance appeared at low frequency, and the cathode process was controlled by diffusion. The lower the pH value, the more easily occurred pitting corrosion, with the pH value increased, aluminum alloy 5083 mainly occurred uniform corrosion.
3. The pitting process of aluminum alloy 5083 in seawater at low temperature and dissolved oxygen was studied. We found the corrosion potential and the pitting potential of aluminum alloy 5083 shifted positively with the immersion time prolonging, the passivation-region-broadened,but passive current density decreased firstly, and then became stably, the impedance modulus increased firstly, and then decreased. We also found when the aluminum alloy 5083 was immersed 0-12h, the oxide film was complete, this period was at pitting initiation. After being immersed 12-48h, a large number of pits generated, this period was at pitting development. After 48-96h, the number of pits decreased, this period was at corrosion middle stage. After 96h, the sample surface generated oxide film, the aluminum alloy 5083 mainly occurred uniform corrosion, this period was at corrosion later stage.
1.研究了5083铝合金在不同温度和不同溶解氧的海水中的腐蚀行为,以及1060和5083两种铝合金在实海中连续挂样一年的月平均腐蚀速率。当溶解氧为6.5 mg/L时,随着温度的降低,5083铝合金自腐蚀电位和点蚀电位正移,维钝电流密度减小；在溶解氧浓度为2 mg/L的状态下,随着温度的降低,5083铝合金自腐蚀电位负移,点蚀电位正移,维钝电流密度增大。随着温度的降低,电化学阻抗谱中容抗弧直径逐渐增大,阻抗模值增大。低温时,阻抗谱为一容抗弧,温度升高时,低频出现Warburg阻抗。腐蚀微观形貌分析结果表明铝合金在高温高氧状态下主要以均匀腐蚀为主,而在低温低氧状态下发生了明显点蚀。在实海中,温度是影响1060和5083铝合金在海水中腐蚀速率的主要因素,两种铝合金的腐蚀规律相似,5083铝合金腐蚀速率稍高于1060。
2.研究了5083铝合金在低温低氧下不同pH的海水中的腐蚀行为。随着pH值的升高,5083铝合金自腐蚀电位负移,维钝电流密度增大,钝化区范围扩大,但点蚀电位变化不大。交流阻抗谱结果表明：随着pH值的升高,容抗弧直径逐渐减小,阻抗模值减小,这说明铝合金在碱性海水中腐蚀速度增大,当pH值为7.2、7.7、8.2时,低频出现Warburg阻抗,阴极过程受扩散控制。pH值越低,5083铝合金表面越容易发生点蚀,随着pH值的升高,5083铝合金以均匀腐蚀为主。
3.研究了5083铝合金在低温低氧环境下孔蚀发展过程,发现随着浸泡时间的延长,5083铝合金自腐蚀电位和点蚀电位正移,钝化区范围扩大,而维钝电流密度先减小,而后基本稳定,阻抗模值先增大,后减小。同时,5083铝合金电极在浸泡0-12 h后,铝合金表面氧化膜较为完整,处于点蚀诱发期,浸泡至12-48 h后,有大量的点蚀坑生成,处于点蚀发展期,浸泡至48-96 h时,蚀坑数量减少,处于腐蚀过渡期,96 h以后,试样表面生成了一层氧化膜,铝合金发生均匀腐蚀,处于腐蚀后期。
Aluminum alloys are commonly used in marine application with excellent corrosion resistance. Since seawater is recognized to be very corrosive for metals, the oxide film breaks down at specific points leading to the formation of pits on the aluminum surface. It is necessary to study the corrosion and its protection of aluminum alloy in deep-sea and-corrosion rate of aluminum alloys in different kinds of seawater is an important corrosion parameter which is widely used in marine engineering. In this paper, potentiodynamic scanning, electrochemical impedance spectroscopy(EIS) electrochemical techniques and scanning electron microscopy(SEM),3D screen materials research tools were used to study the corrosion behaviors of aluminum alloys 1060 and 5083 in different kinds of seawater. The research results of this paper are as follows:
1. The effect of temperature and dissolved oxygen on the corrosion behavior of aluminum alloy 5083 in seawater and the change of average monthly corrosion rate of aluminum alloys 1060 and 5083 in real sea were studied. When the dissolved oxygen was 6.5mg/L with decrease of the temperature, the corrosion potential of aluminum alloy 5083 and pitting potential shifted positively, passive current density decreased; when the dissolved oxygen was 2mg/L with decreased of the temperature, the corrosion potential of aluminum alloy 5083 shifted negatively, the pitting potential shifted positively, and passive current density increased. With decreasing temperature, capacitance arc diameter increased, so the impedance modulus increased. Impedance spectroscopy showed a capacitance arc in low temperature, low-frequency Warburg impedance appeared in high temperature. The morphology of the alloy 5083 showed that the alloy 5083 suffered obvious pitting corrosion in seawater at low temperature and low content of dissolved oxygen, while the oxide films were prone to form on the alloy 5083 at high temperature and dissoved oxygen. Temperature was the main factor affecting corrosion rate of aluminum alloy 1060 and 5083 in real sea, corrosion rate of the two aluminum alloys had similar a law, but the corrosion rate of aluminum alloy 5083 was higher than that of aluminum alloy 1060.
2. The effect of pH on the corrosion behavior of aluminum alloy 5083 in seawater at low temperature and dissolved oxygen was studied. The corrosion potential of aluminum alloy 5083 shifted negatively, passive current density increased and the passivation region broadened, but the pitting potential changed little with the increase of pH value. The result obtained from AC impedance test indicated that capacitance arc diameter decreased, the impedance modulus decreased with the he increase of pH value, showing the fastest corrosion rate of aluminum alloy 5083 in alkaline seawater. When the pH value was 7.2,7.7,8.2, Warburg impedance appeared at low frequency, and the cathode process was controlled by diffusion. The lower the pH value, the more easily occurred pitting corrosion, with the pH value increased, aluminum alloy 5083 mainly occurred uniform corrosion.
3. The pitting process of aluminum alloy 5083 in seawater at low temperature and dissolved oxygen was studied. We found the corrosion potential and the pitting potential of aluminum alloy 5083 shifted positively with the immersion time prolonging, the passivation-region-broadened,but passive current density decreased firstly, and then became stably, the impedance modulus increased firstly, and then decreased. We also found when the aluminum alloy 5083 was immersed 0-12h, the oxide film was complete, this period was at pitting initiation. After being immersed 12-48h, a large number of pits generated, this period was at pitting development. After 48-96h, the number of pits decreased, this period was at corrosion middle stage. After 96h, the sample surface generated oxide film, the aluminum alloy 5083 mainly occurred uniform corrosion, this period was at corrosion later stage.
引文
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