海南滨海大气环境中棘孢曲霉对铝合金腐蚀行为影响

图1 液体培养基棘孢曲霉的pH值变化

Fig.1 Changes of pH value of Aspergillus aculeatus in liquid medium

液体培养基中棘孢曲霉产生的有机酸浓度如表1所示。草酸的含量显著高于其他有机酸，随着时间延长，草酸、酒石酸、苹果酸和乙酸的含量持续上升，而乳酸和乙酸、柠檬酸的含量逐渐降低，有报道表明是由于有机物的缺乏，导致棘孢曲霉将有机酸作为碳源来维持其代谢^[22~24]。

表1 液体培养基棘孢曲霉的有机酸浓度

Table 1 Organic acid concentration of Aspergillus aculeatus in liquid medium

Time d	pH	Oxalic acid mg/mL	Tartaric acid mg/mL	Malic acid mg/mL	Lactic acid mg/mL	Acetic acid mg/mL	Citric acid mg/mL
1	6.03	3234.8	18.6	21.3	8.1	25.4	14.9
3	4.38	3571.9	19.5	23.7	2.5	31.5	1.8
5	4.89	4560.0	20.7	30.2	4.3	25.4	2.3
7	5.99	5003.1	21.2	31.2	0.8	18.7	2.9
10	5.23	6074.3	24.7	38.1	1.3	4.5	1.1
14	5.56	6223.9	35.2	67.5	0.4	2.9	0.1

2.2 宏观形貌

图2为在5A02铝合金试样表面喷涂纯PDB培养基的无菌组在不同暴露时间下的宏观形貌。初期部分培养基生成有机物颗粒聚集随机分布在材料表面，随着实验时间的增加，白色有机物团颜色加深，出现结块现象，PDB培养基逐渐失去水分，开始出现裂纹且越来越多，暴露14 d后样品表面结块区域发生腐蚀，腐蚀区域较四周颜色偏黄。

图2

图2 无菌组在不同暴露时间后的5A02铝合金表面宏观形貌

Fig.2 Macroscopic morphologies of 5A02 Al-alloy surface in aseptic group after 1 d (a), 3 d (b), 7 d (c) and 14 d (d) exposure time

图3是经过稀释后的孢子浓度为1 × 10⁵ /mL的棘孢曲霉悬浮液喷涂在5A02铝合金试样上的宏观形貌。1 d后棘孢曲霉孢子开始吸收水分与营养物质生成菌丝，且在溶液的交界处出现棘孢曲霉孢子堆积的现象；3 d后棘孢曲霉不断生长繁殖生成菌丝体，棘孢曲霉不断长大，逐渐生成分生孢子散布在5A02铝合金表面；7 d后在5A02铝合金表面观察到更粗、更大且脉络清晰的菌丝体，到14 d随着菌丝水分的流失，菌丝紧密贴附在5A02铝合金表面。

图3

图3 有菌组在不同暴露时间后的5A02铝合金表面宏观形貌

Fig.3 Macroscopic morphologies of 5A02 Al-alloy surface in bacteria-containing group after 1 d (a), 3 d (b), 7 d (c) and 14 d (d) exposure time

图4为除锈后5A02铝合金试样表面共聚焦形貌。除锈后在无菌和接种棘孢曲霉的样品表面上可以看到不同程度的蚀坑，如图4a和b所示。无菌组的腐蚀区域是随机的，主要发生在有机物聚集的地方，有菌组腐蚀主要集中在棘孢曲霉菌丝附着的区域以及孢子悬浮液边界区域。与无菌样品相比，接种棘孢曲霉的样品的表面损伤更严重。试样表面蚀坑参数如表2所示，接种棘孢曲霉样品表面区域cd的蚀坑水平宽度明显宽于无菌样品表面区域ab，区域cd的蚀坑垂直深度大于区域ab，表明棘孢曲霉一定程度上可以促进5A02铝合金的腐蚀。

图4

图4 暴露14 d试样除锈后表面共聚焦形貌

Fig.4 Confocal morphologies of the surface of the sample after 14 d of exposure after rust removal: (a) sterility, (b) bacterium

表2 在0.01%NaCl薄液膜下试样表面蚀坑参数

Table 2 Parameters of etch pits on the sample surface under 0.01%NaCl thin liquid film

Area	Horizon / μm	Vertical / μm
ab	125.356	4.393
cd	513.086	10.139

2.3 微观形貌观测及成分测定

图5为无菌组5A02铝合金试样表面的微观形貌。初期部分培养基沉积生成有机物颗粒呈片状聚集随机分布在材料表面，部分颗粒嵌入基体缺陷处，随着时间延长，出现结块现象，培养基逐渐失去水分，导致结块出现裂纹和龟裂状产物，伴随着层片结构逐步细化，团絮状腐蚀产物开始在表面生成，形成分层，该层腐蚀产物极为疏松且存在明显的裂纹。

图5

图5 无菌组在不同暴露时间后的5A02铝合金表面微观形貌

Fig.5 Surface morphologies of 5A02 Al-alloy in sterile group after 1 d (a), 3 d (b), 7 d (c) and 14 d (d) exposure time

表3为14 d后无菌组5A02铝合金表面的元素含量。通过能谱扫描可以看出B区域的Al含量远高于其他元素，确定为铝基体。A区域试样表层O、C含量要高于基体，可能为培养基结块和铝的腐蚀产物。

表3 无菌试样表面EDS元素含量 (mass fraction / %)

Table 3 EDS element content on the surface of sterile samples

Position	Al	Cl	O	C	Na	Mg	Total
A	59.68	0.84	20.85	17.03	-	1.6	100
B	85.45	-	6.20	6.30	-	2.05	100

图6为有菌组5A02铝合金试样表面的微观形貌。图6a和b所示，暴露1 d后棘孢曲霉生成大量菌丝覆盖到材料表面，在菌液与5A02铝合金交界处少量孢子定殖到材料表面，发生腐蚀。图6c和d所示，3 d后可以观察到菌丝发育比较完全，菌丝顶端形成大量孢子分散到四周，且在中心区域观察到菌丝与基体表面紧密贴合并且开始出现裂纹，菌丝断裂处有腐蚀产物聚集。图6e和f所示，7 d后铝合金基体表面形成了一层薄薄的、相对致密的腐蚀产物，呈现出不规则片状分布和龟裂状态，随时间延长腐蚀产物逐渐堆积成块状，且内部产生了较深的裂纹，同时棘孢曲霉菌丝连同菌丝顶端孢子囊由于水分流失发生裂解。图6g和h所示，14 d后腐蚀产物上出现表面光滑的球状物体，同时观察到棘孢曲霉通过裂纹将菌丝延伸到腐蚀产物层，加速了铝合金的腐蚀。与最终周期的无菌样品相比，接种棘孢曲霉的样品的表面粗糙度更高，并且含有更多的腐蚀产物，这些腐蚀产物与微生物活性分泌物相互混合。

图6

图6 有菌组在不同暴露时间后的5A02铝合金表面微观形貌

Fig.6 Surface morphologies of 5A02 Al-alloy after 1 d (a, b), 3 d (c, d), 7 d (e, f) and 14 d (g, h) exposure time in the bacterial group

表4为14 d后有菌组5A02铝合金表面的元素含量。从EDS结果得出A区域主要由Al、O、C组成，说明Al基体表层被一层产物膜覆盖，通过与无菌组基体成分比较，碳含量明显升高，说明A区域为PDB培养基析出的有机物。区域B主要由Al、Cl、O、C组成，相较于A区，B区的Al和C明显降低，O和Cl明显升高；A区O主要来源于培养基，含量为8.66%，B区氧含量为24.09%，明显高于A区，说明B区O主要来源于Al的腐蚀产物，同时可以看到该区的Cl含量很高，达31.32%，表明B区的主要腐蚀产物由铝的氧化物和氯化物共同构成。区域C以Al、O为主，说明该区的主要腐蚀产物为铝的氧化物。

表4 有菌组试样表面EDS元素含量 (mass fraction / %)

Table 4 EDS element content on the surface of samples with bacteria group

Position	Al	Cl	O	C	Na	Mg	Total
A	51.21	0.32	8.66	38.13	0.53	1.15	100.00
B	28.77	31.21	24.09	15.12	0.49	0.32	100.00
C	32.14	3.73	57.58	4.28	1.58	0.69	100.00

通过对有菌组A区域与无菌组B区域作比较可以看出，菌组A区域O含量低于无菌组B区域，表明无菌组B区域存在腐蚀产物。进一步比较以上5个区域看出无菌组B区与有菌组A、B、C区域均含有Cl，并且随着Cl含量的增加，结块现象越严重，说明Cl是本次实验影响腐蚀结果的主要因素之一。图7为霉菌腐蚀后的5A02铝合金样品表面的能谱面扫描元素分布图，可以看出右侧结块区域Cl、O含量要高于左侧区域，且菌丝处Cl^-含量很高。一定浓度的Cl^-对铝合金的均匀腐蚀使霉菌迅速附着，其菌丝结构可以从周围环境中吸收Cl^-以维持细胞内的离子平衡，棘孢曲霉在生长代谢过程中释放酸性有机物改变材料表面pH，协同Cl^-加快铝合金的腐蚀^[25~28]。

图7

图7 霉菌腐蚀后的5A02铝合金样品表面的能谱面扫描元素分布图

Fig.7 EDS mapping of 5A02 Al-alloy sample surface after mold degradation: (a) SEM, (b) Al, (c) Cl, (d) Na, (e) C, (f) O

2.4 腐蚀产物XPS测定

利用XPS对5A02铝合金的腐蚀产物进行了分析。图8为经过14 d棘孢曲霉腐蚀后的5A02铝合金样品表面全谱与元素的高分辨图谱，总体谱图显示了Al 2p、O 1s和C 2p的特征峰位。为了更深入的探究可能存在的腐蚀产物，进一步对各个元素的高分辨图谱做了细致的分峰处理。

图8

图8 霉菌腐蚀后的5A02铝合金样品表面的XPS谱图

Fig.8 XPS full spectrum and high-resolution spectra of elements on the surface of 5A02 Al-alloy samples after mold degradation: (a) full spectrum, (b) Al 2p spectrum, (c) C 1s spectrum, (d) O 1s spectrum

Al 2p谱图主要在74.2 eV处出现1个峰，对应于样品表面的AlO(OH)，另外在74.6 eV处的峰对应于样品表面的Al₂O₃，在72.9 eV处的峰对应于样品表面的Al。在O 1s谱图中，531.1 eV处的峰对应于Al₂O₃，531.5处的峰对应于AlO(OH)，结合Al 2p谱图可以推断出铝合金表面腐蚀产物主要由AlO(OH)和Al₂O₃组成，除此之外，在529.8 eV处的峰对应于MgO，532.5 eV处的峰对应于C=O基团，对应于C 1s的XPS光谱。C 1s谱图显示位于284，284.8和287.8 eV的峰分别对应于C-H，C-C和C=O基团，可能来源于培养基以及棘孢曲霉代谢物。

2.5 SKP测定

由于5A02铝合金试样表面均被棘孢曲霉所覆盖，裸露出基体的部位相当稀少，因此选择了有菌落或培养基结块覆盖的区域作为测试区域。图9所示为5A02铝合金试样在棘孢曲霉腐蚀实验不同时间后表面SKP电位分布图。从图中可以观察到，有菌组的整体伏打电位低于无菌组。棘孢曲霉是好氧菌，其菌丝在繁殖过程需要消耗O₂，因此被菌丝覆盖的区域氧气浓度相对周围裸露基体区域低，从而形成了以菌丝覆盖地区为阳极、周围裸露基体区域为阴极的氧浓差电池^[29,30]。

图9

图9 5A02铝合金试样暴露不同时间后表面SKP电位分布图

Fig.9 SKP potential distribution on the surface of 5A02 aluminum alloy sample after exposure test in bacteria group (a-d) and sterile group (e-h) for 1 d (a, e), 3 d (b, f), 7 d (c, g) and 14 d (d, h)

对有菌组样品表面SKP电位进行分析显示，随着腐蚀时间的增加，5A02铝合金表面电位出现先升高后降低的趋势，且在14 d后电位出现最负值。试验1~3 d，棘孢曲霉大量繁殖并堆积在试样表面，棘孢曲霉在其生长区域和周边裸露区域之间构成腐蚀电偶，并在代谢时分泌出大量的有机酸和无机酸，一定程度上加速了腐蚀过程的发生，使得表面电位逐渐升高。虽然在棘孢曲霉生物膜下Al基体会继续发生腐蚀，其表层电位会随着棘孢曲霉的生长而越来越正，但如图9f所示，在实验后期7~14 d，菌丝与基体紧密连接，导致局部腐蚀现象，所以探针可以检测到样品表面的实际电位信号，显示为越来越负。棘孢曲霉的生长活动加剧了局部腐蚀，进而导致整体腐蚀更加严重。

通过扫描Kelvin探针测到的电位 $φ_{k p}$ 与工作电极在大气环境下腐蚀电位 $φ_{c o r r}$ 有下列关系：

φ_{c o r r} = (\frac{W_{r e f}}{F} - \frac{φ_{r e f}}{2}) + φ_{k p}

(1)

其中，F为Faraday常数，W_ref为电极的功函数，φ_ref/2为参比电极的半电池电位。振动探针用作参考电极，对于测量系统来说，W_ref和φ_ref/2的数值是恒定的。因此，φ_kp与φ_corr呈正相关，可以反映样品在大气下的腐蚀情况。

表5为对应Gaussian拟合参数，拟合公式如式(2)所示，y为高斯分布的方差，用来表示电位分布的集中程度，y值越小表明电位分布越趋近于期望值，表现出更为集中的分布特性^[31]。从表5可以看出，有菌组的电位变化幅度更大且整体电位较无菌组更负。

y = y_{0} + \frac{A}{σ \sqrt[]{π / 2}} e x p [- 2 {(x - μ)}^{2} / σ^{2}]

(2)

其中，μ是电势分布的期望值，而σ是高斯分布的标准偏差，表示电势分布的分散程度。

表5 5A02铝合金样品表面Kelvin电势分布的高斯拟合参数

Table 5 Gaussian fitting parameters of Kelvin potential distribution on the surface of 5A02 aluminum alloy sample

Aspergillus aculeatus	μ / V	σ²	Sterile	μ / V	σ²
a	-0.76880	1.30991²	e	-0.31640	0.87380²
b	0.11045	0.12054²	f	0.22938	0.119191²
c	-0.75514	6.62063²	g	-0.39034	0.14449²
d	-0.82554	0.53990²	h	-0.50451	0.53199²

2.6 腐蚀机理研究

铝合金腐蚀首先是表面钝化膜的局部损伤，Cl^-会对铝合金表面钝化膜造成侵蚀，棘孢曲霉可以直接从铝合金中获取一些Fe、Cu、Mg元素作为营养物质，以提高它们的代谢活性^[32]，并且棘孢曲霉分泌的由蛋白质、多糖和有机酸组成的胞外聚合物(EPS)会降低钝化膜的稳定性，加快铝合金的腐蚀速率^[33]。此外，Cui等^[34]、Dong等^[35]也曾指出微生物可以直接或间接地促进钝化膜的部分溶解。

棘孢曲霉对5A02铝合金的腐蚀过程可分为3个阶段。前期主要为化学腐蚀，如式(3)~(8)所示。培养基中的营养物质与水分能够充分满足霉菌的生长需求，棘孢曲霉孢子在第1 d迅速“萌发”生成菌丝，霉菌生长代谢过程产生以草酸为主的大量有机酸。草酸在水中溶解度很高，霉菌产生的草酸溶解在铝合金薄液膜上发生化学腐蚀，将Al氧化为Al³⁺，Al³⁺在酸性环境下与Cl^-结合生成络合离子AlOHCl⁺，在5A02铝表面上产生酸腐蚀性介质，从而破坏表面氧化膜促进基体腐蚀。Wang等^[36]的研究也证实了霉菌代谢会产生大量草酸，引起介质酸化的同时加速铝合金的腐蚀，霉菌的存在引起的有机酸腐蚀是铝合金腐蚀的主要原因。

有机酸的电离和水解(以草酸为例)：

H_{2} C_{2} O_{4} ⇌ H C_{2} O_{4}^{-} + H^{+}

(3)

H C_{2} O_{4}^{-} ⇌ C_{2} O_{4}^{2 -} + H^{+}

(4)

H C_{2} O_{4}^{-} + H ₂ O ⇌ H_{2} C_{2} O_{4} + O H ⁻

(5)

化学腐蚀：阳极：

A l \to A l^{3 +} + 3 e^{-}

(6)

阴极：

3 H^{+} + 3 e^{-} \to 3 / 2 H_{2}

(7)

A l^{3 +} + H_{2} O + C l^{-} \to H^{+} + A l O H C l^{+}

(8)

中期主要为氧浓差腐蚀，如式(9)~(11)所示。对于氧浓差电池，富氧区电极电位较正，为金属阴极；而贫氧区电极电位较负，为金属阳极。伴随着水分的流失与pH升高，棘孢曲霉通过生长代谢在5A02铝合金样品表面逐渐生成菌落，棘孢曲霉在生长过程中会消耗氧气形成贫氧区，另外，腐蚀产物局部堆积也会限制氧的扩散从而也会导致贫氧区的产生^[37]，因此棘孢曲霉生长覆盖区域的电势就相对较负，从而与周边无菌生长区域形成氧浓差电池。腐蚀则发生在贫氧富氧区域交界处的贫氧侧，由此形成了以棘孢曲霉为中心的腐蚀区域。随着时间的流逝，棘孢曲霉生长，阳极反应的区域逐渐扩大，贫氧腐蚀区域向外扩展，从而形成了相对较浅但较宽的腐蚀区域。

电化学腐蚀：阳极：

A l \to A l^{3 +} + 3 e^{-}

(9)

M g \to M g^{2 +} + 2 e^{-}

(10)

阴极：

O_{2} + 4 H^{+} + 4 e^{-} \to 2 H_{2} O

(11)

后期主要为点蚀。随着暴露实验进行，棘孢曲霉逐渐干涸，样品表面逐渐显漏出来。部分棘孢曲霉孢子定殖蚀坑内部伴随着氯离子的富集与棘孢曲霉代谢产酸，使腐蚀沿着样品更深处发生。

3 结论

(1) 通过对5A02铝合金试样的宏观形貌、微观形貌进行观测，棘孢曲霉在5A02铝合金表面经历以下3个阶段：孢子萌发形成菌丝体、生成的分生孢子吸收营养物质形成菌丝、菌丝干涸与材料表面连接紧密。棘孢曲霉在生长代谢过程中可以分泌各种有机酸，以草酸为主，提高了5A02铝合金的腐蚀速率。

(2) 利用EDS和XPS对5A02铝合金的腐蚀产物成分进行分析，主要由AlO(OH)、Al₂O₃和MgO组成。对5A02铝合金样品表面进行伏打电位测定，结果表明有菌组的电位变化幅度更大且整体电位较无菌组更负，且有菌组电位随着时间的延长出现先升高后降低的趋势。

(3) 棘孢曲霉对5A02铝合金腐蚀的影响表现为：前期在棘孢曲霉与材料的交界处孢子嵌入到样品里，伴随着腐蚀产物的生成；中期在棘孢曲霉定殖的地方以及Cl^-富集的地方出现干裂现象，且棘孢曲霉失去水分，出现裂解现象；后期腐蚀产物逐渐堆积成块状，且内部产生了较深的裂纹，棘孢曲霉菌丝通过腐蚀产物裂纹接触到铝合金基体，加速其腐蚀。

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