CN110938786A - High-corrosion-resistance Al-TM-RE amorphous aluminum alloy - Google Patents
High-corrosion-resistance Al-TM-RE amorphous aluminum alloy Download PDFInfo
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Abstract
The invention discloses a high-corrosion-resistance Al-TM-RE amorphous aluminum alloy, belonging to the technical field of amorphous alloy materials. The Al-TM-RE series amorphous aluminum alloy is designed to have the following chemical components in percentage by mole: 85-87% of Al, 5.5-6.5% of Ni, 1.5-2.5% of Co, 4.0-5.0% of Y and 0.5-1.5% of RE; RE is Ce element, or RE is the combination of La and Ce element. The Al-TM-RE amorphous aluminum alloy has strong amorphous forming capability and high corrosion resistance, and compared with the traditional Al-TM-RE quinary aluminum-based amorphous alloy system, the pitting potential is improved by 60-140mV in the environment of 3.5 wt.% NaCl solutionSCEThe passive film formed by anode polarization is thicker and has better corrosion resistance.
Description
Technical Field
The invention relates to the technical field of amorphous alloy materials, in particular to a high-corrosion-resistance Al-TM-RE amorphous aluminum alloy, which can also provide scientific guidance for regulating and controlling the corrosion resistance of other amorphous alloys.
Background
Generally, the corrosion resistance of the aluminum alloy is shown in that a layer of denser oxide film is formed on the surface of the aluminum alloy, so that the aluminum alloy has better atmospheric corrosion resistance, but has poorer local corrosion resistance in a harsh environment (such as chlorine ions), and especially the local corrosion damage of the high-strength aluminum alloy for aerospace is one of the main failure damage modes of the high-strength aluminum alloy. The traditional aluminum alloy corrosion protection methods mainly comprise the following three methods: mechanical coatings, coating corrosion inhibiting paints and chromate conversion coatings. The mechanical aluminum coating method is a widely used method, plays a role in cathodic protection of the sacrificial anode, and can also effectively inhibit local pitting, stress corrosion, denudation and the like. But also has a plurality of defects: if the active corrosion inhibitor is lacked, the environmental protection at high pH value is greatly reduced; failure during local surface repair; and is not field replaceable. Corrosion inhibiting paints and chromate conversion coatings contain chromium and are now increasingly restricted and banned from use in the construction of environmentally friendly society due to the toxicity and carcinogenicity of high-valent chromium. In some harsh environments, such as alternate sea and land environments where amphibious aircraft are located, the problem of local corrosion protection of aluminum alloy is difficult to solve by traditional corrosion protection methods. Therefore, there is an urgent need to develop an effective corrosion protection method for the corrosion protection problem of high-strength aluminum alloy.
The amorphous alloy can be solid-dissolved with a large amount of corrosion-resistant and corrosion-inhibition components, and the like, so that the amorphous alloy has higher local corrosion resistance. For example, the pitting corrosion resistance of the Al-TM-RE (TM ═ transition group metal elements, RE ═ rare earth elements) system amorphous alloy is much higher than that of the conventional aluminum alloy. In view of this, the system was tried as an amorphous coating for surface corrosion protection of conventional 2024 aluminum alloys and exhibited multiple protective functions[73]. Compared with the traditional aluminum alloy material, the aluminum-based amorphous alloy has the performance far superior to that of the traditional aluminum alloy, such as low density, high strength, high toughness and excellent corrosion resistance, and can be applied to energy chemical industry andthe advantages in the corrosion resistance protection of the surface in the fields of aerospace and the like are obvious. However, the research on the aluminum-based amorphous coating at home and abroad is in the initial stage at present, and the actual engineering requirements are difficult to meet. Therefore, the aluminum-based amorphous alloy is optimized in composition, the corrosion resistance of the alloy is improved, the alloy meets the requirement of practical working conditions, and the method has important guiding significance for promoting the engineering application of the aluminum-based amorphous alloy.
Disclosure of Invention
The invention aims to provide a high-corrosion-resistance Al-TM-RE amorphous aluminum alloy, which improves the corrosion resistance of a quinary Al-TM-RE amorphous aluminum alloy through component design.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the high-corrosion-resistance Al-TM-RE amorphous aluminum alloy comprises the following chemical components in percentage by mole:
85-87% of Al, 5.5-6.5% of Ni, 1.5-2.5% of Co1, 4.0-5.0% of Y and 0.5-1.5% of RE; RE is Ce element, or RE is the combination of La and Ce element.
The Al-TM-RE series amorphous aluminum alloy comprises the following preferable chemical components in percentage by mole: 86% of Al, 6.0% of Ni0%, 2.0% of Co, 4.5% of Y and 0.5-1.5% of Ce.
The Al-TM-RE series amorphous aluminum alloy comprises the following preferable chemical components in percentage by mole: al 86%, ni 6.0%, Co 2.0%, Y4.5%, 0.1% < La < 1.5%, 0.1% < Ce < 1.5%.
When the Al-TM-RE amorphous aluminum alloy is prepared, a raw material Al with the purity not less than 99.99 percent and other elements with the purity not less than 99.999 percent is selected, and after a master alloy is prepared in a high-purity argon environment, a single-roller melt quenching method is adopted to prepare a strip sample. The final solidification structure of the prepared strip sample is a completely amorphous structure, the thickness of the strip sample is 25-35 mu m, and the width of the strip sample is 2.5-3.5 mm.
The prepared Al-TM-RE amorphous aluminum alloy strip sample has high corrosion resistance, and compared with the traditional Al-TM-RE quinary aluminum-based amorphous alloy system, the pitting potential energy is increased to-0.1V in a 3.5 wt.% NaCl solution environment, and a passivation film formed by anodic polarization is thicker.
The invention has the following advantages and beneficial effects:
1. aiming at the existing quinary aluminum-based amorphous alloy forming system Al-TM-RE (such as Al)86Ni6Y4.5Co2La1.5) The Al-TM-RE amorphous aluminum alloy provided by the invention comprises the following components in percentage by mole: 85-87% of Al, 5.5-6.5% of Ni, 1.5-2.5% of Co, 4.0-5.0% of Y and 0.5-1.5% of RE; wherein RE is Ce element or the combination of La and Ce element, the Al-TM-RE series amorphous aluminum alloy has good glass forming ability.
2. Compared with the traditional Al-TM-RE quinary aluminum-based amorphous alloy system (such as Al), the Al-TM-RE amorphous aluminum alloy designed by the invention86Ni6Y4.5Co2La1.5) The corrosion resistance of the material can be improved, and the pitting potential can be improved by 60-140mV in the environment of 3.5 wt.% NaCl solutionSCEThe passivation film formed by anodic polarization is thicker.
Drawings
FIG. 1 is a comparison of XRD patterns of amorphous alloy strips prepared by the methods of example 1 and comparative example 1; in the figure: curve a is the spectrum of comparative example 1, curve b is the XRD spectrum of alloy b in example 1, and curve c is the XRD spectrum of alloy c in example 1.
FIG. 2 is a DSC spectrum comparison of amorphous alloy strips prepared by the method of example 1 and comparative example 1; in the figure: curve a is the DSC pattern of comparative example 1, curve b is the DSC pattern of alloy b in example 1, and curve c is the DSC pattern of alloy c in example 1.
FIG. 3 is a comparison of polarization curves of amorphous alloy ribbons prepared by the methods of example 1 and comparative example 1; in the figure: curve a is the polarization curve of comparative example 1, curve b is the polarization curve of alloy b in example 1, and curve c is the polarization curve of alloy c in example 1.
FIG. 4 is a comparison of full spectra of anodic polarization XPS analysis of amorphous alloy ribbons prepared by the methods of example 1 and comparative example 1; wherein: (a) is comparative example 1, (b) is the alloy b in example 1, and (c) is the alloy c in example 1.
FIG. 5 is a comparison of XPS analysis fine spectra of anodic polarization of amorphous alloy ribbons prepared by the methods of example 1 and comparative example 1; wherein: (a) comparative example 1, (b) is the alloy c of example 1.
Detailed Description
The invention is described in detail below with reference to the accompanying drawings and examples.
Example 1:
the composition design of the highly corrosion-resistant Al-TM-RE amorphous aluminum alloy provided by the embodiment is as follows: 2 alloy compositions are designed: alloy b and alloy c, wherein: alloy b chemical composition (mole percentage content): 86% of Al, 6.0% of Ni, 2.0% of Co2, 4.5% of Y, 0.75% of La and 0.75% of Ce; alloy c chemical composition (mole percentage content): 86% of Al, 6.0% of Ni0%, 2.0% of Co, 4.5% of Y and 1.5% of Ce; the method comprises the steps of selecting a raw material Al with the purity of more than or equal to 99.99 percent and other elements with the purity of more than or equal to 99.999 percent, preparing a master alloy in a high-purity argon environment, and then preparing a strip sample by adopting a single-roll melt quenching method, wherein the final solidification structure is a completely amorphous structure, the thickness is 25-35 mu m, and the width is about 2.5-3.5 mm.
The aluminum-based strip sample designed and prepared in example 1 has a completely amorphous structure, as shown by the curves b and c in fig. 1, both are steamed bread peaks without sharp crystal peaks, and has good glass forming ability. Meanwhile, DSC comparison results are shown in a curve and a curve c in figure 2, and the Al-TM-RE aluminum-based amorphous alloy sample optimized by the method of the embodiment shows three exothermic peaks in the temperature rising process, so that the Al-TM-RE aluminum-based amorphous alloy sample has good glass forming capability. Meanwhile, in the environment of 3.5 wt.% NaCl solution, the corrosion resistance of the amorphous aluminum alloy designed by the method is improved, and the pitting potential is improved by about 60-140mVSCEAs shown by the curves and c-curves in fig. 3. It can be clearly seen by comparing the XPS analysis full spectrum and the fine spectrum that the content of O in the passivation film formed by anodic polarization is higher, the content of Ce in the oxidation state in the passivation film is higher when the sputtering time is 40s, the passivation film is thicker, and the corrosion resistance is better, as shown in fig. 4(b), 4(c), and 5 (b).
Comparative example 1:
the difference from the embodiment 1 is that: the aluminum-based amorphous alloy is prepared by adopting a traditional Al-TM-RE quinary aluminum-based amorphous alloy system, and comprises the following chemical components in percentage by mole: 86% of Al, 6.0% of Ni, 2.0% of Co, 4.5% of Y and 1.5% of La1, and the corrosion resistance is relatively low, as shown by a curve in figure 3.
XPS analysis of the aluminum-based amorphous alloy prepared by adopting the traditional Al-TM-RE quinary aluminum-based amorphous alloy system in the comparative example 1 shows that the full spectrum is shown in figure 4(a), the content of O in the passivation film is relatively low, the passivation film is relatively thin, and the corrosion resistance of the alloy is relatively low.
XPS analysis of the aluminum-based amorphous alloy prepared by adopting the traditional Al-TM-RE quinary aluminum-based amorphous alloy system in the comparative example 1 shows that a fine spectrum is shown in FIG. 5(a), when the sputtering time is 40s, the content of La in an oxidation state in a passivation film is relatively low and tends to be flat, the passivation film is thin, and the corrosion resistance of the alloy is low.
Comparative example 2:
the difference from the embodiment 1 is that: when the components of the alloy and the components (mol percentage content) of the components are optimally designed as follows: the corrosion resistance of the alloy is not improved when the alloy comprises 86% of Al, 6.0% of Ni, 2.0% of Co, 4.5% of Y, 0.75% of La and 0.75% of Nd.
Comparative example 3:
the difference from the embodiment 1 is that: when the components of the alloy and the components (mol percentage content) of the components are optimally designed as follows: al 86%, Ni 6.0%, Co 2.0%, Y4.5%, and Nd 1.5%, the glass forming ability is lowered, and the corrosion resistance is lowered.
As shown by the above examples and comparative examples, the highly corrosion-resistant Al-TM-RE amorphous aluminum alloy provided by the invention comprises the following components (by mol percent): 85-87% of Al, 5.5-6.5% of Ni, 1.5-2.5% of Co, 4.0-5.0% of Y and 0.5-1.5% of RE; RE is Ce element, or RE is the combination of La and Ce element. The prepared high-corrosion-resistance Al-TM-RE amorphous aluminum alloy has good glass forming capability and higher corrosion resistance, and the pitting potential is improved by 60-140mV in an environment of 3.5 wt.% NaCl solution compared with the traditional Al-TM-RE quinary alloy systemSCEThe passive film formed by anode polarization is thicker, and meanwhile, the amorphous alloy sample has strong glass forming capability. The invention can also be used for other amorphousThe control of the corrosion resistance of the alloy provides scientific guidance.
Claims (6)
1. A high corrosion resistant Al-TM-RE series amorphous aluminum alloy is characterized in that: the Al-TM-RE series amorphous aluminum alloy comprises the following components in percentage by mol:
85-87% of Al, 5.5-6.5% of Ni, 1.5-2.5% of Co, 4.0-5.0% of Y and 0.5-1.5% of RE; RE is Ce element, or RE is the combination of La and Ce element.
2. The highly corrosion-resistant Al-TM-RE amorphous aluminum alloy according to claim 1, wherein: the Al-TM-RE series amorphous aluminum alloy comprises the following components in percentage by mol: 86% of Al, 6.0% of Ni, 2.0% of Co2, 4.5% of Y and 0.5-1.5% of Ce.
3. The highly corrosion-resistant Al-TM-RE amorphous aluminum alloy according to claim 1, wherein: the Al-TM-RE series amorphous aluminum alloy comprises the following components in percentage by mol: al 86%, Ni 6.0%, co 2.0%, Y4.5%, 0.1% < La < 1.5%, 0.1% < Ce < 1.5%.
4. The highly corrosion-resistant Al-TM-RE amorphous aluminum alloy according to claim 1, wherein: when the Al-TM-RE amorphous aluminum alloy is prepared, a raw material Al with the purity not less than 99.99 percent and other elements with the purity not less than 99.999 percent is selected, and after a master alloy is prepared in a high-purity argon environment, a single-roller melt quenching method is adopted to prepare a strip sample.
5. The highly corrosion-resistant Al-TM-RE amorphous aluminum alloy according to claim 4, wherein: the final solidification structure of the prepared strip sample is a completely amorphous structure, the thickness of the strip sample is 25-35 mu m, and the width of the strip sample is 2.5-3.5 mm.
6. The Al-TM-RE amorphous aluminum alloy with high corrosion resistance as set forth in any one of claims 1 to 5, wherein: the pitting potential energy of the high-corrosion-resistance Al-TM-RE amorphous aluminum alloy is increased to-0.1V in a 3.5 wt.% NaCl solution environment, and a passivation film formed by anodic polarization is thicker.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112064058A (en) * | 2020-08-05 | 2020-12-11 | 北京航空航天大学 | Nano-porous Al-Ni-M-RE-R amorphous alloy used as hydrogen evolution catalytic electrode and preparation method thereof |
| CN114420914A (en) * | 2021-12-15 | 2022-04-29 | 深圳先进技术研究院 | Aluminum-based amorphous negative electrode active material, composite negative electrode active material, battery negative electrode material and battery |
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| CN114420914A (en) * | 2021-12-15 | 2022-04-29 | 深圳先进技术研究院 | Aluminum-based amorphous negative electrode active material, composite negative electrode active material, battery negative electrode material and battery |
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