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Study on the corrosion mechanisms evolution of dual-phase tin-lead bronze
双相锡铅青铜腐蚀机理演变研究
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Highlights
- •Phase corrosion mechanisms evolution of tin bronze was first discovered.
- •Tin bronze evolves from the initial α phase corrosion to the later (δ+α(II)) eutectoid phase corrosion.
- •The consumption of dissolved oxygen is the key to phase corrosion mechanisms evolution.
- •The transformation of corrosion products of α phase and δ phase is the main reason for phase corrosion mechanisms evolution.
Abstract
The corrosion behavior of tin-lead bronze in a weakly alkaline soil environment was studied. The results showed that the corrosion of the sample evolves from the initial α phase to the (δ + α(II)) eutectoid phase.
研究了锡铅青铜在弱碱性土壤环境中的腐蚀行为。结果表明，样品的腐蚀从初始α相演变为 （δ + α（II）） 共析相。
Combined with the experiments, it was found that oxygen is the key factor causing corrosion mechanisms evolution of dual-phase bronze alloys.
结合实验发现，氧是导致双相青铜合金腐蚀机理演变的关键因素。
Furthermore, the main reason for the phase corrosion evolution of the bronze alloy was the transformation between the corrosion products (metal chlorides) of the Cu-rich phase (α phase) and the Sn-rich phase (δ phase).
此外，青铜合金相腐蚀演变的主要原因是富铜相（α相）和富锡相（δ相）的腐蚀产物（金属氯化物）之间的转变。
研究了锡铅青铜在弱碱性土壤环境中的腐蚀行为。结果表明，样品的腐蚀从初始α相演变为 （δ + α（II）） 共析相。
Combined with the experiments, it was found that oxygen is the key factor causing corrosion mechanisms evolution of dual-phase bronze alloys.
结合实验发现，氧是导致双相青铜合金腐蚀机理演变的关键因素。
Furthermore, the main reason for the phase corrosion evolution of the bronze alloy was the transformation between the corrosion products (metal chlorides) of the Cu-rich phase (α phase) and the Sn-rich phase (δ phase).
此外，青铜合金相腐蚀演变的主要原因是富铜相（α相）和富锡相（δ相）的腐蚀产物（金属氯化物）之间的转变。
Keywords 关键字
Tin-lead bronze
Double-layer capacitance
Corrosion mechanisms evolution
Dissolved oxygen
锡铅青铜
双层电容
腐蚀机理演变
溶解氧
1. Introduction 1. 引言
Tin-lead bronze is an alloy composed of elements such as Cu, Sn, and Pb.
锡铅青铜是一种由 Cu、Sn 和 Pb 等元素组成的合金。
In the past (10th B.C.–7th B.C.), due to its excellent properties, such as a low melting point, good castability, and good wear resistance, it was frequently smelted into various daily necessities, weapons, and funerary objects [1], [2], [3], [4]. In bronze alloys, the composition of its phase structure is often related to the Sn content. When the Sn content is higher than 6 %, the bronze alloy exhibits a dual-phase structure, which is composed of an α solid solution and an (α + δ) eutectoid phase [5], [6].
在过去（公元前 10 世纪-公元前 7 世纪），由于其熔点低、铸造性好、耐磨性好等优良性能，经常被冶炼成各种日用品、武器和陪葬品 [1]， [2]， [3]， [4].在青铜合金中，其相结构的组成通常与 Sn 含量有关。当 Sn 含量高于 6 % 时，青铜合金呈现双相结构，由α固溶体和 （α + δ） 共析相 [5]、[6] 组成。
锡铅青铜是一种由 Cu、Sn 和 Pb 等元素组成的合金。
In the past (10th B.C.–7th B.C.), due to its excellent properties, such as a low melting point, good castability, and good wear resistance, it was frequently smelted into various daily necessities, weapons, and funerary objects [1], [2], [3], [4]. In bronze alloys, the composition of its phase structure is often related to the Sn content. When the Sn content is higher than 6 %, the bronze alloy exhibits a dual-phase structure, which is composed of an α solid solution and an (α + δ) eutectoid phase [5], [6].
在过去（公元前 10 世纪-公元前 7 世纪），由于其熔点低、铸造性好、耐磨性好等优良性能，经常被冶炼成各种日用品、武器和陪葬品 [1]， [2]， [3]， [4].在青铜合金中，其相结构的组成通常与 Sn 含量有关。当 Sn 含量高于 6 % 时，青铜合金呈现双相结构，由α固溶体和 （α + δ） 共析相 [5]、[6] 组成。
So far, a significant amount of research has been conducted on the corrosion behavior of duplex tin-lead bronze alloys. Wang et al. [7] investigated the corrosion behavior of duplex tin bronze in a neutral salt spray environment and found that the α phase in the copper-rich structure corroded preferentially over the δ phase.
到目前为止，已经对双相锡铅青铜合金的腐蚀行为进行了大量研究。Wang 等 [7] 研究了双相锡青铜在中性盐雾环境中的腐蚀行为，发现富铜结构中的α相优先于δ相腐蚀。
They attributed this to the higher potential of the δ phase compared to the α phase, which facilitated the occurrence of a galvanic effect between the two phases during the corrosion process, thereby accelerating the corrosion of the α phase.
他们将此归因于δ相比 α 相具有更高的电位，这促进了腐蚀过程中两相之间电偶效应的发生，从而加速了 α相的腐蚀。
This finding is consistent with the results reported by Cao et al. [8]. The results of this study can be verified through the analysis of certain unearthed bronze artifacts. For instance, when Li [9], [10], [11] examined an ancient bronze sword, he found that it had corroded preferentially along the α phase in the soil. However, Fan et al. [12] studied bronze coins from the Western Han dynasty unearthed in Xi'an and found that it had corroded along the (δ + α(II)) eutectic phase, a result that contrasts completely with previous reports.
这一发现与 Cao 等人 [8] 报告的结果一致。这项研究的结果可以通过对某些出土的青铜器的分析来验证。例如，当李 [9]、[10]、[11] 检查一把古老的青铜剑时，他发现它沿着土壤中的α相优先腐蚀。然而，Fan 等 [12] 研究了习安出土的西汉铜币，发现它沿着（δ + α（II）））共晶相腐蚀，这一结果与以前的报道完全相反。
Based on the above research, it could be found that there were few studies on the factors affecting the corrosion of bronze alloy phases. Based on research on the corrosion of other bronze alloy phases, some scholars believed that it might have been influenced by the pH value.
基于上述研究，可以发现对影响青铜合金相腐蚀的因素的研究很少。根据对其他青铜合金相腐蚀的研究，一些学者认为它可能受到了 pH 值的影响。
Lv et al. [13] studied the corrosion behavior of cast NiAl bronze alloy at different pH and found that when the pH value was 3.5, each phase corroded uniformly.
Lv 等 [13] 研究了铸造镍铝青铜合金在不同 pH 下的腐蚀行为，发现当 pH 值为 3.5 时，各相腐蚀均匀。
However, when the pH value was below 3.5, selective phase corrosion (SPC) primarily depended on the potential difference between the phases, leading to Kappa and retained beta SPC. At pH value above 3.5, the α phase adjacent to the kappa phases corroded preferentially.
然而，当 pH 值低于 3.5 时，选择性相腐蚀 （SPC） 主要取决于相之间的电位差，导致 Kappa 和保留的 β SPC。当 pH 值高于 3.5 时，与 kappa 相相邻的 α 相优先腐蚀。
In addition, some scholars also believe that the corrosion of phase is also affected by the internal phase composition of the alloy and the morphology of the constituent alloys. Yi et al. [14] studied two types of marine aluminum bronzes and found that the β phase (rich in Al and Ni) in the MAB alloy is more susceptible to large-scale dealloying corrosion due to its higher connectivity in seawater environments.
此外，一些学者还认为，相的腐蚀还受合金内部相组成和组成合金的形貌的影响。Yi 等 [14] 研究了两种类型的海洋铝青铜，发现 MAB 合金中的β相（富含 Al 和 Ni）由于其在海水环境中的连通性较高，更容易受到大规模脱合金腐蚀。
However, in the NAB alloy, the β phase is separated by the α phase (rich in Cu), which inhibits the expansion of dealloying corrosion, and the corrosion mainly manifests as selective phase dissolution.
然而，在 NAB 合金中，β相被α相（富含 Cu）分离，抑制了脱合金腐蚀的扩展，腐蚀主要表现为选择性相溶解。
到目前为止，已经对双相锡铅青铜合金的腐蚀行为进行了大量研究。Wang 等 [7] 研究了双相锡青铜在中性盐雾环境中的腐蚀行为，发现富铜结构中的α相优先于δ相腐蚀。
They attributed this to the higher potential of the δ phase compared to the α phase, which facilitated the occurrence of a galvanic effect between the two phases during the corrosion process, thereby accelerating the corrosion of the α phase.
他们将此归因于δ相比 α 相具有更高的电位，这促进了腐蚀过程中两相之间电偶效应的发生，从而加速了 α相的腐蚀。
This finding is consistent with the results reported by Cao et al. [8]. The results of this study can be verified through the analysis of certain unearthed bronze artifacts. For instance, when Li [9], [10], [11] examined an ancient bronze sword, he found that it had corroded preferentially along the α phase in the soil. However, Fan et al. [12] studied bronze coins from the Western Han dynasty unearthed in Xi'an and found that it had corroded along the (δ + α(II)) eutectic phase, a result that contrasts completely with previous reports.
这一发现与 Cao 等人 [8] 报告的结果一致。这项研究的结果可以通过对某些出土的青铜器的分析来验证。例如，当李 [9]、[10]、[11] 检查一把古老的青铜剑时，他发现它沿着土壤中的α相优先腐蚀。然而，Fan 等 [12] 研究了习安出土的西汉铜币，发现它沿着（δ + α（II）））共晶相腐蚀，这一结果与以前的报道完全相反。
Based on the above research, it could be found that there were few studies on the factors affecting the corrosion of bronze alloy phases. Based on research on the corrosion of other bronze alloy phases, some scholars believed that it might have been influenced by the pH value.
基于上述研究，可以发现对影响青铜合金相腐蚀的因素的研究很少。根据对其他青铜合金相腐蚀的研究，一些学者认为它可能受到了 pH 值的影响。
Lv et al. [13] studied the corrosion behavior of cast NiAl bronze alloy at different pH and found that when the pH value was 3.5, each phase corroded uniformly.
Lv 等 [13] 研究了铸造镍铝青铜合金在不同 pH 下的腐蚀行为，发现当 pH 值为 3.5 时，各相腐蚀均匀。
However, when the pH value was below 3.5, selective phase corrosion (SPC) primarily depended on the potential difference between the phases, leading to Kappa and retained beta SPC. At pH value above 3.5, the α phase adjacent to the kappa phases corroded preferentially.
然而，当 pH 值低于 3.5 时，选择性相腐蚀 （SPC） 主要取决于相之间的电位差，导致 Kappa 和保留的 β SPC。当 pH 值高于 3.5 时，与 kappa 相相邻的 α 相优先腐蚀。
In addition, some scholars also believe that the corrosion of phase is also affected by the internal phase composition of the alloy and the morphology of the constituent alloys. Yi et al. [14] studied two types of marine aluminum bronzes and found that the β phase (rich in Al and Ni) in the MAB alloy is more susceptible to large-scale dealloying corrosion due to its higher connectivity in seawater environments.
此外，一些学者还认为，相的腐蚀还受合金内部相组成和组成合金的形貌的影响。Yi 等 [14] 研究了两种类型的海洋铝青铜，发现 MAB 合金中的β相（富含 Al 和 Ni）由于其在海水环境中的连通性较高，更容易受到大规模脱合金腐蚀。
However, in the NAB alloy, the β phase is separated by the α phase (rich in Cu), which inhibits the expansion of dealloying corrosion, and the corrosion mainly manifests as selective phase dissolution.
然而，在 NAB 合金中，β相被α相（富含 Cu）分离，抑制了脱合金腐蚀的扩展，腐蚀主要表现为选择性相溶解。
From the above studies, it can be found that the relevant research on what factors affect the corrosion of duplex tin bronze alloys is still unclear.
从以上研究中可以发现，关于哪些因素影响双相锡青铜合金腐蚀的相关研究尚不清楚。
Therefore, in this study, a two-year (720 days) accelerated soil burial test was conducted using duplex tin-lead bronze alloy with a Sn content of 11.4 wt%.
因此，在本研究中，使用 Sn 含量为 11.4 wt% 的双相锡铅青铜合金进行了为期两年（720 天）的加速土埋测试。
The results revealed that the corrosion of the duplex tin-lead bronze alloy progressed from the initial α phase corrosion to the later (δ + α(II)) eutectoid phase corrosion.
结果表明，双相锡铅青铜合金的腐蚀从初始α相腐蚀发展到后期 （δ + α（II）） 共析相腐蚀。
This study had shown that the main reason for phase corrosion mechanisms evolution was related to the oxygen concentration in the corrosive environment.
本研究表明，相腐蚀机理演变的主要原因与腐蚀环境中的氧浓度有关。
In the later stage of corrosion, the corrosion products obtained by the two phases (α phase and δ phase) in an oxygen-free environment could transform into each other, causing the (δ + α(II)) eutectoid phase to be more susceptible to corrosion than the α phase on a macroscopic scale.
在腐蚀后期，两相（α相和δ相）在无氧环境中得到的腐蚀产物会相互转化，导致 （δ + α（II）） 共析相在宏观尺度上比 α 相更容易受到腐蚀。
The relevant results of this study will provide certain guidance for the corrosion research of duplex tin-lead bronze alloys.
本研究的相关结果将为双相锡铅青铜合金的腐蚀研究提供一定的指导。
从以上研究中可以发现，关于哪些因素影响双相锡青铜合金腐蚀的相关研究尚不清楚。
Therefore, in this study, a two-year (720 days) accelerated soil burial test was conducted using duplex tin-lead bronze alloy with a Sn content of 11.4 wt%.
因此，在本研究中，使用 Sn 含量为 11.4 wt% 的双相锡铅青铜合金进行了为期两年（720 天）的加速土埋测试。
The results revealed that the corrosion of the duplex tin-lead bronze alloy progressed from the initial α phase corrosion to the later (δ + α(II)) eutectoid phase corrosion.
结果表明，双相锡铅青铜合金的腐蚀从初始α相腐蚀发展到后期 （δ + α（II）） 共析相腐蚀。
This study had shown that the main reason for phase corrosion mechanisms evolution was related to the oxygen concentration in the corrosive environment.
本研究表明，相腐蚀机理演变的主要原因与腐蚀环境中的氧浓度有关。
In the later stage of corrosion, the corrosion products obtained by the two phases (α phase and δ phase) in an oxygen-free environment could transform into each other, causing the (δ + α(II)) eutectoid phase to be more susceptible to corrosion than the α phase on a macroscopic scale.
在腐蚀后期，两相（α相和δ相）在无氧环境中得到的腐蚀产物会相互转化，导致 （δ + α（II）） 共析相在宏观尺度上比 α 相更容易受到腐蚀。
The relevant results of this study will provide certain guidance for the corrosion research of duplex tin-lead bronze alloys.
本研究的相关结果将为双相锡铅青铜合金的腐蚀研究提供一定的指导。
2. Materials and methods 2. 材料和方法
2.1. Experimental materials
2.1. 实验材料
Dual-phase tin-lead bronze alloy was prepared by the mold casting method [15]. The method involved first mixing copper, tin, and lead in the proportions shown in the composition table (Table 1), melting them, pouring the mixture into the mold, and finally air cooling it to obtain the finished product. During the casting process, the melting temperature was 1100 ℃ ± 20 ℃, the casting temperature was 1000 ℃ ± 30 ℃, and the thickness of the casting sample was 3 mm.
采用模铸法制备了双相锡铅青铜合金 [15]。 该方法包括首先按成分表（ 表 1）中显示的比例混合铜、锡和铅，熔化它们，将混合物倒入模具中，最后风冷以获得成品。铸造过程中熔化温度为 1100 °C ± 20 °C，铸造温度为 1000 °C ± 30 °C，铸样厚度为 3 mm。
The specimens were made into two sizes: 20 mm × 10 mm × 3 mm and 10 mm × 10 mm × 3 mm by wire cutting.
通过线切割将试样制成两种尺寸：20 mm × 10 mm × 3 mm 和 10 mm × 10 mm × 3 mm。
In order to avoid the influence of uneven surface and contaminants on the sample after wire cutting, the sample after cutting needed to be cleaned and polished to the corresponding roughness of 4000 # sandpaper to make the surface of the sample reach the same smooth state (Ra is about 0.1 μm-0.2 μm) to eliminate the crevice corrosion caused by the sample.
为避免线切割后样品表面不平整和污染物对样品的影响，切割后的样品需要清洗抛光至相应的粗糙度为 4000#砂纸，使样品表面达到相同的光滑状态（Ra 约为 0.1μm-0.2μm），以消除样品造成的缝隙腐蚀。
Finally, it was cleaned with anhydrous ethanol and dried for 24 hours before storage.
最后用无水乙醇清洗，干燥 24 h 后再贮存。
采用模铸法制备了双相锡铅青铜合金 [15]。 该方法包括首先按成分表（ 表 1）中显示的比例混合铜、锡和铅，熔化它们，将混合物倒入模具中，最后风冷以获得成品。铸造过程中熔化温度为 1100 °C ± 20 °C，铸造温度为 1000 °C ± 30 °C，铸样厚度为 3 mm。
The specimens were made into two sizes: 20 mm × 10 mm × 3 mm and 10 mm × 10 mm × 3 mm by wire cutting.
通过线切割将试样制成两种尺寸：20 mm × 10 mm × 3 mm 和 10 mm × 10 mm × 3 mm。
In order to avoid the influence of uneven surface and contaminants on the sample after wire cutting, the sample after cutting needed to be cleaned and polished to the corresponding roughness of 4000 # sandpaper to make the surface of the sample reach the same smooth state (Ra is about 0.1 μm-0.2 μm) to eliminate the crevice corrosion caused by the sample.
为避免线切割后样品表面不平整和污染物对样品的影响，切割后的样品需要清洗抛光至相应的粗糙度为 4000#砂纸，使样品表面达到相同的光滑状态（Ra 约为 0.1μm-0.2μm），以消除样品造成的缝隙腐蚀。
Finally, it was cleaned with anhydrous ethanol and dried for 24 hours before storage.
最后用无水乙醇清洗，干燥 24 h 后再贮存。
Table 1. Material composition.
表 1.材料成分。
| Element 元素 | Sn 锡 | Pb 铅 | P | S | Fe 铁 | Zn 锌 | Cu 跟 |
|---|---|---|---|---|---|---|---|
| Content (wt%) 含量 （wt%） | 11.43 | 4.40 | < 0.001 | < 0.001 | 0.019 | 0.020 | Balance 平衡 |
2.2. Corrosion experiment in soil
2.2. 土壤腐蚀实验
In order to observe the corrosion behavior of duplex tin-lead bronze artifacts in weakly alkaline soil environment, simulated corrosion was carried out by casting duplex tin-lead bronze alloy.
为了观察双相锡铅青铜文物在弱碱性土壤环境中的腐蚀行为，通过铸造双相锡铅青铜合金进行了模拟腐蚀。
The soil relevant to the experiment in this paper was obtained from an archaeological excavation site at a depth of 5 m in Xi’an, Shaanxi Province. Table 2 shows the relevant parameters after testing by the testing agency. In order to accelerate the test process, the Cl concentration measured in the soil was expanded by 100 times (Cl concentration was 7.5 g/Kg).
本文实验相关土壤来自陕西省习安市 5 m 深的考古发掘现场。 表 2 显示了检测机构检测后的相关参数。为了加快测试过程，土壤中测得的 Cl 浓度增加了 100 倍（Cl 浓度为 7.5 g/Kg）。
The soil burial process was as follows: First, a sealed container was prepared, and soil was spread on the bottom of the container. Then, the samples were evenly distributed on the upper layer of the soil, with a spacing of more than 5 cm between the samples.
土埋过程如下：首先，准备一个密封的容器，并将土壤铺在容器的底部。然后，将样品均匀分布在土壤的上层，样品之间的间距超过 5 cm。
Finally, it was covered with soil and sealed. The ambient temperature of the sample was room temperature.
最后，它被泥土覆盖并密封。样品的环境温度为室温。
为了观察双相锡铅青铜文物在弱碱性土壤环境中的腐蚀行为，通过铸造双相锡铅青铜合金进行了模拟腐蚀。
The soil relevant to the experiment in this paper was obtained from an archaeological excavation site at a depth of 5 m in Xi’an, Shaanxi Province. Table 2 shows the relevant parameters after testing by the testing agency. In order to accelerate the test process, the Cl concentration measured in the soil was expanded by 100 times (Cl concentration was 7.5 g/Kg).
本文实验相关土壤来自陕西省习安市 5 m 深的考古发掘现场。 表 2 显示了检测机构检测后的相关参数。为了加快测试过程，土壤中测得的 Cl 浓度增加了 100 倍（Cl 浓度为 7.5 g/Kg）。
The soil burial process was as follows: First, a sealed container was prepared, and soil was spread on the bottom of the container. Then, the samples were evenly distributed on the upper layer of the soil, with a spacing of more than 5 cm between the samples.
土埋过程如下：首先，准备一个密封的容器，并将土壤铺在容器的底部。然后，将样品均匀分布在土壤的上层，样品之间的间距超过 5 cm。
Finally, it was covered with soil and sealed. The ambient temperature of the sample was room temperature.
最后，它被泥土覆盖并密封。样品的环境温度为室温。
Table 2. Concentration of various ions and pH of a soil sample excavated at 5 m depth on the archaeological site of Xi’an, Shaanxi.
表 2.在陕西习安考古遗址 5 m 深处出土的土壤样品的各种离子浓度和 pH 值。
| Parameters 参数 (g Kg−1) （克千克 −1） | Cl- | SO42- | Na+ 开 + | HCO32- | CO32- | K+ | pH 酸碱度 | Moisture content 含水量 (wt%) （重量%） |
|---|---|---|---|---|---|---|---|---|
| Value 价值 | 0.079 | 0.13 | 12.4 | 0.477 | 4.75 × 10−3 | 2.1 | 8.6 | 8 |
Since the test container was a closed device, the corrosion of the sample was not affected by the outside world, and the ions in the container would not disappear. The test periods were 30 days, 90 days, 180 days, 360 days, 540 days and 720 days.
由于测试容器是密闭装置，样品的腐蚀不受外界影响，容器内的离子不会消失。测试时间为 30 天、 90 天、 180 天、 360 天、 540 天和 720 天。
There were 3 parallel samples, which were used for surface observation, cross-section observation, corrosion product morphology observation and surface corrosion observation after corrosion product removal (Table 3). During the experiment, the macroscopic morphology of the sample was photographed and the corrosion products were tested immediately after sampling. Corrosion products were inspected using XRD testing.
有 3 个平行样品，分别用于表面观察、横截面观察、腐蚀产物形貌观察和腐蚀产物去除后的表面腐蚀观察（ 表 3）。实验过程中，对样品的宏观形貌进行了拍照，并在取样后立即对腐蚀产物进行了检测。使用 XRD 测试对腐蚀产物进行检查。
由于测试容器是密闭装置，样品的腐蚀不受外界影响，容器内的离子不会消失。测试时间为 30 天、 90 天、 180 天、 360 天、 540 天和 720 天。
There were 3 parallel samples, which were used for surface observation, cross-section observation, corrosion product morphology observation and surface corrosion observation after corrosion product removal (Table 3). During the experiment, the macroscopic morphology of the sample was photographed and the corrosion products were tested immediately after sampling. Corrosion products were inspected using XRD testing.
有 3 个平行样品，分别用于表面观察、横截面观察、腐蚀产物形貌观察和腐蚀产物去除后的表面腐蚀观察（ 表 3）。实验过程中，对样品的宏观形貌进行了拍照，并在取样后立即对腐蚀产物进行了检测。使用 XRD 测试对腐蚀产物进行检查。
Table 3. Purpose of use of soil replicates.
表 3.土壤重复的使用目的。
| Sample 样本 | Ι | ΙΙ 第二 | ΙΙΙ 第三 |
|---|---|---|---|
| Purpose of use 使用目的 | Corrosion product analysis 腐蚀产物分析 | Electrochemical testing 电化学测试 | Surface morphology observation 表面形貌观察 |
| Cross-section observation 截面观察 | Surface corrosion observation after corrosion product removal 去除腐蚀产物后的表面腐蚀观察 |
2.3. Microstructure analysis
2.3. 微观结构分析
In order to observe the phase composition, microstructure and element distribution of the dual-phase tin-lead bronze alloy, specimens with a size of 10 mm × 10 mm × 3 mm were mounted.
After the mounting was completed, the specimen surface was ground to 7000 # sandpaper (Ra was about 0.05 μm-0.1 μm) and then polished with a diamond polishing paste (particle size 1.5 microns) until no obvious surface scratches remained (Ra ≤ 0.05 μm).
The sample(s) (n = 3) were then cleaned with anhydrous ethanol before being blow dried and stored. The optical metallographic structure of the bronze alloy was observed and photographed by an optical metallographic microscope (Leica Metallographic Microscope DM2700M).
After this, the microstructure and elemental distribution of the alloy were examined through scanning electron microscopy (Thermo Fisher/Apreo Shivac) coupled with energy dispersive spectroscopy (Oxford Aztec Ultim Live 100 X).
Finally, the phase distribution of the alloy substrate was characterized using electron backscatter diffraction (EBSD) technology (Oxford Symmetry).
The acceleration voltage of EBSD was 20 eV-30 keV, the current was 1 pA-400 nA, the EDS detector was an analytical silicon drift electric cooler (Aztec Ultim Live 100X), the element scanning range was 4 Be-98 Cf, and the resolution was 20 nm-100 μm.
Due to the presence of surface stress layer on the sample following mechanical polishing, vibratory polishing was employed to eliminate this layer. The procedure involved an initial vibration with an Al2O3 polishing slurry (particle size 0.05 μm), followed by second vibration using SiO2 polishing slurry (particle size 0.05 μm). Subsequently, the samples were subjected to ultrasonic cleaning with anhydrous ethanol and allowed to dry for 24 hours prior to testing. The resulting data were analyzed utilizing Aztec and Aztec Crystal software.
After the mounting was completed, the specimen surface was ground to 7000 # sandpaper (Ra was about 0.05 μm-0.1 μm) and then polished with a diamond polishing paste (particle size 1.5 microns) until no obvious surface scratches remained (Ra ≤ 0.05 μm).
The sample(s) (n = 3) were then cleaned with anhydrous ethanol before being blow dried and stored. The optical metallographic structure of the bronze alloy was observed and photographed by an optical metallographic microscope (Leica Metallographic Microscope DM2700M).
After this, the microstructure and elemental distribution of the alloy were examined through scanning electron microscopy (Thermo Fisher/Apreo Shivac) coupled with energy dispersive spectroscopy (Oxford Aztec Ultim Live 100 X).
Finally, the phase distribution of the alloy substrate was characterized using electron backscatter diffraction (EBSD) technology (Oxford Symmetry).
The acceleration voltage of EBSD was 20 eV-30 keV, the current was 1 pA-400 nA, the EDS detector was an analytical silicon drift electric cooler (Aztec Ultim Live 100X), the element scanning range was 4 Be-98 Cf, and the resolution was 20 nm-100 μm.
Due to the presence of surface stress layer on the sample following mechanical polishing, vibratory polishing was employed to eliminate this layer. The procedure involved an initial vibration with an Al2O3 polishing slurry (particle size 0.05 μm), followed by second vibration using SiO2 polishing slurry (particle size 0.05 μm). Subsequently, the samples were subjected to ultrasonic cleaning with anhydrous ethanol and allowed to dry for 24 hours prior to testing. The resulting data were analyzed utilizing Aztec and Aztec Crystal software.
The phase and microstructure of the duplex tin-lead bronze alloy were further observed by high-resolution transmission electron microscopy (JEOL, JEM-2100 UHR STEM/EDS).
通过高分辨率透射电子显微镜 （JEOL， JEM-2100 UHR STEM/EDS） 进一步观察了双相锡铅青铜合金的相和微观结构。
The acceleration voltage of TEM was 80–200 keV, the element scanning range was 5Be-92U, and the resolution was 0.1–100 nm. The sample was fabricated into a circular slice with diameter of 3 mm.
TEM 的加速电压为 80–200 keV，元素扫描范围为 5Be-92U，分辨率为 0.1–100 nm。将样品制成直径为 3 mm 的圆形切片。
An ion thinning instrument (Gatan/695.C) was employed to prepare the thin regions for observation.
使用离子稀释仪器 （Gatan/695.C） 制备用于观察的薄区域。
The various phase structures within the sample were subsequently subjected to microscopic examination, energy dispersive spectroscopy (EDS) analysis, and selected area electron diffraction (SAED).
随后对样品内的各种相结构进行显微镜检查、能量色散谱 （EDS） 分析和选定区域电子衍射 （SAED）。
通过高分辨率透射电子显微镜 （JEOL， JEM-2100 UHR STEM/EDS） 进一步观察了双相锡铅青铜合金的相和微观结构。
The acceleration voltage of TEM was 80–200 keV, the element scanning range was 5Be-92U, and the resolution was 0.1–100 nm. The sample was fabricated into a circular slice with diameter of 3 mm.
TEM 的加速电压为 80–200 keV，元素扫描范围为 5Be-92U，分辨率为 0.1–100 nm。将样品制成直径为 3 mm 的圆形切片。
An ion thinning instrument (Gatan/695.C) was employed to prepare the thin regions for observation.
使用离子稀释仪器 （Gatan/695.C） 制备用于观察的薄区域。
The various phase structures within the sample were subsequently subjected to microscopic examination, energy dispersive spectroscopy (EDS) analysis, and selected area electron diffraction (SAED).
随后对样品内的各种相结构进行显微镜检查、能量色散谱 （EDS） 分析和选定区域电子衍射 （SAED）。
2.4. Corrosion product analysis
2.4. 腐蚀产物分析
X-ray diffraction (Rigaku Smart Lab SE) was used to analyze the corrosion products on the sample surface.
X 射线衍射 （Rigaku Smart Lab SE） 用于分析样品表面的腐蚀产物。
The radiation source was Cu-Kα, the detector was an analytical silicon drift type and its angular resolution was 0.01°- 0.05°. The sample scanning range was 10–100 °, the scanning speed was 8 °/min, and the test data was analyzed by Highscore software.
辐射源为 Cu-Kα，探测器为解析硅漂移型，其角分辨率为 0.01°- 0.05°。样品扫描范围为 10–100°，扫描速度为 8°/min，测试数据采用 Highscore 软件进行分析。
Then, scanning electron microscope and an energy dispersive spectrometer (FE-SEM, Nova Nano 400) were used to observe the microscopic morphology of the sample surface after the corrosion products were removed, the corrosion morphology of the rusted section and the distribution of related elements in the section was observed.
然后，利用扫描电子显微镜和能量色散光谱仪（FE-SEM，Nova Nano 400）观察去除腐蚀产物后样品表面的微观形貌，观察生锈段的腐蚀形貌和相关元素在断面中的分布。
The acceleration voltage of SEM was 15–18 keV, the EDS detector was a field emission-backscattered electron detection type, and its resolution is 5–50 μm. In addition, the corrosion product removal standard of copper alloy adopts GB/T 16545–2015 (Chinese standard).
SEM 的加速电压为 15–18 keV，EDS 探测器为场发射背散射电子检测类型，分辨率为 5–50 μm。此外，铜合金腐蚀产物去除标准采用 GB/T 16545–2015（中国标准）。
X 射线衍射 （Rigaku Smart Lab SE） 用于分析样品表面的腐蚀产物。
The radiation source was Cu-Kα, the detector was an analytical silicon drift type and its angular resolution was 0.01°- 0.05°. The sample scanning range was 10–100 °, the scanning speed was 8 °/min, and the test data was analyzed by Highscore software.
辐射源为 Cu-Kα，探测器为解析硅漂移型，其角分辨率为 0.01°- 0.05°。样品扫描范围为 10–100°，扫描速度为 8°/min，测试数据采用 Highscore 软件进行分析。
Then, scanning electron microscope and an energy dispersive spectrometer (FE-SEM, Nova Nano 400) were used to observe the microscopic morphology of the sample surface after the corrosion products were removed, the corrosion morphology of the rusted section and the distribution of related elements in the section was observed.
然后，利用扫描电子显微镜和能量色散光谱仪（FE-SEM，Nova Nano 400）观察去除腐蚀产物后样品表面的微观形貌，观察生锈段的腐蚀形貌和相关元素在断面中的分布。
The acceleration voltage of SEM was 15–18 keV, the EDS detector was a field emission-backscattered electron detection type, and its resolution is 5–50 μm. In addition, the corrosion product removal standard of copper alloy adopts GB/T 16545–2015 (Chinese standard).
SEM 的加速电压为 15–18 keV，EDS 探测器为场发射背散射电子检测类型，分辨率为 5–50 μm。此外，铜合金腐蚀产物去除标准采用 GB/T 16545–2015（中国标准）。
2.5. Immersion test 2.5. 浸入试验
In order to verify whether dissolved oxygen had an impact on the corrosion process, simulated seawater immersion experiments were carried out on the samples.
为了验证溶解氧是否对腐蚀过程有影响，对样品进行了模拟海水浸泡实验。
The simulated seawater immersion test was based on the GB/T 6384–2008 (Chinese standard), the immersed specimen was bare bronze.
模拟海水浸泡试验以 GB/T 6384–2008（中国标准）为基础，浸泡试样为裸铜。
Before the experiment, constant potential polarization was required to remove the oxide film formed on the surface of the sample to prevent errors caused by it in the experiment.
实验前，需要恒定电位极化以去除样品表面形成的氧化膜，以防止在实验中由此引起的误差。
Specific experimental process: First, the sample was placed in 3.5 % NaCl solution and −0.5 V was applied to the sample for 20 minutes. After removing the oxide film, the sample was immersed in the solution for 30 days.
具体实验过程：首先，将样品置于 3.5% NaCl 溶液中，对样品施加 −0.5 V 20 分钟。去除氧化膜后，将样品浸入溶液中 30 天。
为了验证溶解氧是否对腐蚀过程有影响，对样品进行了模拟海水浸泡实验。
The simulated seawater immersion test was based on the GB/T 6384–2008 (Chinese standard), the immersed specimen was bare bronze.
模拟海水浸泡试验以 GB/T 6384–2008（中国标准）为基础，浸泡试样为裸铜。
Before the experiment, constant potential polarization was required to remove the oxide film formed on the surface of the sample to prevent errors caused by it in the experiment.
实验前，需要恒定电位极化以去除样品表面形成的氧化膜，以防止在实验中由此引起的误差。
Specific experimental process: First, the sample was placed in 3.5 % NaCl solution and −0.5 V was applied to the sample for 20 minutes. After removing the oxide film, the sample was immersed in the solution for 30 days.
具体实验过程：首先，将样品置于 3.5% NaCl 溶液中，对样品施加 −0.5 V 20 分钟。去除氧化膜后，将样品浸入溶液中 30 天。
The immersion solutions were divided into two groups. One group of solutions did not require deoxygenation treatment, while the other group of solutions needed to be passed through N2 for 1 h before the sample was treated to remove the oxide film and N2 needed to be continuously passed through during the immersion process to ensure that the solution system was always in oxygen-free environment.
将浸泡溶液分为两组。一组溶液不需要脱氧处理，而另一组溶液需要在处理样品前通过 N2 1 h 以去除氧化膜，并且在浸泡过程中需要连续通过 N2，以确保溶液系统始终处于无氧环境中。
将浸泡溶液分为两组。一组溶液不需要脱氧处理，而另一组溶液需要在处理样品前通过 N2 1 h 以去除氧化膜，并且在浸泡过程中需要连续通过 N2，以确保溶液系统始终处于无氧环境中。
2.6. Electrochemical test
2.6. 电化学测试
In order to analyze the corrosion behavior and process change of duplex tin-lead bronze alloy, electrochemical impedance spectroscopy and polarization curve tests were performed on the corrosion samples after each cycle test. First, use a clamp to clamp the side of the sample and fix it.
为了分析双相锡铅青铜合金的腐蚀行为和过程变化，在每次循环试验后对腐蚀样品进行了电化学阻抗谱和极化曲线测试。首先，用夹子夹住样品的侧面并固定。
Then, use a knife to scrape off the corrosion products on a square surface (exposed area of 1 cm2) of the sample. After the surface corrosion products were removed and the metal substrate was exposed, it was necessary to use 7000 # sandpaper to gently rub and remove the oxide film. Then, the rust-free square surface was reliably electrically connected to the copper wire.
然后，用刀刮掉样品的方形表面（暴露面积为 1 cm2）上的腐蚀产物。去除表面腐蚀产物，露出金属基材后，需要用 7000#砂纸轻轻摩擦并去除氧化膜。然后，将不生锈的方形表面可靠地与铜线电气连接。
Finally, use 704 solid glue to seal the five surfaces other than the test surface.
最后，使用 704 固体胶密封测试表面以外的五个表面。
The test adopted three-electrode system, with the bronze sample as the working electrode, the saturated calomel electrode (SCE) as the reference electrode, and the platinum electrode as the auxiliary electrode.
测试采用三电极系统，以青铜样品为工作电极，饱和甘汞电极 （SCE） 为参比电极，铂电极为辅助电极。
The electrochemical workstation selected was CorrTestCS310, and the test solution was 1:5 mixture of dry soil and distilled water [14]. Before the test, the open circuit potential of the sample was measured for 7200 s to ensure that the surface was in stable state during the test. The EIS measurement frequency range was 100 kHz - 0.01 Hz, and the perturbation voltage was 10 mV.
选择的电化学工作站是 CorrTestCS310，测试溶液是干土和蒸馏水的 1：5 混合物 [14]。 测试前，测量样品的开路电位 7200 s，以确保测试过程中表面处于稳定状态。EIS 测量频率范围为 100 kHz - 0.01 Hz，扰动电压为 10 mV。
The polarization curve test selected measurement range of −1000 mV to 1500 mV relative to the open circuit potential, with scan rate of 0.33 mV/s. The M-S （Mott-Schottky）curve test selected measurement range of −1000–2000 mV relative open circuit potential, scan rate of 0.1 V/s.
极化曲线测试选择的测量范围为相对于开路电位的 −1000 mV 至 1500 mV，扫描速率为 0.33 mV/s。M-S（莫特-肖特基）曲线测试选择了 −1000–2000 mV 相对开路电位的测量范围，扫描速率为 0.1 V/s。
To ensure the integrity of the test, we chose the potential range and scan rate based on those used in previous literature [7], [10], [11], [16].
为了确保测试的完整性，我们根据以前文献 [7]、[10]、[11]、[16] 中使用的电位范围和扫描速率选择了电位范围和扫描速率。
为了分析双相锡铅青铜合金的腐蚀行为和过程变化，在每次循环试验后对腐蚀样品进行了电化学阻抗谱和极化曲线测试。首先，用夹子夹住样品的侧面并固定。
Then, use a knife to scrape off the corrosion products on a square surface (exposed area of 1 cm2) of the sample. After the surface corrosion products were removed and the metal substrate was exposed, it was necessary to use 7000 # sandpaper to gently rub and remove the oxide film. Then, the rust-free square surface was reliably electrically connected to the copper wire.
然后，用刀刮掉样品的方形表面（暴露面积为 1 cm2）上的腐蚀产物。去除表面腐蚀产物，露出金属基材后，需要用 7000#砂纸轻轻摩擦并去除氧化膜。然后，将不生锈的方形表面可靠地与铜线电气连接。
Finally, use 704 solid glue to seal the five surfaces other than the test surface.
最后，使用 704 固体胶密封测试表面以外的五个表面。
The test adopted three-electrode system, with the bronze sample as the working electrode, the saturated calomel electrode (SCE) as the reference electrode, and the platinum electrode as the auxiliary electrode.
测试采用三电极系统，以青铜样品为工作电极，饱和甘汞电极 （SCE） 为参比电极，铂电极为辅助电极。
The electrochemical workstation selected was CorrTestCS310, and the test solution was 1:5 mixture of dry soil and distilled water [14]. Before the test, the open circuit potential of the sample was measured for 7200 s to ensure that the surface was in stable state during the test. The EIS measurement frequency range was 100 kHz - 0.01 Hz, and the perturbation voltage was 10 mV.
选择的电化学工作站是 CorrTestCS310，测试溶液是干土和蒸馏水的 1：5 混合物 [14]。 测试前，测量样品的开路电位 7200 s，以确保测试过程中表面处于稳定状态。EIS 测量频率范围为 100 kHz - 0.01 Hz，扰动电压为 10 mV。
The polarization curve test selected measurement range of −1000 mV to 1500 mV relative to the open circuit potential, with scan rate of 0.33 mV/s. The M-S （Mott-Schottky）curve test selected measurement range of −1000–2000 mV relative open circuit potential, scan rate of 0.1 V/s.
极化曲线测试选择的测量范围为相对于开路电位的 −1000 mV 至 1500 mV，扫描速率为 0.33 mV/s。M-S（莫特-肖特基）曲线测试选择了 −1000–2000 mV 相对开路电位的测量范围，扫描速率为 0.1 V/s。
To ensure the integrity of the test, we chose the potential range and scan rate based on those used in previous literature [7], [10], [11], [16].
为了确保测试的完整性，我们根据以前文献 [7]、[10]、[11]、[16] 中使用的电位范围和扫描速率选择了电位范围和扫描速率。
3. Results 3. 结果
3.1. Material structure analysis
3.1. 材料结构分析
Fig. 1 shows the analysis test results of microstructure. From the metallographic microstructure (Fig. 1a), it could be seen that there were relatively thick branches in the bronze alloy, which was mainly caused by the casting-cooling process. In addition, from Fig. 1b (partial enlargement of Fig. 1a), it could be found that there were obvious three-phase structures inside the bronze alloy, which was typical dual-phase tin bronze alloy. From the EBSD and EDS test results of the dual-phase bronze alloy matrix structure (Fig. 1c, Fig. 1d and Table 4), it could be found that the main component of the α(I) phase was Cu13.7Sn (Cu content is 89.83 wt%), while the main component of the (δ+α(II)) eutectoid structure was Cu41Sn11 (Sn content is 39.48 wt%), and Pb is distributed in the matrix in a free state. Inside the bronze alloy, Cu13.7Sn accounts for approximately 84.3 wt%, Cu41Sn11 accounts for approximately 7.1 wt% and Pb accounts for approximately 8.6 wt%.
图 1 显示了微观结构的分析测试结果。从金相微观组织（ 图 1a）可以看出，青铜合金中有相对较厚的树枝，这主要是由铸造-冷却过程引起的。此外，从图 1b（ 图 1a 的部分放大）可以发现青铜合金内部有明显的三相结构，这是典型的双相锡青铜合金。从双相青铜合金基体结构的 EBSD 和 EDS 测试结果（ 图 1c、 图 1d 和表 4）可以发现，α（I） 相的主要成分是 Cu13.7Sn（Cu 含量为 89.83 wt%），而 （δ+α（II）） 共析结构的主要成分是 Cu41Sn11（Sn 含量为 39.48 wt%），Pb 以游离态分布在基质中。在青铜合金中，Cu13.7Sn 约占 84.3 wt%，Cu41Sn11 约占 7.1 wt%，Pb 约占 8.6 wt%。
图 1 显示了微观结构的分析测试结果。从金相微观组织（ 图 1a）可以看出，青铜合金中有相对较厚的树枝，这主要是由铸造-冷却过程引起的。此外，从图 1b（ 图 1a 的部分放大）可以发现青铜合金内部有明显的三相结构，这是典型的双相锡青铜合金。从双相青铜合金基体结构的 EBSD 和 EDS 测试结果（ 图 1c、 图 1d 和表 4）可以发现，α（I） 相的主要成分是 Cu13.7Sn（Cu 含量为 89.83 wt%），而 （δ+α（II）） 共析结构的主要成分是 Cu41Sn11（Sn 含量为 39.48 wt%），Pb 以游离态分布在基质中。在青铜合金中，Cu13.7Sn 约占 84.3 wt%，Cu41Sn11 约占 7.1 wt%，Pb 约占 8.6 wt%。
Fig. 1. Analysis results of duplex tin-lead bronze alloy. (a-b) metallographic microstructure, (c) SEM-BSE diagram and (d) EBSD-Phase diagram.
图 1.双相锡铅青铜合金的分析结果。（a-b） 金相显微组织，（c） SEM-BSE 图和 （d） EBSD 相图。
On this basis, TEM was used to observe the internal structure of the duplex tin-lead bronze alloy. Fig. 2 shows the bright field TEM image and the selected area electron diffraction (SAED) image of different phases. By observing the SAED images of the three regions in Fig. 2a, it can be found that region 1 was surrounded by region 2. Comparing the standard PDF card and EDS data (Fig. 2b), it could be seen that the region 1 (Cu content about 85.5 wt%) and region 3 (Cu content about 83.8 wt%) were high in Cu content and was α phase (Cu13.7Sn, PDF: # 03–065–6821) [17], [18]. The region 2 (Sn content about 30.71 wt%) was high in Sn content and was δ phase (Cu41Sn11, PDF: # 01–071–0094) [17], [18], [19]. This corresponds to the metallographic microstructure in Table 1.
在此基础上，采用 TEM 观察双相锡铅青铜合金的内部结构。 图 2 显示了不同相的明场 TEM 图像和选定区域电子衍射 （SAED） 图像。通过观察图 2a 中三个区域的 SAED 图像，可以发现区域 1 被区域 2 包围。比较标准 PDF 卡和 EDS 数据（ 图 2b），可以看出区域 1（铜含量约为 85.5 wt%）和区域 3（Cu 含量约为 83.8 wt%）的铜含量较高，并且处于α相（Cu13.7Sn，PDF：# 03–065–6821）[17]、[18]。 区域 2 （Sn 含量约为 30.71 wt%） 的 Sn 含量很高，并且处于δ相 （Cu41Sn11， PDF： # 01–071–0094） [17]， [18]， [19]。 这与表 1 中的金相微观结构相对应。
在此基础上，采用 TEM 观察双相锡铅青铜合金的内部结构。 图 2 显示了不同相的明场 TEM 图像和选定区域电子衍射 （SAED） 图像。通过观察图 2a 中三个区域的 SAED 图像，可以发现区域 1 被区域 2 包围。比较标准 PDF 卡和 EDS 数据（ 图 2b），可以看出区域 1（铜含量约为 85.5 wt%）和区域 3（Cu 含量约为 83.8 wt%）的铜含量较高，并且处于α相（Cu13.7Sn，PDF：# 03–065–6821）[17]、[18]。 区域 2 （Sn 含量约为 30.71 wt%） 的 Sn 含量很高，并且处于δ相 （Cu41Sn11， PDF： # 01–071–0094） [17]， [18]， [19]。 这与表 1 中的金相微观结构相对应。
Fig. 2. TEM analysis results of duplex tin-lead bronze alloy. (a) Selected area electron diffraction of microstructure and different phases and (b) Point scanning results of different areas.
图 2.双相锡铅青铜合金的 TEM 分析结果。（a） 微观结构和不同相的选定区域电子衍射和 （b） 不同区域的点扫描结果。
3.2. Corrosion morphology analysis
3.2. 腐蚀形态分析
To investigate the changes in corrosion morphology of the bronze alloy, samples at various stages of exposure were documented. Fig. 3a presented the initial morphology of the sample, characterized by a brown surface. After 90 days of burial (Fig. 3b), the metallic luster of the test surface was entirely lost, and the surface was predominantly covered by a layer of reddish-brown corrosion products, interspersed with dot-shaped dark green corrosion products (Red circle).
为了研究青铜合金腐蚀形态的变化，记录了不同暴露阶段的样品。 图 3a 显示了样品的初始形态，其特征是棕色表面。埋藏 90 天后（ 图 3b），测试表面的金属光泽完全消失，表面主要被一层红棕色腐蚀产物覆盖，点状深绿色腐蚀产物（红色圆圈）。
As burial time increased, the dark green corrosion products gradually obscured the reddish-brown layers. By the end of the 720 days test (Fig. 3f), it was observed that the green corrosion products on the sample's surface had flaked off, revealing the underlying reddish-brown corrosion products.
随着埋藏时间的增加，深绿色腐蚀产物逐渐掩盖了红棕色层。到 720 天测试结束时（ 图 3f），观察到样品表面的绿色腐蚀产物已经剥落，露出潜在的红棕色腐蚀产物。
Furthermore, the dark green corrosion products exhibited greater density compared to earlier stages, resulting in a smoother surface texture.
此外，与早期阶段相比，深绿色腐蚀产物表现出更大的密度，从而产生更光滑的表面纹理。
为了研究青铜合金腐蚀形态的变化，记录了不同暴露阶段的样品。 图 3a 显示了样品的初始形态，其特征是棕色表面。埋藏 90 天后（ 图 3b），测试表面的金属光泽完全消失，表面主要被一层红棕色腐蚀产物覆盖，点状深绿色腐蚀产物（红色圆圈）。
As burial time increased, the dark green corrosion products gradually obscured the reddish-brown layers. By the end of the 720 days test (Fig. 3f), it was observed that the green corrosion products on the sample's surface had flaked off, revealing the underlying reddish-brown corrosion products.
随着埋藏时间的增加，深绿色腐蚀产物逐渐掩盖了红棕色层。到 720 天测试结束时（ 图 3f），观察到样品表面的绿色腐蚀产物已经剥落，露出潜在的红棕色腐蚀产物。
Furthermore, the dark green corrosion products exhibited greater density compared to earlier stages, resulting in a smoother surface texture.
此外，与早期阶段相比，深绿色腐蚀产物表现出更大的密度，从而产生更光滑的表面纹理。
Fig. 3. Macroscopic corrosion morphology of bronze alloy at different periods. (a) 0 d, (b) 90 d, (c) 180 d, (d) 360 d, (e) 540 d and (f) 720 d.
图 3.青铜合金在不同时期的宏观腐蚀形貌。（a） 0 d， （b） 90 d， （c） 180 d， （d） 360 d， （e） 540 d 及 （f） 720 d。
In addition, X-ray diffraction analysis was used to characterize the composition of corrosion products of the samples at different periods. From the above analysis, it could be seen that the main components of the original bronze alloy sample are Pb, Cu13.7Sn and Cu41Sn11. The X-ray diffraction results (Fig. 4) revealed that the corrosion level of the samples was relatively low during the initial stage (30 days), with the emergence of corrosion products such as Cu(OH)2, SnO2, Cu2O, and Pb3(CO3)2(OH)2 on the surface. As the corrosion time extended further, the corrosion product Cu(OH)2 had almost completely disappeared, while the content of SnCl2 and Cu2(OH)3Cl increased. the XRD results obtained from samples buried for 360 days to 720 days were largely similarly. Additionally, due to the samples being buried in soil, SiO₂ particles were detected at all stages of the experiment.
此外，采用 X 射线衍射分析表征了不同时期样品腐蚀产物的成分。从以上分析可以看出，原始青铜合金样品的主要成分是 Pb、Cu13.7Sn 和 Cu41Sn11。X 射线衍射结果（ 图 4）显示样品的初始阶段（30 天）腐蚀水平相对较低，表面出现了 Cu（OH）2、SnO2、Cu2O 和 Pb3（CO3）2（OH）2 等腐蚀产物。随着腐蚀时间的进一步延长，腐蚀产物 Cu（OH）2 几乎完全消失，而 SnCl2 和 Cu2（OH）3Cl 的含量增加。从埋藏 360 天到 720 天的样品中获得的 XRD 结果大致相似。此外，由于样品被埋在土壤中，因此在实验的所有阶段都检测到了 SiO₂ 颗粒。
此外，采用 X 射线衍射分析表征了不同时期样品腐蚀产物的成分。从以上分析可以看出，原始青铜合金样品的主要成分是 Pb、Cu13.7Sn 和 Cu41Sn11。X 射线衍射结果（ 图 4）显示样品的初始阶段（30 天）腐蚀水平相对较低，表面出现了 Cu（OH）2、SnO2、Cu2O 和 Pb3（CO3）2（OH）2 等腐蚀产物。随着腐蚀时间的进一步延长，腐蚀产物 Cu（OH）2 几乎完全消失，而 SnCl2 和 Cu2（OH）3Cl 的含量增加。从埋藏 360 天到 720 天的样品中获得的 XRD 结果大致相似。此外，由于样品被埋在土壤中，因此在实验的所有阶段都检测到了 SiO₂ 颗粒。
Fig. 4. X-ray diffraction patterns of duplex tin-lead bronze alloy at different stages.
图 4.双相锡铅青铜合金在不同阶段的 X 射线衍射图谱。
On the basis of the above, to further investigate the corrosion extent of the duplex tin-lead bronze alloy in mildly alkaline soil environment, corrosion products removal treatments were conducted on samples buried for 90 d, 360 d and 720 d. Fig. 5 presents the microscopic morphology images. After 90 days of burial (Fig. 5a), the sample surface exhibited noticeable scratches with relatively shallow corrosion, making it difficult to clearly distinguish the corroded phases. In contrast, significant corrosion differences were observed in the microscopic morphology of samples buried for 360 days (Fig. 5b) and 720 days (Fig. 5c). Analysis of the SEM-SE and EDS map results for the 720 days sample revealed slight corrosion of the eutectoid phase in the matrix, which remained relatively intact, while the α phase was severely corroded.
在此基础上，为进一步研究双相锡铅青铜合金在弱碱性土壤环境中的腐蚀程度，对埋藏 90 d、360 d 和 720 d 的样品进行了腐蚀产物去除处理。 图 5 显示了显微形貌图像。埋藏 90 天后（ 图 5a），样品表面出现明显的划痕，腐蚀相对较浅，因此难以清楚地区分腐蚀相。相比之下，在埋藏 360 天（ 图 5b）和 720 天（ 图 5c）的样品的微观形态中观察到显着的腐蚀差异。对 720 天样品的 SEM-SE 和 EDS 图结果的分析显示，基质中的共构造相有轻微腐蚀，保持相对完整，而α相受到严重腐蚀。
Additionally, the region at the boundary between the α(I) phase and the eutectoid phase showed more severe corrosion compared to the center of the α(I) phase, likely due to greater surface roughness, resulting in brighter imaging in those areas.
此外，与 α（I） 相的中心相比，α（I） 相和共外相之间边界的区域显示出更严重的腐蚀，这可能是由于表面粗糙度更高，导致这些区域的成像更亮。
在此基础上，为进一步研究双相锡铅青铜合金在弱碱性土壤环境中的腐蚀程度，对埋藏 90 d、360 d 和 720 d 的样品进行了腐蚀产物去除处理。 图 5 显示了显微形貌图像。埋藏 90 天后（ 图 5a），样品表面出现明显的划痕，腐蚀相对较浅，因此难以清楚地区分腐蚀相。相比之下，在埋藏 360 天（ 图 5b）和 720 天（ 图 5c）的样品的微观形态中观察到显着的腐蚀差异。对 720 天样品的 SEM-SE 和 EDS 图结果的分析显示，基质中的共构造相有轻微腐蚀，保持相对完整，而α相受到严重腐蚀。
Additionally, the region at the boundary between the α(I) phase and the eutectoid phase showed more severe corrosion compared to the center of the α(I) phase, likely due to greater surface roughness, resulting in brighter imaging in those areas.
此外，与 α（I） 相的中心相比，α（I） 相和共外相之间边界的区域显示出更严重的腐蚀，这可能是由于表面粗糙度更高，导致这些区域的成像更亮。
Fig. 5. Microstructure after removing corrosion products. (a) 90 d, (b) 360 d and (c) 720 d.
图 5.去除腐蚀产物后的微观结构。（a） 90 天、（b） 360 天和 （c） 720 天。
3.3. Cross-sectional corrosion morphology analysis
3.3. 截面腐蚀形貌分析
In order to analyze the corrosion behavior of duplex tin-lead bronze alloy from microscopic perspective, the cross-sections of samples buried for 30 days, 180 days, 360 days, 540 days and 720 days were analyzed and observed. Fig. 6 shows the cross-sectional corrosion morphology and EDS diagram. From the corrosion morphology after burial for 30 days (Fig. 6a), it could be seen that the corrosion degree of the substrate was weak and the corrosion tendency could not be distinguished. As the corrosion time increases, it could be found that the sample presents α phase corrosion at 180 days (Fig. 6b). At 360 days (Fig. 6c), the sample showed δ phase corrosion and a layer of band-shaped corrosion products appeared on the surface of the sample. By comparing 540 d (Fig. 6d) and 720 d (Fig. 6e), it could be found that with the continued extension of corrosion time, obvious phase corrosion evolution occurred inside the substrate, that was, the corrosion degree of the (δ+α(II)) eutectic increased along the corrosion front, while the corrosion degree of the α phase decreased.
为了从微观角度分析双相锡铅青铜合金的腐蚀行为，对埋藏 30 d、180 d、360 d、540 d 和 720 d 的样品截面进行了分析和观察。 图 6 显示了横截面腐蚀形态和 EDS 图。从埋藏 30 天后的腐蚀形态（ 图 6a）可以看出，基材的腐蚀程度较弱，无法区分腐蚀倾向。随着腐蚀时间的增加，可以发现样品在 180 天时呈现α相腐蚀（ 图 6b）。在 360 天时（ 图 6c），样品出现δ相腐蚀，样品表面出现一层带状腐蚀产物。通过比较 540 d（ 图 6d）和 720 d（ 图 6e），可以发现，随着腐蚀时间的持续延长，基体内部发生了明显的相腐蚀演变，即 （δ+α（II）） 共晶的腐蚀程度沿腐蚀前沿增加，而 α 相的腐蚀程度降低。
In other words, the overall corrosion tendency of the sample changes from the α phase to the (δ+α(II)) eutectic structure. In this process, the thickness of the corrosion product layer on the surface shows an upward trend. In addition, at 720 days (Fig. 6e), a relatively dense corrosion product belt could be seen in the outermost layer of the sample.
换句话说，样品的整体腐蚀趋势从 α 相变为 （δ+α（II）） 共晶结构。在此过程中，表面腐蚀产物层的厚度呈上升趋势。此外，在 720 天时（ 图 6e），可以在样品的最外层看到相对致密的腐蚀产物带。
为了从微观角度分析双相锡铅青铜合金的腐蚀行为，对埋藏 30 d、180 d、360 d、540 d 和 720 d 的样品截面进行了分析和观察。 图 6 显示了横截面腐蚀形态和 EDS 图。从埋藏 30 天后的腐蚀形态（ 图 6a）可以看出，基材的腐蚀程度较弱，无法区分腐蚀倾向。随着腐蚀时间的增加，可以发现样品在 180 天时呈现α相腐蚀（ 图 6b）。在 360 天时（ 图 6c），样品出现δ相腐蚀，样品表面出现一层带状腐蚀产物。通过比较 540 d（ 图 6d）和 720 d（ 图 6e），可以发现，随着腐蚀时间的持续延长，基体内部发生了明显的相腐蚀演变，即 （δ+α（II）） 共晶的腐蚀程度沿腐蚀前沿增加，而 α 相的腐蚀程度降低。
In other words, the overall corrosion tendency of the sample changes from the α phase to the (δ+α(II)) eutectic structure. In this process, the thickness of the corrosion product layer on the surface shows an upward trend. In addition, at 720 days (Fig. 6e), a relatively dense corrosion product belt could be seen in the outermost layer of the sample.
换句话说，样品的整体腐蚀趋势从 α 相变为 （δ+α（II）） 共晶结构。在此过程中，表面腐蚀产物层的厚度呈上升趋势。此外，在 720 天时（ 图 6e），可以在样品的最外层看到相对致密的腐蚀产物带。
Fig. 6. Cross-sectional microstructure and EDS maps of Sn-Pb bronze alloy at different stages. (a) 30d, (b) 180d, (c) 360d, (d) 540 d, (e) 720d and (f) EDS maps. (SEM images are from the blue squares, EDS maps are from the green squares).
图 6.Sn-Pb 青铜合金在不同阶段的横截面微观组织和 EDS 图。（a） 30d、（b） 180d、（c） 360d、（d） 540 d、（e） 720d 和 （f） EDS 地图。（SEM 图像来自蓝色方块，EDS 图来自绿色方块）。
Combined with the EDS maps (Fig. 6f), it could be found that the outer corrosion products mainly contain Cu, O and Cl elements, and the banded corrosion products are Cl-rich layers.
重试
错误原因
In addition, the α phase corrosion area shows that Cu and Sn elements were lost, while the (δ+α(II)) eutectoid corrosion area had higher Sn and Cl content and less O content. 重试 错误原因
In addition, the α phase corrosion area shows that Cu and Sn elements were lost, while the (δ+α(II)) eutectoid corrosion area had higher Sn and Cl content and less O content. 重试 错误原因
3.4. Electrochemical analysis
3.4. 电化学分析
To further investigate the corrosion characteristics and surface corrosion layer status of the duplex tin-lead bronze alloy in mildly alkaline soil environment, impedance spectroscopy analysis was conducted on samples with different exposure periods. Fig. 7 presented the EIS test results. The equivalent circuit in Fig. 7d effectively fitted the EIS data [20], [21], [22], with the fitting results summarized in Table 5. Due to the diffusion effect observed in the actual experiments and the fact that the double-layer capacitance could not be considered an ideal capacitor, a constant phase element (Q) was introduced to replace the ideal capacitor element. The impedance of Q was represented by Eq. 1 [23], [24], [25].
为进一步研究双相锡铅青铜合金在弱碱性土壤环境中的腐蚀特性和表面腐蚀层状态，对不同暴露时间的样品进行了阻抗谱分析。 图 7 显示了 EIS 测试结果。 图 7d 中的等效电路有效地拟合了 EIS 数据 [20]、[21]、[22]，拟合结果总结在表 5 中。由于在实际实验中观察到的扩散效应以及双层电容不能被视为理想电容器的事实，因此引入了恒相元件 （Q） 来代替理想电容器元件。Q 的阻抗由方程 1[23]、[24]、[25] 表示。(1)Where Z is the impedance of Q, j is the unit imaginary part, ω is the angular frequency, Y0 is a constant, and n is the diffusion effect index of Q (0 < n < 1). In the fitting results, Rs is the solution resistance, Rf and Yf correspond to the resistance and capacitance of the surface corrosion product film, respectively. Rct and Ydl are the charge transfer resistance and double layer capacitance, and ZW is the Warburg diffusion impedance in the low frequency region.
其中 Z 是 Q 的阻抗，j 是单位虚部，ω 是角频率，Y0 是常数，n 是 Q 的扩散效应指数 （0 < n < 1）。在拟合结果中，Rs 是固溶电阻，Rf 和 Yf 分别对应于表面腐蚀产物膜的电阻和电容。Rct 和 Ydl 是电荷转移电阻和双电层电容，ZW 是低频区的 Warburg 扩散阻抗。
为进一步研究双相锡铅青铜合金在弱碱性土壤环境中的腐蚀特性和表面腐蚀层状态，对不同暴露时间的样品进行了阻抗谱分析。 图 7 显示了 EIS 测试结果。 图 7d 中的等效电路有效地拟合了 EIS 数据 [20]、[21]、[22]，拟合结果总结在表 5 中。由于在实际实验中观察到的扩散效应以及双层电容不能被视为理想电容器的事实，因此引入了恒相元件 （Q） 来代替理想电容器元件。Q 的阻抗由方程 1[23]、[24]、[25] 表示。(1)Where Z is the impedance of Q, j is the unit imaginary part, ω is the angular frequency, Y0 is a constant, and n is the diffusion effect index of Q (0 < n < 1). In the fitting results, Rs is the solution resistance, Rf and Yf correspond to the resistance and capacitance of the surface corrosion product film, respectively. Rct and Ydl are the charge transfer resistance and double layer capacitance, and ZW is the Warburg diffusion impedance in the low frequency region.
其中 Z 是 Q 的阻抗，j 是单位虚部，ω 是角频率，Y0 是常数，n 是 Q 的扩散效应指数 （0 < n < 1）。在拟合结果中，Rs 是固溶电阻，Rf 和 Yf 分别对应于表面腐蚀产物膜的电阻和电容。Rct 和 Ydl 是电荷转移电阻和双电层电容，ZW 是低频区的 Warburg 扩散阻抗。
Fig. 7. EIS of duplex tin-lead bronze alloy at different stages. (a) Nyquist diagram, (b) Bode-|Z| diagram, (c) Bode-phase diagram and (d) equivalent circuit diagram.
图 7.双相锡铅青铜合金在不同阶段的 EIS。（a） 奈奎斯特图，（b） 波特图 |Z|图，（c） 波特相图和 （d） 等效电路图。
Table 5. Fitting parameters of EIS for duplex tin-lead bronze alloy at different time periods.
表 5.不同时期双相锡铅青铜合金的 EIS 拟合参数。
| Time/ 时间/ day(s) 天 | Rs (Ω·cm2) （Ω·厘米 2） | Y0 f 和 0 f (F cm−2 sn−1) （F cm-2 sn-1） | nf | Rf 射频 (Ω·cm2) （Ω·厘米 2） | Y0 dl 并且 0 分升 (F cm−2 sn−1) （F cm-2 sn-1） | ndl | Rct (Ω·cm2) （Ω·厘米 2） | Zw (Ω·cm2) （Ω·厘米 2） |
|---|---|---|---|---|---|---|---|---|
| 0 | 188.1 | — | — | — | 7.25 × 10−5 | 0.7581 | 7481 | 3.52 × 10−4 |
| 30 | 85.3 | — | — | — | 1.59 × 10−4 | 0.7394 | 1386 | 8.31 × 10−3 |
| 180 | 55.39 | — | — | — | 2.36 × 10−4 | 0.2091 | 247 | 7.45 × 10−5 |
| 360 | 86.45 | — | — | — | 2.47 × 10−4 | 0.2069 | 354.4 | 7.65 × 10−5 7.65 × 10-5 |
| 540 | 57.45 | — | — | — | 2.33 × 10−5 | 0.797 | 8553 | 4.03 × 10−5 |
| 720 | 34.29 | 8.21 × 10−5 | 0.4239 | 212.1 | 5.11 × 10−5 | 0.839 | 1.04 × 104 | — |
By comparing the Nyquist plots of samples with different cycles (Fig. 7a), it was found that the samples were almost entirely affected by the Warburg impedance throughout the entire corrosion process. In addition, only one capacitive reactance appeared in the sample at the initial stage of corrosion.
通过比较不同循环样品的奈奎斯特图（ 图 7a），发现在整个腐蚀过程中，样品几乎完全受到 Warburg 阻抗的影响。此外，在腐蚀初期，样品中仅出现一个电容电抗。
As the corrosion time increased, two capacitive reactance appeared in the sample after 720 days of burial, which corresponded to the time constants observed in the Bode-phase plot. From the fitting results, the value of ndl showed a trend of initially decreasing and then increasing. Similarly, the charge transfer resistance Rct also exhibited a trend of decreasing first and then increasing. In contrast, the Warburg impedance gradually decreased as the corrosion time extended.
随着腐蚀时间的增加，埋藏 720 d 后样品中出现两个电容电抗，这与波特相图中观察到的时间常数相对应。从拟合结果来看，ndl 的值呈现先减小后增加的趋势。同样，电荷转移电阻 Rct 也表现出先下降后增加的趋势。相比之下，Warburg 阻抗随着腐蚀时间的延长而逐渐减小。
通过比较不同循环样品的奈奎斯特图（ 图 7a），发现在整个腐蚀过程中，样品几乎完全受到 Warburg 阻抗的影响。此外，在腐蚀初期，样品中仅出现一个电容电抗。
As the corrosion time increased, two capacitive reactance appeared in the sample after 720 days of burial, which corresponded to the time constants observed in the Bode-phase plot. From the fitting results, the value of ndl showed a trend of initially decreasing and then increasing. Similarly, the charge transfer resistance Rct also exhibited a trend of decreasing first and then increasing. In contrast, the Warburg impedance gradually decreased as the corrosion time extended.
随着腐蚀时间的增加，埋藏 720 d 后样品中出现两个电容电抗，这与波特相图中观察到的时间常数相对应。从拟合结果来看，ndl 的值呈现先减小后增加的趋势。同样，电荷转移电阻 Rct 也表现出先下降后增加的趋势。相比之下，Warburg 阻抗随着腐蚀时间的延长而逐渐减小。
On this basis, in order to characterize the change of the double-layer capacitance of the sample surface during the corrosion process, the double-layer capacitance was calculated using (2), (3) [26], [27], [28], [29]. Fig. 8 shows the calculation results.
在此基础上，为了表征腐蚀过程中样品表面双电层电容的变化，用 （2）、（3）[26]、[27]、[28]、[29] 计算双电层电容。 图 8 显示了计算结果。(2)(3)Where Cdl is the double layer capacitance, n is the test index, usually between 0 and 1. Rs is the solution resistance, and Rf is the membrane resistance. In addition, the double layer capacitance can also be calculated using Eq. 4 [30], [31]:
其中 Cdl 是双电层电容， n 是测试指数，通常介于 0 和 1 之间。Rs 是溶液阻力，Rf 是膜阻力。此外，双电层电容也可以使用公式 4[30]、[31] 计算：(4)Where ε and ε0 are dielectric constants, A is the exposed area, and d is the thickness of the double layer capacitor. It could be seen from Eq. 4 that the double layer capacitance was inversely proportional to the thickness of the double layer capacitance.
其中 ε 和 ε0 是介电常数，A 是暴露面积，d 是双层电容器的厚度。从公式 4 中可以看出，双层电容与双层电容的厚度成反比。
Therefore, the results show that before 360 days, the double-layer capacitance on the sample surface exhibited a downward trend, indicating that the thickness of the double-layer capacitance on the sample surface increased over time.
因此，结果表明，在 360 天之前，样品表面的双电层电容呈下降趋势，表明样品表面双电层电容的厚度随着时间的推移而增加。
This result is similar to our previous research findings [32], which indicated that an oxygen-free environment can lead to a decrease in the double-layer capacitance of the sample. After 360 days, the thickness of the double-layer capacitance gradually decreased, reaching a level close to that of the initial sample at 540 days.
这一结果与我们之前的研究结果相似 [32]，后者表明无氧环境会导致样品的双电层电容降低。360 天后，双层电容的厚度逐渐减小，在 540 天时达到接近初始样品的水平。
Therefore, the results suggest that the phase corrosion mechanisms evolution of the bronze alloy is influenced by the double-layer capacitance, which is, in turn, affected by the dissolved oxygen.
因此，结果表明，青铜合金的相腐蚀机理演变受双层电容的影响，而双电层电容又受溶解氧的影响。
在此基础上，为了表征腐蚀过程中样品表面双电层电容的变化，用 （2）、（3）[26]、[27]、[28]、[29] 计算双电层电容。 图 8 显示了计算结果。(2)(3)Where Cdl is the double layer capacitance, n is the test index, usually between 0 and 1. Rs is the solution resistance, and Rf is the membrane resistance. In addition, the double layer capacitance can also be calculated using Eq. 4 [30], [31]:
其中 Cdl 是双电层电容， n 是测试指数，通常介于 0 和 1 之间。Rs 是溶液阻力，Rf 是膜阻力。此外，双电层电容也可以使用公式 4[30]、[31] 计算：(4)Where ε and ε0 are dielectric constants, A is the exposed area, and d is the thickness of the double layer capacitor. It could be seen from Eq. 4 that the double layer capacitance was inversely proportional to the thickness of the double layer capacitance.
其中 ε 和 ε0 是介电常数，A 是暴露面积，d 是双层电容器的厚度。从公式 4 中可以看出，双层电容与双层电容的厚度成反比。
Therefore, the results show that before 360 days, the double-layer capacitance on the sample surface exhibited a downward trend, indicating that the thickness of the double-layer capacitance on the sample surface increased over time.
因此，结果表明，在 360 天之前，样品表面的双电层电容呈下降趋势，表明样品表面双电层电容的厚度随着时间的推移而增加。
This result is similar to our previous research findings [32], which indicated that an oxygen-free environment can lead to a decrease in the double-layer capacitance of the sample. After 360 days, the thickness of the double-layer capacitance gradually decreased, reaching a level close to that of the initial sample at 540 days.
这一结果与我们之前的研究结果相似 [32]，后者表明无氧环境会导致样品的双电层电容降低。360 天后，双层电容的厚度逐渐减小，在 540 天时达到接近初始样品的水平。
Therefore, the results suggest that the phase corrosion mechanisms evolution of the bronze alloy is influenced by the double-layer capacitance, which is, in turn, affected by the dissolved oxygen.
因此，结果表明，青铜合金的相腐蚀机理演变受双层电容的影响，而双电层电容又受溶解氧的影响。
Fig. 8. Calculation results of Cdl of bronze alloys at different periods.
图 8.青铜合金在不同时期的 Cdl 计算结果。
Fig. 9 shows the polarization curves of the duplex tin bronze alloy at different burial periods in a weakly alkaline soil simulation solution. Overall, there were obvious differences in the polarization curves of the samples.
图 9 显示了双相锡青铜合金在弱碱性土壤模拟溶液中不同埋藏期的极化曲线。总体而言，样品的极化曲线存在明显差异。
In the early stage of corrosion (0 d-180 d), there was a relatively obvious potential peak in the anode section of the sample, which was similar to the test results of Wang et al. [7], [32]. In the later stage of corrosion (360 d-720 d), the potential peak of the anode segment gradually weakened and disappeared at 720 d. At this time, the sample as a whole exhibited activation polarization.
在腐蚀初期（0 d-180 d），样品的阳极段存在一个相对明显的电位峰，这与 Wang 等[7]、[32] 的测试结果相似。在腐蚀后期（360 d-720 d），阳极段的电位峰逐渐减弱，并在 720 d 时消失。此时，样品作为一个整体表现出活化极化。
This result indicated that the corrosion layer on the surface of the sample differed between the two periods, suggesting that the structure of the surface state had changed.
这一结果表明，样品表面的腐蚀层在两个时期不同，表明表面状态的结构发生了变化。
图 9 显示了双相锡青铜合金在弱碱性土壤模拟溶液中不同埋藏期的极化曲线。总体而言，样品的极化曲线存在明显差异。
In the early stage of corrosion (0 d-180 d), there was a relatively obvious potential peak in the anode section of the sample, which was similar to the test results of Wang et al. [7], [32]. In the later stage of corrosion (360 d-720 d), the potential peak of the anode segment gradually weakened and disappeared at 720 d. At this time, the sample as a whole exhibited activation polarization.
在腐蚀初期（0 d-180 d），样品的阳极段存在一个相对明显的电位峰，这与 Wang 等[7]、[32] 的测试结果相似。在腐蚀后期（360 d-720 d），阳极段的电位峰逐渐减弱，并在 720 d 时消失。此时，样品作为一个整体表现出活化极化。
This result indicated that the corrosion layer on the surface of the sample differed between the two periods, suggesting that the structure of the surface state had changed.
这一结果表明，样品表面的腐蚀层在两个时期不同，表明表面状态的结构发生了变化。
Fig. 9. Polarization curves of duplex tin-lead bronze alloy at different stages. (a) 0 d-180 d and (b) 360 d-720 d.
图 9.双相锡铅青铜合金在不同阶段的极化曲线。（a） 0 D-180 D 和 （B） 360 D-720 D。
Secondly, it can be seen from the polarization curve fitting results (Table 6) that Ecorr first decreases and then increases, while icorr shows an increasing trend overall. From the perspective of thermodynamics and kinetics, the corrosion resistance of bronze alloys first weakens and then increases with the extension of corrosion time. However, its corrosion rate consistently shows an increasing trend.
其次，从极化曲线拟合结果（ 表 6）可以看出，Ecorr 先减小后增加，而 icorr 总体上呈上升趋势。从热力学和动力学的角度来看，青铜合金的耐蚀性随着腐蚀时间的延长而先减弱后增大。然而，它的腐蚀速率始终呈上升趋势。
The corrosion rate increased rapidly before 360 days, but after that, the corrosion rate was not much different and maintained a relatively stable corrosion rate.
腐蚀速率在 360 天之前迅速增加，但之后腐蚀速率相差不大，保持了相对稳定的腐蚀速率。
其次，从极化曲线拟合结果（ 表 6）可以看出，Ecorr 先减小后增加，而 icorr 总体上呈上升趋势。从热力学和动力学的角度来看，青铜合金的耐蚀性随着腐蚀时间的延长而先减弱后增大。然而，它的腐蚀速率始终呈上升趋势。
The corrosion rate increased rapidly before 360 days, but after that, the corrosion rate was not much different and maintained a relatively stable corrosion rate.
腐蚀速率在 360 天之前迅速增加，但之后腐蚀速率相差不大，保持了相对稳定的腐蚀速率。
Table 6. Fitting parameters of polarization curves.
表 6.极化曲线的拟合参数。
| Time/d 时间/天 | Ecorr/V E 更正 /V | icorr/μA·cm−2 i 更正 /μA·cm−2 |
|---|---|---|
| 0 | −0.63 | 9.11 |
| 30 | −0.62 | 16.89 |
| 180 | −0.63 | 20.11 |
| 360 | −0.67 | 23.53 |
| 540 | −0.71 | 25.96 |
| 720 | −0.61 | 25.31 |
4. Discussion 4. 讨论
In ancient times, bronze was often buried deep in the soil as a burial object. In today’s society, copper alloys are often made into materials for communications and buried in urban soil [33], [34]. However, the properties of the soil in which the copper alloy is located may change over time. These changes are crucial to the corrosion of bronze alloys, because they can change the corrosion rate and corrosion mechanism of the metal.
在古代，青铜通常作为陪葬品深埋在土壤中。在当今社会，铜合金经常被制成通讯材料，并埋在城市土壤中 [33]、[34]。 然而，铜合金所在土壤的特性可能会随着时间的推移而改变。这些变化对青铜合金的腐蚀至关重要，因为它们可以改变金属的腐蚀速率和腐蚀机理。
Therefore, this study can not only study the corrosion mechanism of ancient bronze artifacts, but also provide a basis for the preparation of corrosion-resistant copper alloy materials.
因此，本研究不仅可以研究古代青铜器物的腐蚀机理，而且可以为制备耐腐蚀铜合金材料提供依据。
在古代，青铜通常作为陪葬品深埋在土壤中。在当今社会，铜合金经常被制成通讯材料，并埋在城市土壤中 [33]、[34]。 然而，铜合金所在土壤的特性可能会随着时间的推移而改变。这些变化对青铜合金的腐蚀至关重要，因为它们可以改变金属的腐蚀速率和腐蚀机理。
Therefore, this study can not only study the corrosion mechanism of ancient bronze artifacts, but also provide a basis for the preparation of corrosion-resistant copper alloy materials.
因此，本研究不仅可以研究古代青铜器物的腐蚀机理，而且可以为制备耐腐蚀铜合金材料提供依据。
Based on the above purposes, through 720 days (2 years) burial test of the duplex tin-lead bronze alloy in mildly alkaline soil, it was found that there was a tendency for phase corrosion mechanisms evolution during the corrosion process, Fig. 10 was a schematic diagram of the corrosion mechanism of duplex tin bronze alloy in a weakly alkaline soil environment.
基于上述目的，通过对双相锡铅青铜合金在弱碱性土壤中进行 720 d（2 年）的埋设试验，发现在腐蚀过程中存在相腐蚀机理演变的趋势， 图 10 是双相锡青铜合金在弱碱性土壤环境中腐蚀机理的示意图。
In the early stages of burial, a reddish-brown corrosion product first appeared on the sample surface, but the phase corrosion trend within the substrate was not clearly defined.
在埋藏的早期阶段，红棕色腐蚀产物首先出现在样品表面，但基材内的相腐蚀趋势并不明确。
As the corrosion time increased, it was obvious that the corrosion proceeded along the α phase at 360 days. At this time, the surface of the sample was covered with a layer of rough dark green corrosion products.
随着腐蚀时间的增加，很明显腐蚀在 360 天时沿着 α 相进行。此时，样品表面覆盖着一层粗糙的深绿色腐蚀产物。
In the later stage of corrosion (540 days), the corrosion tendency also changed significantly and evolved from the initial α phase (Cu content is 89.83 wt%) to the (δ + α(II)) eutectoid phase (Sn content is 39.48 wt%).
在腐蚀后期（540 d），腐蚀趋势也发生了显著变化，从初始α期（Cu 含量为 89.83 wt%）演变为（δ + α（II）））共析期（Sn 含量为 39.48 wt%）。
At the same time, some loose green products fell off and exposed reddish-brown corrosion products. Since the corrosion environment of the sample was a closed container, we considered the influence of various factors on the phase corrosion mechanisms evolution of bronze alloy [35], [36].
同时，一些松散的绿色产品脱落，露出红棕色的腐蚀产物。由于样品的腐蚀环境是一个封闭的容器，我们考虑了各种因素对青铜合金相腐蚀机理演变的影响 [35]、[36]。
基于上述目的，通过对双相锡铅青铜合金在弱碱性土壤中进行 720 d（2 年）的埋设试验，发现在腐蚀过程中存在相腐蚀机理演变的趋势， 图 10 是双相锡青铜合金在弱碱性土壤环境中腐蚀机理的示意图。
In the early stages of burial, a reddish-brown corrosion product first appeared on the sample surface, but the phase corrosion trend within the substrate was not clearly defined.
在埋藏的早期阶段，红棕色腐蚀产物首先出现在样品表面，但基材内的相腐蚀趋势并不明确。
As the corrosion time increased, it was obvious that the corrosion proceeded along the α phase at 360 days. At this time, the surface of the sample was covered with a layer of rough dark green corrosion products.
随着腐蚀时间的增加，很明显腐蚀在 360 天时沿着 α 相进行。此时，样品表面覆盖着一层粗糙的深绿色腐蚀产物。
In the later stage of corrosion (540 days), the corrosion tendency also changed significantly and evolved from the initial α phase (Cu content is 89.83 wt%) to the (δ + α(II)) eutectoid phase (Sn content is 39.48 wt%).
在腐蚀后期（540 d），腐蚀趋势也发生了显著变化，从初始α期（Cu 含量为 89.83 wt%）演变为（δ + α（II）））共析期（Sn 含量为 39.48 wt%）。
At the same time, some loose green products fell off and exposed reddish-brown corrosion products. Since the corrosion environment of the sample was a closed container, we considered the influence of various factors on the phase corrosion mechanisms evolution of bronze alloy [35], [36].
同时，一些松散的绿色产品脱落，露出红棕色的腐蚀产物。由于样品的腐蚀环境是一个封闭的容器，我们考虑了各种因素对青铜合金相腐蚀机理演变的影响 [35]、[36]。
Fig. 10. Schematic diagram of the corrosion mechanism of duplex tin-lead bronze alloy in weakly alkaline accelerated soil burial environment at different stages. (a-b) early corrosion stage (before 360 days) and (c-d) late corrosion stage (after 360 days).
图 10.双相锡铅青铜合金在弱碱性加速土埋藏环境中不同阶段的腐蚀机理示意图。（a-b） 早期腐蚀阶段（360 天之前）和 （c-d） 晚期腐蚀阶段（360 天后）。
4.1. Effect of Cl ions and pH value
4.1. Cl 离子和 pH 值的影响
In the above results, the study found that bronze alloys underwent significant evolution during the corrosion process. According to previous literature surveys, the corrosion evolution of metals may be affected by pH and Cl ion concentration [37], [38]. After the phase corrosion evolution (540 days and 720 days), we tested the pH value of the soil (where the sample was buried). The study found that its value fluctuated at 8.4 ± 0.1, which was not much different from the initial value.
在上述结果中，研究发现青铜合金在腐蚀过程中发生了显着的演变。根据以往的文献调查，金属的腐蚀演变可能受到 pH 值和 Cl 离子浓度的影响 [37]、[38]。 在相腐蚀演变（540 天和 720 天）之后，我们测试了土壤（样品埋藏的地方）的 pH 值。研究发现，其值在 8.4 ± 0.1 之间波动，与初始值相差不大。
In addition, regarding the effect of pH value on the corrosion behavior of duplex tin-lead bronze alloys, our research team has previously conducted research on the corrosion behavior of duplex tin-lead bronze alloys in acidic solutions and found that duplex tin-lead bronze alloys did not undergo eutectic phase corrosion [39], [40]. Therefore, we can conclude that pH value has little effect on the corrosion evolution of duplex bronze alloys.
此外，关于 pH 值对双相锡铅青铜合金腐蚀行为的影响，我们的研究团队之前对双相锡铅青铜合金在酸性溶液中的腐蚀行为进行了研究，发现双相锡铅青铜合金没有发生共晶相腐蚀 [39]，[40]。 因此，我们可以得出结论，pH 值对双相青铜合金的腐蚀演变影响不大。
在上述结果中，研究发现青铜合金在腐蚀过程中发生了显着的演变。根据以往的文献调查，金属的腐蚀演变可能受到 pH 值和 Cl 离子浓度的影响 [37]、[38]。 在相腐蚀演变（540 天和 720 天）之后，我们测试了土壤（样品埋藏的地方）的 pH 值。研究发现，其值在 8.4 ± 0.1 之间波动，与初始值相差不大。
In addition, regarding the effect of pH value on the corrosion behavior of duplex tin-lead bronze alloys, our research team has previously conducted research on the corrosion behavior of duplex tin-lead bronze alloys in acidic solutions and found that duplex tin-lead bronze alloys did not undergo eutectic phase corrosion [39], [40]. Therefore, we can conclude that pH value has little effect on the corrosion evolution of duplex bronze alloys.
此外，关于 pH 值对双相锡铅青铜合金腐蚀行为的影响，我们的研究团队之前对双相锡铅青铜合金在酸性溶液中的腐蚀行为进行了研究，发现双相锡铅青铜合金没有发生共晶相腐蚀 [39]，[40]。 因此，我们可以得出结论，pH 值对双相青铜合金的腐蚀演变影响不大。
At the same time, a review of past literature shows that bronze alloys in salt spray environments and a large number of unearthed bronze artifacts are all α-phase corrosion [9], [10]. The result was consistent with the early corrosion results of this soil corrosion experiment. Therefore, the results show that the concentration of Cl ions is not the main cause of the corrosion evolution of the duplex bronze alloy.
同时，对以往文献的回顾表明，盐雾环境中的青铜合金和大量出土的青铜文物都是α相腐蚀 [9]、[10]。 结果与该土壤腐蚀实验的早期腐蚀结果一致。因此，结果表明，Cl 离子的浓度并不是双相青铜合金腐蚀演变的主要原因。
However, in the later stage of corrosion, the excessive Cl ion content does cause changes in the structure of the corrosion product layer on the surface of the sample, that is, a layer of Cl-rich corrosion product band structure is produced (Fig. 5g, Fig. 5j, Fig. 5m). In previous studies [32], we found that the Cl-rich layer is crucial to the evolution between Cu and Sn, and this fact is sufficient to cause phase corrosion evolution in bronze alloys. The relevant content is explained in Section 4.3.
但在腐蚀后期，过量的 Cl 离子含量确实会导致样品表面腐蚀产物层的结构发生变化，即产生一层富含 Cl 的腐蚀产物带结构（ 图 5g、 图 5j、 图 5m）。在以前的研究中 [32]，我们发现富 Cl 层对 Cu 和 Sn 之间的演化至关重要，这一事实足以引起青铜合金的相腐蚀演化。相关内容在 Section 4.3 中解释。
同时，对以往文献的回顾表明，盐雾环境中的青铜合金和大量出土的青铜文物都是α相腐蚀 [9]、[10]。 结果与该土壤腐蚀实验的早期腐蚀结果一致。因此，结果表明，Cl 离子的浓度并不是双相青铜合金腐蚀演变的主要原因。
However, in the later stage of corrosion, the excessive Cl ion content does cause changes in the structure of the corrosion product layer on the surface of the sample, that is, a layer of Cl-rich corrosion product band structure is produced (Fig. 5g, Fig. 5j, Fig. 5m). In previous studies [32], we found that the Cl-rich layer is crucial to the evolution between Cu and Sn, and this fact is sufficient to cause phase corrosion evolution in bronze alloys. The relevant content is explained in Section 4.3.
但在腐蚀后期，过量的 Cl 离子含量确实会导致样品表面腐蚀产物层的结构发生变化，即产生一层富含 Cl 的腐蚀产物带结构（ 图 5g、 图 5j、 图 5m）。在以前的研究中 [32]，我们发现富 Cl 层对 Cu 和 Sn 之间的演化至关重要，这一事实足以引起青铜合金的相腐蚀演化。相关内容在 Section 4.3 中解释。
4.2. Effect of oxygen 4.2. 氧气的影响
For bronze alloys with passive characteristics, oxygen was a crucial factor in the corrosion process [32], [38], [41]. In order to verify that oxygen was the main factor causing the phase corrosion mechanisms evolution of bronze alloys, simulated immersion experiments of bronze alloys in aerobic and anaerobic environments were conducted. Fig. 11 shows the test results. The results showed that the sample in an aerobic environment eventually corroded along the α phase. In contrast, the sample in an anaerobic environment exhibited (δ + α(II)) eutectoid corrosion.
对于具有钝化特性的青铜合金，氧是腐蚀过程中的关键因素 [32]、[38]、[41]。 为了验证氧是导致青铜合金相腐蚀机理演变的主要因素，对青铜合金在好氧和厌氧环境中进行了模拟浸泡实验。 图 11 显示了测试结果。结果表明，在好氧环境中的样品最终沿α相腐蚀。相比之下，厌氧环境中的样品表现出 （δ + α（II）） 共析腐蚀。
对于具有钝化特性的青铜合金，氧是腐蚀过程中的关键因素 [32]、[38]、[41]。 为了验证氧是导致青铜合金相腐蚀机理演变的主要因素，对青铜合金在好氧和厌氧环境中进行了模拟浸泡实验。 图 11 显示了测试结果。结果表明，在好氧环境中的样品最终沿α相腐蚀。相比之下，厌氧环境中的样品表现出 （δ + α（II）） 共析腐蚀。
Fig. 11. Immersion test results. (a) aerobic environment and (b) anaerobic environment.
图 11.浸入测试结果。（a） 好氧环境和 （b） 厌氧环境。
In addition, the EDS results show that the corrosion of the sample in an aerobic environment caused the loss of Cu and Sn, while the corrosion in an anaerobic environment showed the enrichment of Sn and Cl elements.
此外，EDS 结果表明，样品在好氧环境中的腐蚀导致 Cu 和 Sn 的损失，而在厌氧环境中的腐蚀表明 Sn 和 Cl 元素的富集。
Based on the results of the soil corrosion experiment, it could be found that the corrosion trend of the duplex bronze alloy in the early stage of soil corrosion was consistent with that in an aerobic environment (both were α phase corrosion), while the corrosion trend in the late stage of soil corrosion was consistent with that in an anaerobic environment (both were eutectoid phase corrosion).
基于土体腐蚀试验结果可发现，双相青铜合金在土体腐蚀初期的腐蚀趋势与好氧环境下的腐蚀趋势一致（均为α相腐蚀），而土体腐蚀后期的腐蚀趋势与厌氧环境下的腐蚀趋势一致（均为共析相腐蚀）。
此外，EDS 结果表明，样品在好氧环境中的腐蚀导致 Cu 和 Sn 的损失，而在厌氧环境中的腐蚀表明 Sn 和 Cl 元素的富集。
Based on the results of the soil corrosion experiment, it could be found that the corrosion trend of the duplex bronze alloy in the early stage of soil corrosion was consistent with that in an aerobic environment (both were α phase corrosion), while the corrosion trend in the late stage of soil corrosion was consistent with that in an anaerobic environment (both were eutectoid phase corrosion).
基于土体腐蚀试验结果可发现，双相青铜合金在土体腐蚀初期的腐蚀趋势与好氧环境下的腐蚀趋势一致（均为α相腐蚀），而土体腐蚀后期的腐蚀趋势与厌氧环境下的腐蚀趋势一致（均为共析相腐蚀）。
On this basis, M-S curves were used to characterize the effect of oxygen on the bronze alloy and the properties of the surface film. Fig. 12 presented the test results. The experimental findings indicated that the samples in an oxygen-rich environment could form a distinct passivation film. Whereas in an oxygen-free environment, the samples did not develop a stable passivation film.
在此基础上，采用 M-S 曲线表征氧对青铜合金的影响和表面膜的性能。 图 12 显示了测试结果。实验结果表明，样品在富氧环境中可以形成明显的钝化膜。而在无氧环境中，样品不会形成稳定的钝化膜。
The M-S curve obtained in an aerobic environment was fitted and calculated using (5), (6) [42], [43]:
在有氧环境中获得的 M-S 曲线使用 （5）、（6）[42]、[43] 进行拟合和计算：(5)(6)
在此基础上，采用 M-S 曲线表征氧对青铜合金的影响和表面膜的性能。 图 12 显示了测试结果。实验结果表明，样品在富氧环境中可以形成明显的钝化膜。而在无氧环境中，样品不会形成稳定的钝化膜。
The M-S curve obtained in an aerobic environment was fitted and calculated using (5), (6) [42], [43]:
在有氧环境中获得的 M-S 曲线使用 （5）、（6）[42]、[43] 进行拟合和计算：(5)(6)
Fig. 12. M-S curve test results.
图 12.M-S 曲线测试结果。
In the formula, e represented the charge energy, valued at 1.602 × 10−19 C, m was the slope of the linear region in the M-S curve, ND was the donor density, which could be obtained from the slope. E, EFB, K and T represent the applied potential, flat band potential, Boltzmann constant, and absolute temperature, respectively. The fitting results (Table 7) showed that the slope was positive, with a donor density of 11.29 × 1029 cm−3. This indicated that the oxide film on the surface of the bronze alloy behaves as an N type semiconductor and exhibits strong sensitivity to oxygen atoms [44], [45]. Therefore, by combining the immersion and M-S curve test results, it could be inferred that the oxide film on the surface of the bronze alloy was the primary reason for the phase corrosion mechanisms evolution.
在公式中，e 表示电荷能，值为 1.602 × 10−19 C，m 是 M-S 曲线中线性区域的斜率 ，ND 是供体密度，可以从斜率中获得。E、EFB、K 和 T 分别代表施加的电势、平带电势、玻尔兹曼常数和绝对温度。拟合结果（ 表 7）显示斜率为正，供体密度为 11.29 × 1029 cm−3。这表明青铜合金表面的氧化膜表现为 N 型半导体，对氧原子表现出很强的敏感性 [44]、[45]。 因此，结合浸泡和 M-S 曲线测试结果，可以推断青铜合金表面的氧化膜是相腐蚀机理演变的主要原因。
在公式中，e 表示电荷能，值为 1.602 × 10−19 C，m 是 M-S 曲线中线性区域的斜率 ，ND 是供体密度，可以从斜率中获得。E、EFB、K 和 T 分别代表施加的电势、平带电势、玻尔兹曼常数和绝对温度。拟合结果（ 表 7）显示斜率为正，供体密度为 11.29 × 1029 cm−3。这表明青铜合金表面的氧化膜表现为 N 型半导体，对氧原子表现出很强的敏感性 [44]、[45]。 因此，结合浸泡和 M-S 曲线测试结果，可以推断青铜合金表面的氧化膜是相腐蚀机理演变的主要原因。
Table 7. M-S curve fitting results.
表 7.M-S 曲线拟合结果。
| Solution 溶液 | ND1021(cm−3) 北 D1021（厘米 −3） | EFB (V) EFB （V） |
|---|---|---|
| Aerobic 健美操 | 11.29 | 0.0667 |
| Anaerobic 厌氧 | - | 0.0453 |
4.3. Effect of Chloride 4.3. 氯化物的作用
Through the above research results, it could be found that oxygen was the main cause of the corrosion evolution of the duplex bronze alloy.
通过上述研究结果可以发现，氧是双相青铜合金腐蚀演变的主要原因。
From the electrochemical test results, it could be found that the double-layer capacitance measured in this experimental system first decreases and then increases, and the lowest value of the double-layer capacitance is at 360 d. In addition, it could be clearly observed from Fig. 5g-m that there was a Cl-rich layer on the surface of the sample. This research result was similar to the corrosion behavior of bronze alloys in an oxygen-free environment studied by Fan et al. [32], [46]. At the same time, they pointed out that the double-layer capacitance value of bronze alloys always remains extremely low in an oxygen-free environment. The results of both indicate that the duplex bronze alloy enters an oxygen-free corrosion state at 360 d.
从电化学测试结果可以发现，在该实验系统中测得的双电层电容先减小后增大，双电层电容的最低值在 360 d 时。此外，从图 5g-m 中可以清楚地观察到样品表面有一层富含 Cl 的层。该研究结果类似于 Fan 等人 [32]、[46] 研究的青铜合金在无氧环境中的腐蚀行为。同时，他们指出，在无氧环境中，青铜合金的双电层电容值始终保持极低。两者的结果表明，双相青铜合金在 360 d 时进入无氧腐蚀状态。
通过上述研究结果可以发现，氧是双相青铜合金腐蚀演变的主要原因。
From the electrochemical test results, it could be found that the double-layer capacitance measured in this experimental system first decreases and then increases, and the lowest value of the double-layer capacitance is at 360 d. In addition, it could be clearly observed from Fig. 5g-m that there was a Cl-rich layer on the surface of the sample. This research result was similar to the corrosion behavior of bronze alloys in an oxygen-free environment studied by Fan et al. [32], [46]. At the same time, they pointed out that the double-layer capacitance value of bronze alloys always remains extremely low in an oxygen-free environment. The results of both indicate that the duplex bronze alloy enters an oxygen-free corrosion state at 360 d.
从电化学测试结果可以发现，在该实验系统中测得的双电层电容先减小后增大，双电层电容的最低值在 360 d 时。此外，从图 5g-m 中可以清楚地观察到样品表面有一层富含 Cl 的层。该研究结果类似于 Fan 等人 [32]、[46] 研究的青铜合金在无氧环境中的腐蚀行为。同时，他们指出，在无氧环境中，青铜合金的双电层电容值始终保持极低。两者的结果表明，双相青铜合金在 360 d 时进入无氧腐蚀状态。
By analyzing the metal system composed of Cu, Sn and Pb and combining the polarization curve fitting results (Table 6), the study found that the metal element dissolution occurred first [7], [23]. In addition, since the corrosion potential of Pb was the lowest compared with the corrosion potential of Cu and Sn [7], [11]. Therefore, in the early stage of bronze alloy corrosion (before 360 days), the corrosion of Pb mainly occurs, and its electrochemical reactions mainly include [23], [41], [42]:
通过分析由 Cu、Sn 和 Pb 组成的金属体系并结合极化曲线拟合结果（ 表 6），研究发现金属元素溶解首先发生 [7]、[23]。 此外，由于 Pb 的腐蚀电位与 Cu 和 Sn 的腐蚀电位相比最低 [7]， 因此 [11]。 因此，在青铜合金腐蚀的早期阶段（360 天之前），主要发生 Pb 的腐蚀，其电化学反应主要包括 [23]、[41]、[42]：(7)(8)(9)(10)
通过分析由 Cu、Sn 和 Pb 组成的金属体系并结合极化曲线拟合结果（ 表 6），研究发现金属元素溶解首先发生 [7]、[23]。 此外，由于 Pb 的腐蚀电位与 Cu 和 Sn 的腐蚀电位相比最低 [7]， 因此 [11]。 因此，在青铜合金腐蚀的早期阶段（360 天之前），主要发生 Pb 的腐蚀，其电化学反应主要包括 [23]、[41]、[42]：(7)(8)(9)(10)
Then, there was sufficient dissolved oxygen in the soil to satisfy the reaction between Cu and Sn. However, oxygen and dissolved oxygen in the soil were unevenly distributed in the environment, resulting in the corrosion process being diffusion-controlled [24], [25], [26], [42], [43]:
然后，土壤中有足够的溶解氧来满足 Cu 和 Sn 之间的反应。然而，土壤中的氧和溶解氧在环境中分布不均匀，导致腐蚀过程受到扩散控制 [24]、[25]、[26]、[42]、[43]：(11)(12)
然后，土壤中有足够的溶解氧来满足 Cu 和 Sn 之间的反应。然而，土壤中的氧和溶解氧在环境中分布不均匀，导致腐蚀过程受到扩散控制 [24]、[25]、[26]、[42]、[43]：(11)(12)
In the late stage of corrosion (after 360 days), considering that the dissolved oxygen in the corrosion environment is exhausted, but the Cl ions are still sufficient and active, the oxidation products on the surface of the sample react quickly with the Cl ions and cause the consumption of the oxide film.
在腐蚀后期（360 天后），考虑到腐蚀环境中的溶解氧已经耗尽，但 Cl 离子仍然充足和活跃，样品表面的氧化产物与 Cl 离子迅速反应，引起氧化膜的消耗。(13)(14)
在腐蚀后期（360 天后），考虑到腐蚀环境中的溶解氧已经耗尽，但 Cl 离子仍然充足和活跃，样品表面的氧化产物与 Cl 离子迅速反应，引起氧化膜的消耗。(13)(14)
Due to the large consumption of oxidation products on the sample surface, the thickness of the double-layer capacitor of the sample rapidly thinned under the action of Cl ions and was approximately 0 at 540 days.
由于样品表面氧化产物消耗量大，样品双电层电容器的厚度在 Cl 离子的作用下迅速变薄，在 540 天时约为 0。
At this time, the structure of the double-layer capacitor changed significantly during the whole process. The diffusion layer (Warbug impedance) in the double-layer capacitor tended to disappear, while the compact layer thinned rapidly.
此时，双层电容器的结构在整个过程中发生了明显的变化。双层电容器中的扩散层（Warbug 阻抗）趋于消失，而致密层迅速变薄。
Due to the reduction of the double-layer capacitor on the metal surface, the Cl ions in the soil can easily pass through the corrosion layer and directly reach the various matrix tissues inside the substrate and react with it to form chlorides, rather than oxide structures.
由于金属表面的双层电容器的还原，土壤中的 Cl 离子可以很容易地穿过腐蚀层，直接到达基底内部的各种基体组织，并与之反应形成氯化物，而不是氧化物结构。(15)(16)(17)
由于样品表面氧化产物消耗量大，样品双电层电容器的厚度在 Cl 离子的作用下迅速变薄，在 540 天时约为 0。
At this time, the structure of the double-layer capacitor changed significantly during the whole process. The diffusion layer (Warbug impedance) in the double-layer capacitor tended to disappear, while the compact layer thinned rapidly.
此时，双层电容器的结构在整个过程中发生了明显的变化。双层电容器中的扩散层（Warbug 阻抗）趋于消失，而致密层迅速变薄。
Due to the reduction of the double-layer capacitor on the metal surface, the Cl ions in the soil can easily pass through the corrosion layer and directly reach the various matrix tissues inside the substrate and react with it to form chlorides, rather than oxide structures.
由于金属表面的双层电容器的还原，土壤中的 Cl 离子可以很容易地穿过腐蚀层，直接到达基底内部的各种基体组织，并与之反应形成氯化物，而不是氧化物结构。(15)(16)(17)
From the previous TEM analysis, it was known that the α phase was a Cu-rich phase, and the δ phase in the eutectoid phase was a Sn-rich phase.
从之前的 TEM 分析中可以知道，α相是富铜相，共构造相中的 δ 相是富 Sn 相。
Based on the electrochemical analysis results and phase structure composition, it could be seen that the metal chlorides in the Cu-rich phase were mainly CuCl and CuCl2, while the metal chlorides in the Sn-rich phase were mainly SnCl2 and SnCl4. Chang et al. [41], [46], [47], [48] pointed out that SnCl2 has strong reducing properties and can cause the corrosion product CuCl2 obtained in the oxidation process to undergo a reduction reaction. The corrosion product SnCl4 obtained by the reaction between the two is easily hydrolyzed in aqueous solution and finally obtains the corrosion product SnO2. Secondly, the increase of H+ ions lowers the pH value in the environment and accelerates the transformation of CuCl to CuCl2[41], [48]. In addition, the main reason CuCl and CuCl2 were not detected on the surface of the sample was that these two compounds are extremely unstable in the air. Once taken out of the soil, they could quickly react with oxygen in the air to form Cu2(OH)3Cl [37], [38], [49], [50].
根据电化学分析结果和相结构组成，可以看出富铜相中的金属氯化物主要为 CuCl 和 CuCl2，而富 Sn 相中的金属氯化物主要为 SnCl2 和 SnCl4。Chang 等[41]、[46]、[47]、[48] 指出，SnCl2 具有很强的还原性能，可使氧化过程中得到的腐蚀产物 CuCl2 发生还原反应。两者反应得到的腐蚀产物 SnCl4 在水溶液中易水解，最后得到腐蚀产物 SnO2。其次，H+ 离子的增加降低了环境中的 pH 值，加速了 CuCl 向 CuCl2 的转化 [41]、[48]。 此外，在样品表面未检测到 CuCl 和 CuCl2 的主要原因是这两种化合物在空气中极不稳定。一旦从土壤中取出，它们就会迅速与空气中的氧气反应形成 Cu2（OH）3Cl[37]、[38]、[49]、[50]。(18)(19)
从之前的 TEM 分析中可以知道，α相是富铜相，共构造相中的 δ 相是富 Sn 相。
Based on the electrochemical analysis results and phase structure composition, it could be seen that the metal chlorides in the Cu-rich phase were mainly CuCl and CuCl2, while the metal chlorides in the Sn-rich phase were mainly SnCl2 and SnCl4. Chang et al. [41], [46], [47], [48] pointed out that SnCl2 has strong reducing properties and can cause the corrosion product CuCl2 obtained in the oxidation process to undergo a reduction reaction. The corrosion product SnCl4 obtained by the reaction between the two is easily hydrolyzed in aqueous solution and finally obtains the corrosion product SnO2. Secondly, the increase of H+ ions lowers the pH value in the environment and accelerates the transformation of CuCl to CuCl2[41], [48]. In addition, the main reason CuCl and CuCl2 were not detected on the surface of the sample was that these two compounds are extremely unstable in the air. Once taken out of the soil, they could quickly react with oxygen in the air to form Cu2(OH)3Cl [37], [38], [49], [50].
根据电化学分析结果和相结构组成，可以看出富铜相中的金属氯化物主要为 CuCl 和 CuCl2，而富 Sn 相中的金属氯化物主要为 SnCl2 和 SnCl4。Chang 等[41]、[46]、[47]、[48] 指出，SnCl2 具有很强的还原性能，可使氧化过程中得到的腐蚀产物 CuCl2 发生还原反应。两者反应得到的腐蚀产物 SnCl4 在水溶液中易水解，最后得到腐蚀产物 SnO2。其次，H+ 离子的增加降低了环境中的 pH 值，加速了 CuCl 向 CuCl2 的转化 [41]、[48]。 此外，在样品表面未检测到 CuCl 和 CuCl2 的主要原因是这两种化合物在空气中极不稳定。一旦从土壤中取出，它们就会迅速与空气中的氧气反应形成 Cu2（OH）3Cl[37]、[38]、[49]、[50]。(18)(19)
Since the corrosion products (chlorides) between the α(II) phase and the δ phase in the eutectoid phase can be mutually transformed, the bronze alloy shows eutectoid corrosion in the macroscopic stage in the late stage of corrosion.
由于共构造相中 α（II） 相和 δ 相之间的腐蚀产物（氯化物）可以相互转化，因此青铜合金在腐蚀后期的宏观阶段表现出共析腐蚀。
At the same time, there is also mutual transformation between the corrosion products between the α(I) and δ phases, and finally it shows corrosion diffusion into the δ phase.
同时，α（I） 相和 δ 相之间的腐蚀产物之间也存在相互转变，最后表现为腐蚀扩散到 δ 相中。
In addition, based on the above electrochemical analysis results, the Warburg impedance ran through the entire corrosion process of the sample. However, its value gradually weakened as the test prolonged.
此外，根据上述电化学分析结果，Warburg 阻抗贯穿了样品的整个腐蚀过程。然而，随着测试的延长，它的价值逐渐减弱。
This was mainly due to the difficulty of dissolved oxygen in the environment diffusing through the surface product layer to the substrate. In other words, the Cu on the sample surface easily combined with OH⁻ to form a reddish-brown solid product Cu2O, thereby hindering the contact between the substrate and chloride ions. This was the main factor affecting the mass transfer rate of bronze alloys in the early stage of corrosion.
这主要是由于环境中的溶解氧难以通过表面产物层扩散到基材。换句话说，样品表面的 Cu 很容易与 OH⁻ 结合，形成红棕色的固体产物 Cu2O，从而阻碍衬底与氯离子的接触。这是影响青铜合金腐蚀初期传质速率的主要因素。
At this time, due to different diffusion rates at various locations on the sample substrate surface, the corrosion degree varied across the sample. This caused uneven corrosion, which was numerically reflected as a rapid decrease in the ndl value (180 d-360 d). As time goes by, the consumption of dissolved oxygen caused the formation rate of oxidation products to slow down. At the same time, Cl ions reacted rapidly with oxides and convert them into metal chlorides.
此时，由于样品基底表面不同位置的扩散速率不同，整个样品的腐蚀程度各不相同。这导致了不均匀的腐蚀，这在数值上反映为 ndl 值 （180 d-360 d） 的快速下降。随着时间的推移，溶解氧的消耗导致氧化产物的形成速度减慢。同时，Cl 离子与氧化物迅速反应并将其转化为金属氯化物。
The corrosion process of the two leads to the rapid consumption of surface oxidation products, resulted in a rapid decrease in the thickness of the double layer. In the later stage of corrosion, due to the presence of sufficient Cl ions in the corrosion environment.
两者的腐蚀过程导致表面氧化产物的快速消耗，导致双电层的厚度迅速减小。在腐蚀后期，由于腐蚀环境中存在足够的 Cl 离子。
The sample was in overall corrosion, and the double layer capacitance ndl value (540 d) increases. At this time, the Warburg impedance weakened and disappeared, and the corrosion process was then dominated by the charge transfer resistance.
样品整体腐蚀，双电层电容 ndl 值 （540 d） 增加。此时，Warburg 阻抗减弱并消失，然后腐蚀过程由电荷转移电阻主导。
Therefore, the double electrical layer structure was the main reason for the great differences in the corrosion process of bronze alloys, and the presence of dissolved oxygen was the key to the changes in the double electrical layer structure.
因此，双电层结构是青铜合金腐蚀过程差异较大的主要原因，而溶解氧的存在是双电层结构发生变化的关键。
由于共构造相中 α（II） 相和 δ 相之间的腐蚀产物（氯化物）可以相互转化，因此青铜合金在腐蚀后期的宏观阶段表现出共析腐蚀。
At the same time, there is also mutual transformation between the corrosion products between the α(I) and δ phases, and finally it shows corrosion diffusion into the δ phase.
同时，α（I） 相和 δ 相之间的腐蚀产物之间也存在相互转变，最后表现为腐蚀扩散到 δ 相中。
In addition, based on the above electrochemical analysis results, the Warburg impedance ran through the entire corrosion process of the sample. However, its value gradually weakened as the test prolonged.
此外，根据上述电化学分析结果，Warburg 阻抗贯穿了样品的整个腐蚀过程。然而，随着测试的延长，它的价值逐渐减弱。
This was mainly due to the difficulty of dissolved oxygen in the environment diffusing through the surface product layer to the substrate. In other words, the Cu on the sample surface easily combined with OH⁻ to form a reddish-brown solid product Cu2O, thereby hindering the contact between the substrate and chloride ions. This was the main factor affecting the mass transfer rate of bronze alloys in the early stage of corrosion.
这主要是由于环境中的溶解氧难以通过表面产物层扩散到基材。换句话说，样品表面的 Cu 很容易与 OH⁻ 结合，形成红棕色的固体产物 Cu2O，从而阻碍衬底与氯离子的接触。这是影响青铜合金腐蚀初期传质速率的主要因素。
At this time, due to different diffusion rates at various locations on the sample substrate surface, the corrosion degree varied across the sample. This caused uneven corrosion, which was numerically reflected as a rapid decrease in the ndl value (180 d-360 d). As time goes by, the consumption of dissolved oxygen caused the formation rate of oxidation products to slow down. At the same time, Cl ions reacted rapidly with oxides and convert them into metal chlorides.
此时，由于样品基底表面不同位置的扩散速率不同，整个样品的腐蚀程度各不相同。这导致了不均匀的腐蚀，这在数值上反映为 ndl 值 （180 d-360 d） 的快速下降。随着时间的推移，溶解氧的消耗导致氧化产物的形成速度减慢。同时，Cl 离子与氧化物迅速反应并将其转化为金属氯化物。
The corrosion process of the two leads to the rapid consumption of surface oxidation products, resulted in a rapid decrease in the thickness of the double layer. In the later stage of corrosion, due to the presence of sufficient Cl ions in the corrosion environment.
两者的腐蚀过程导致表面氧化产物的快速消耗，导致双电层的厚度迅速减小。在腐蚀后期，由于腐蚀环境中存在足够的 Cl 离子。
The sample was in overall corrosion, and the double layer capacitance ndl value (540 d) increases. At this time, the Warburg impedance weakened and disappeared, and the corrosion process was then dominated by the charge transfer resistance.
样品整体腐蚀，双电层电容 ndl 值 （540 d） 增加。此时，Warburg 阻抗减弱并消失，然后腐蚀过程由电荷转移电阻主导。
Therefore, the double electrical layer structure was the main reason for the great differences in the corrosion process of bronze alloys, and the presence of dissolved oxygen was the key to the changes in the double electrical layer structure.
因此，双电层结构是青铜合金腐蚀过程差异较大的主要原因，而溶解氧的存在是双电层结构发生变化的关键。
Based on the above analysis, it can be found that oxygen is the key to the phase corrosion evolution of duplex bronze alloys. In the early stage of corrosion, the bronze alloy corrodes along the α phase.
基于以上分析，可以发现氧是双相青铜合金相腐蚀演变的关键。在腐蚀的早期阶段，青铜合金沿α相腐蚀。
This conclusion is consistent with the research results of most scholars at present, which is mainly attributed to the sensitivity of bronze alloys with passivation properties to oxygen and the lower potential of the α phase than the δ phase (i.e., potential theory) [7], [40]. In the later stage of corrosion (the bronze alloy enters the oxygen-free corrosion state), the corrosion products (metal chlorides) between the two phases (α phase and δ phase) transform into each other, causing the duplex bronze alloy to exhibit eutectoid phase corrosion.
这一结论与目前大多数学者的研究结果一致，主要归因于具有钝化性能的青铜合金对氧的敏感性以及α相的电位低于δ相（即电位理论）[7]、[40]。 在腐蚀后期（青铜合金进入无氧腐蚀状态），两相（α相和δ相）之间的腐蚀产物（金属氯化物）相互转变，导致双相青铜合金表现出共析相腐蚀。
基于以上分析，可以发现氧是双相青铜合金相腐蚀演变的关键。在腐蚀的早期阶段，青铜合金沿α相腐蚀。
This conclusion is consistent with the research results of most scholars at present, which is mainly attributed to the sensitivity of bronze alloys with passivation properties to oxygen and the lower potential of the α phase than the δ phase (i.e., potential theory) [7], [40]. In the later stage of corrosion (the bronze alloy enters the oxygen-free corrosion state), the corrosion products (metal chlorides) between the two phases (α phase and δ phase) transform into each other, causing the duplex bronze alloy to exhibit eutectoid phase corrosion.
这一结论与目前大多数学者的研究结果一致，主要归因于具有钝化性能的青铜合金对氧的敏感性以及α相的电位低于δ相（即电位理论）[7]、[40]。 在腐蚀后期（青铜合金进入无氧腐蚀状态），两相（α相和δ相）之间的腐蚀产物（金属氯化物）相互转变，导致双相青铜合金表现出共析相腐蚀。
5. Conclusion 5. 总结
The following conclusions were drawn from the corrosion behavior of duplex tin-lead bronze alloy in weakly alkaline soil environment:
从双相锡铅青铜合金在弱碱性土壤环境中的腐蚀行为中得出以下结论：
从双相锡铅青铜合金在弱碱性土壤环境中的腐蚀行为中得出以下结论：
- 1.The corrosion of the two-phase tin-lead bronze alloy changes from the initial α phase to the later (δ + α(II)) eutectoid phase.
两相锡铅青铜合金的腐蚀从初始α相转变为后期 （δ + α（II）） 共析相。 - 2.The oxygen-free environment is the key to the phase corrosion mechanisms evolution of the bronze alloy.
无氧环境是青铜合金相腐蚀机理演变的关键。 - 3.In the later stage of corrosion, the corrosion products between the two phases (α phase and δ phase) can transform into each other, causing (δ + α(II)) eutectoid phase corrosion.
在腐蚀后期，两相（α相和δ相）之间的腐蚀产物可以相互转变，引起 （δ + α（II）） 共析相腐蚀。
CRediT authorship contribution statement
CRediT 作者贡献声明
Wang Xiuyuan: Writing – original draft, Formal analysis, Conceptualization. Fan Zhiheng: Writing – review & editing, Writing – original draft, Methodology, Conceptualization. Song Jialiang: Writing – review & editing, Formal analysis, Data curation, Conceptualization. Chen Jiachang: Resources, Formal analysis, Conceptualization. Shi Jingrui: Resources, Funding acquisition, Conceptualization. Zhou Herong: Writing – review & editing, Conceptualization. Xiao Kui: Investigation, Conceptualization.
王秀元： 写作 – 原稿、形式分析、概念化。 范志恒： 写作 - 审查和编辑，写作 - 原始草稿，方法论，概念化。 宋佳良： 写作 - 审查和编辑，正式分析，数据管理，概念化。 陈家昌： 资源、形式分析、概念化。 石景睿： 资源、资金获取、概念化。 周和荣： 写作 - 审查和编辑，概念化。 小奎： 调查、概念化。
王秀元： 写作 – 原稿、形式分析、概念化。 范志恒： 写作 - 审查和编辑，写作 - 原始草稿，方法论，概念化。 宋佳良： 写作 - 审查和编辑，正式分析，数据管理，概念化。 陈家昌： 资源、形式分析、概念化。 石景睿： 资源、资金获取、概念化。 周和荣： 写作 - 审查和编辑，概念化。 小奎： 调查、概念化。
Declaration of Competing Interest
利益争夺声明
The authors declared that they have no conflicts of interest to this work. We declare that we do not have any commercial or associative interest that represents a conflict of interest in connection with the work submitted.
作者声明他们对这项工作没有利益冲突。我们声明，我们没有任何与提交的作品相关的商业或关联利益。
作者声明他们对这项工作没有利益冲突。我们声明，我们没有任何与提交的作品相关的商业或关联利益。
Acknowledgements 确认
This work was financially supported by the National Key Research and Development Program of China, No. 2020YFC1522000. The authors thank the School of Cultural Heritage, Northwest University for its kind help in the antique casting bronze alloy smelting.
这项工作得到了中国国家重点研发计划 （No.2020YFC1522000. 作者感谢西北大学文化遗产学院对仿古铸造青铜合金冶炼的友好帮助。
In addition, since this experiment is a long-term corrosion process, the experimental results of 0–360 days (α phase corrosion, not involving the eutectoid phase corrosion part) have been published in the form of a paper.
此外，由于该实验是一个长期的腐蚀过程，因此以论文的形式发表了 0-360 天 （α相腐蚀，不涉及共析相腐蚀部分）的实验结果。
This article quotes some relevant data, including corrosion morphology, polarization curve and EIS testing. The paper is titled Initial Corrosion Behavior of Dual-Phase Bronze with Tin Segregation in Weakly Alkaline Soil Environment. (https://doi.org/10.1007/s11665-025–10844-z)
本文引用了一些相关数据，包括腐蚀形态、极化曲线和 EIS 测试。该论文的标题为《弱碱性土壤环境中锡偏析双相青铜的初始腐蚀行为》。（https://doi.org/10.1007/s11665-025–10844-Z）
这项工作得到了中国国家重点研发计划 （No.2020YFC1522000. 作者感谢西北大学文化遗产学院对仿古铸造青铜合金冶炼的友好帮助。
In addition, since this experiment is a long-term corrosion process, the experimental results of 0–360 days (α phase corrosion, not involving the eutectoid phase corrosion part) have been published in the form of a paper.
此外，由于该实验是一个长期的腐蚀过程，因此以论文的形式发表了 0-360 天 （α相腐蚀，不涉及共析相腐蚀部分）的实验结果。
This article quotes some relevant data, including corrosion morphology, polarization curve and EIS testing. The paper is titled Initial Corrosion Behavior of Dual-Phase Bronze with Tin Segregation in Weakly Alkaline Soil Environment. (https://doi.org/10.1007/s11665-025–10844-z)
本文引用了一些相关数据，包括腐蚀形态、极化曲线和 EIS 测试。该论文的标题为《弱碱性土壤环境中锡偏析双相青铜的初始腐蚀行为》。（https://doi.org/10.1007/s11665-025–10844-Z）
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