發(fā)布時(shí)間：2019-03-01 10:31

【摘要】：金屬包裝飲料罐因其密封性好、保質(zhì)期長(zhǎng)而被廣泛使用在飲料行業(yè)中。而金屬包裝罐的缺點(diǎn)之一就是易腐蝕。金屬包裝罐的腐蝕會(huì)致使飲料受污染或劣變從而威脅人們的身心健康,食品安全問(wèn)題也越來(lái)越突出。目前,金屬包裝罐的腐蝕機(jī)理尚不明確。因此,研究金屬包裝飲料罐的腐蝕行為和失效機(jī)理,預(yù)測(cè)金屬包裝飲料罐的耐蝕壽命,這對(duì)于減少食品安全問(wèn)題的發(fā)生具有極其重要的意義。首先,對(duì)金屬包裝飲料罐原材料馬口鐵在酸性飲料中的腐蝕電化學(xué)行為進(jìn)行了探討。結(jié)果表明,浸泡初期,錫層腐蝕電流密度很高,達(dá)到40μA/cm2。浸泡中期,基體碳鋼開(kāi)始暴露出來(lái),仍以錫層溶解為主。浸泡后期,碳鋼腐蝕速度為14μA/cm2,其能夠承擔(dān)的耐蝕壽命很短。大約經(jīng)過(guò)1個(gè)月的浸泡,錫層完全溶解。研究了酸性飲料罐罐體馬口鐵和罐底鋁之間的電偶腐蝕傾向,結(jié)果表明Sn-Al電偶對(duì)的電偶電位差為100mV左右,電偶電流為16μA/cm2左右。電偶腐蝕行為以Sn的腐蝕過(guò)程為主,屬于弱電偶腐蝕行為,可以忽略電偶腐蝕對(duì)金屬包裝飲料罐貨架壽命的影響。四種相同工藝生產(chǎn)的馬口鐵鈍化前后耐蝕性能的研究表明本文中使用的馬口鐵并未進(jìn)行高效鈍化。而采用我們的鈍化方法對(duì)馬口鐵進(jìn)行鈍化后,四種馬口鐵的耐蝕性明顯提高,其中F1馬口鐵鈍化效果最為明顯,表明我們采用的鈍化方法是合理和有效的。鍍錫量測(cè)定結(jié)果表明,F3馬口鐵鍍錫量誤差最小。在酸性飲料中彩印鐵的耐蝕性研究表明,經(jīng)過(guò)11個(gè)月的浸泡后,彩印鐵的涂層電阻遠(yuǎn)大于106Ω·cm2,表明彩印鐵環(huán)氧酚醛涂層此時(shí)仍然具有防護(hù)能力：低電位陰極極化加速彩印鐵涂層劣化過(guò)程與自然腐蝕狀態(tài)下彩印鐵涂層劣化過(guò)程具有很好的相關(guān)性,表明低電位陰極極化加速方法可以對(duì)彩印鐵的耐蝕壽命進(jìn)行預(yù)測(cè)。其次,在大批次飲料實(shí)罐樣品的基礎(chǔ)上,通過(guò)統(tǒng)計(jì)分析,建立了以實(shí)罐涂層電阻Rc和Fe元素濃度為變量的金屬包裝飲料罐耐蝕壽命預(yù)測(cè)模型。該模型屬于機(jī)理型模型。運(yùn)用該模型解析了紅牛飲料罐防護(hù)體系在飲料液作用下逐漸劣化和失效的兩個(gè)階段：第一階段是涂層快速滲水階段。第二階段是涂層下滲入介質(zhì)積累和腐蝕積累階段。模型的轉(zhuǎn)折參數(shù)Rc.tp和[Fe]tp分別表示涂層滲水已到達(dá)金屬表面的涂層電阻和口味劣化的臨界鐵元素濃度值。從金屬飲料包裝空罐加速耐蝕實(shí)驗(yàn)結(jié)果中可以看出,低電位加速腐蝕試驗(yàn)結(jié)果與自然條件下飲料罐涂層失效過(guò)程的結(jié)果和模型行為一致,表明低電位陰極極化加速涂層失效試驗(yàn)與自然腐蝕試驗(yàn)具有良好的相關(guān)性。兩者結(jié)合可用于預(yù)測(cè)金屬包裝飲料罐的耐蝕質(zhì)量水平,可作為日常檢測(cè)方法。
[Abstract]:Metal-packed beverage cans are widely used in the beverage industry because of their good sealing and long shelf life. And one of the disadvantages of the metal packaging tank is that it is easy to corrode. The corrosion of metal packaging can lead to contamination or deterioration of drinks, which threaten people's physical and mental health, and food safety problems are becoming more and more prominent. At present, the corrosion mechanism of metal packaging tank is not clear. Therefore, it is of great significance to study the corrosion behavior and failure mechanism of metal-packed beverage cans and to predict the corrosion-resistant life of metal-packed beverage cans, which is of great significance to reduce the occurrence of food safety problems. Firstly, the corrosion electrochemical behavior of metal packed drinking pot raw material tinplate in acidic beverage was discussed. The results show that the corrosion current density of tin layer is very high at the initial stage of immersion, which is up to 40 渭 A / cm2.. In the middle of immersion, the matrix carbon steel began to be exposed, still mainly dissolved in tin layer. At the later stage of immersion, the corrosion rate of carbon steel is 14 渭 A / cm2, and the corrosion-resistant life of carbon steel is very short. After about 1 month of immersion, the tin layer completely dissolved. The galvanic corrosion tendency between tinplate and aluminum in acid beverage tank was studied. The results show that the couple potential difference of Sn-Al pair is about 100mV and the galvanic current is about 16 渭 A / cm2. The corrosion behavior of Sn is mainly in the corrosion process, which belongs to weak galvanic corrosion. The influence of galvanic corrosion on shelf life of metal packaging beverage can be ignored. The study of corrosion resistance before and after passivation of four kinds of tinplate produced by the same process shows that the tinplate used in this paper has not been passivated efficiently. After passivation with our passivation method, the corrosion resistance of four kinds of tinplate was improved obviously, and the passivation effect of F1 tinplate was the most obvious, which indicated that the passivation method we used was reasonable and effective. The results of tin plating show that the error of tinning amount in F3 tinplate is the smallest. The corrosion resistance of color printing iron in acid beverage shows that after 11 months' immersion, the coating resistance of color printing iron is far greater than 106 惟 cm2,. The results show that the color printing iron epoxy phenolic coating still has the protective ability at this time: the low potential cathodic polarization accelerates the deterioration process of the color printing iron coating and the degradation process of the color printing iron coating under the natural corrosion condition has a good correlation with the degradation process of the color printing iron coating under the natural corrosion condition. The results show that the low-potential cathodic polarization acceleration method can predict the corrosion-resistant life of color-printed iron. Secondly, on the basis of a large number of solid beverage can samples, a corrosion-resistant life prediction model for metal packaging beverage cans is established, which takes the concentration of Rc and Fe elements as variables, based on the statistical analysis of the coating resistance of the real cans. The model belongs to the mechanical model. This model is used to analyze the two stages of gradual deterioration and failure of the protective system of Red Bull Beverage Tank under the action of beverage liquid. The first stage is the rapid infiltration stage of coating. The second stage is the accumulation of infiltration media and corrosion accumulation under the coating. The transition parameters of the model, Rc.tp and [Fe] tp, respectively, indicate the coating resistance and the critical iron concentration of poor taste when the coating has reached the surface of the metal. From the experimental results of accelerated corrosion resistance of metal beverage packaging empty cans, it can be seen that the results of low potential accelerated corrosion test are consistent with the failure process and model behavior of the coating of beverage cans under natural conditions. The results show that there is a good correlation between low potential cathodic polarization accelerated coating failure test and natural corrosion test. The combination of the two methods can be used to predict the corrosion resistance quality of metal packed beverage cans and can be used as a routine test method.
【學(xué)位授予單位】：中國(guó)海洋大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2014
【分類(lèi)號(hào)】：TB484.4;TG172

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