CN115679138B - Method for improving corrosion damage resistance of conductor aluminum alloy - Google Patents
Method for improving corrosion damage resistance of conductor aluminum alloy Download PDFInfo
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- 150000002910 rare earth metals Chemical class 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 20
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a method for improving corrosion damage resistance of a conductor aluminum alloy, which comprises the steps of firstly adding a proper amount of rare earth element La into an aluminum melt to prepare an Al-La intermediate alloy; then adding the Al-La intermediate alloy into an aluminum alloy melt to prepare a conductor aluminum alloy cast ingot; and finally, carrying out solid solution and aging heat treatment on the conductor aluminum alloy cast ingot. The invention adds rare earth element La in the aluminum alloy, the rare earth element La can be in Mg 2 Forming La-rich layer on the surface of Si particle and Mg 2 The local region near the Si particles releases high concentration of La 3+ La as corrosion inhibitor 3+ To react with water solution to generate La with protective effect 2 O 3 /La(OH) 3 Layer coated with Mg 2 Si particle surface, hinder Mg 2 Selective dissolution of Si particles; meanwhile, the addition of trace La also prevents the growth of Si particles, the Si particles are changed into a short rod-shaped structure from a long sheet-shaped structure, the continuous distribution of the Si particles at the grain boundary is broken, the fine and dispersed Si particles are formed, the corrosion is prevented from being rapidly expanded along the grain boundary region, and the corrosion resistance of the aluminum alloy is further improved.
Description
Technical Field
The invention belongs to the technical field of aluminum alloy surface treatment, and particularly relates to a method for improving corrosion damage resistance of a conductor aluminum alloy.
Background
Aluminum alloy (Al-Mg-Si) is widely applied in the electric field due to higher specific strength, good formability, excellent electric conduction and heat conduction performances and the like, and particularly in the aspect of wire manufacturing, the aluminum alloy (Al-Mg-Si) is a preferred electric conduction material for national long-distance power transmission.
With the rapid development of ultra-high voltage transmission, the sectional area of a wire is larger and larger, meanwhile, the topography of an ultra-high voltage line is changeable, the conditions of large span and large height difference are more and more occurred, and the requirements on the mechanical bearing capacity of the wire and the connecting hardware fitting are higher and higher strength of conductor materials for manufacturing the wire and the hardware fitting are required. Under the background of carbon reaching peak, carbon neutralization, new requirements of green low carbon, energy conservation and emission reduction are provided for a power system, higher requirements are provided for the conductivity of a conductor material so as to reduce line loss in the transmission process, and meanwhile, the transmission line can inevitably contact corrosive media in the service process, particularly in coastal areas with larger salt content, heavy industrial areas and heavy pollution areas, and the corrosion resistance of aluminum alloy (Al-Mg-Si) is directly related to the service life of the line.
However, in order to improve the strength of the aluminum alloy (Al-Mg-Si), some other element is usually added to the aluminum alloy (Al-Mg-Si), which results in a large amount of second phase particles in the aluminum alloy (Al-Mg-Si), and electrochemical properties between the second phase particles and the aluminum alloy matrix are different, so that local micro-cells are easily formed during service, thereby generating pitting corrosion, resulting in poor corrosion resistance, and improving the corrosion resistance of the aluminum alloy (Al-Mg-Si) on the premise of ensuring the strength and conductivity of the aluminum alloy (Al-Mg-Si), which is important for long-distance and trans-regional power transmission.
The Chinese patent with publication number of CN 111500906A discloses a high-strength corrosion-resistant aluminum alloy and a preparation method thereof, wherein Mn, cu, zn, fe, cr, ni, V, ti, zr and multiple elements such as rare earth elements Gd, la and Eu are added into the aluminum alloy, and the addition proportion of the elements and Ni, V, ti, zr are optimized to be matched with the rare earth elements, so that the aluminum alloy can meet the requirement of high strength and simultaneously can meet the corrosion-resistant effect of the aluminum alloy. The Chinese patent with publication number of CN 112831700A discloses a high-strength corrosion-resistant aluminum alloy for overhead lines and a preparation method thereof, wherein the aluminum alloy comprises the following components in percentage by mass: si:0.98-1.35%, mg:1.7-2.2%, cu:0.045-0.087%, fe: 0.04-0.11%, zn:0.01-0.037%, cr:0.1-0.16%, mn:0.47-0.53%, ti:0.01-0.05%, zr:0.1-0.15%, sn:0.04-0.09%, te+Sb: 0.013-0.025%, sc+Be:0.05-0.12%, ag+Sr+Y:0.2-0.8% and the balance of Al, and the aluminum alloy obtained by optimizing the content of each element has high strength, good toughness and excellent corrosion resistance, and can meet the use requirement of a contact net. Although the corrosion resistance of the aluminum alloy can be improved in both patents, the aluminum alloy with high-strength corrosion resistance is prepared by adding a large amount of complex elements, so that the smelting difficulty in the preparation process is high, and the corresponding preparation cost is relatively high.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a method for improving corrosion damage resistance of a conductor aluminum alloy. The lifting method is simple, low in cost and universal for the 6xxx series Al-Mg-Si alloy.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for improving corrosion damage resistance of conductor aluminum alloy comprises the steps of firstly, adding a proper amount of rare earth La into an aluminum melt to prepare an Al-La intermediate alloy; then adding the Al-La intermediate alloy into an aluminum alloy melt to prepare a conductor aluminum alloy cast ingot; and finally, carrying out solid solution and aging heat treatment on the conductor aluminum alloy cast ingot.
Further, the method for improving corrosion damage resistance of the conductor aluminum alloy specifically comprises the following steps:
(1) Preparing an Al-Si prefabricated alloy: placing an industrial pure aluminum ingot into a graphite clay crucible, heating to melt and raise the temperature to form an aluminum melt, adding Si into the aluminum melt for heat preservation, and then casting the aluminum melt after adding the Si into an iron mold to obtain an Al-Si prefabricated alloy ingot;
(2) Al-La intermediate alloy preparation: placing an industrial pure aluminum ingot into a graphite clay crucible, heating to melt and raise the temperature to form an aluminum melt, wrapping rare earth La with aluminum foil, adding the aluminum melt into the aluminum melt, preserving heat, and casting the aluminum melt added with the rare earth La into an iron mold to obtain an Al-La intermediate alloy;
(3) Placing industrial pure aluminum and Al-Si prefabricated alloy cast ingot into a graphite clay crucible, heating to melt and raise the temperature to obtain Al-Si alloy melt, wrapping pure Mg with aluminum foil, adding into the obtained Al-Si alloy melt, stirring to fully dissolve Mg, raising the temperature, and adding NaCl, KCl and Na 3 AlF 6 Refining and standing the mixture for 10-15min to form an aluminum alloy melt;
(4) Adding the Al-La intermediate alloy obtained in the step (2) into the aluminum alloy melt obtained in the step (3), preserving heat and stirring for 8-15min, then cooling to 700-720 ℃, adding 0.2-0.3% of Al-5Ti-1B refiner, blowing high-purity Ar gas into the aluminum alloy melt added with the Al-La intermediate alloy, and finally casting the aluminum alloy melt added with the Al-La intermediate alloy into a preheated iron mold to obtain a conductor aluminum alloy cast ingot;
(5) Heating the conductor aluminum alloy cast ingot obtained in the step (4) to a certain temperature for heat preservation treatment, and then carrying out water quenching treatment;
(6) And (3) heating the conductor aluminum alloy cast ingot after water quenching in the step (5) to a certain temperature for heat preservation, and then performing artificial aging treatment.
Further, the content of impurity oxygen elements in rare earth La of the Al-La intermediate alloy is less than 0.02wt.%, and the total content of rare earth La is more than 99.5wt.%.
Furthermore, the preparation of the Al-La intermediate alloy is carried out in a pure Ar inert gas atmosphere protection smelting furnace.
Further, before the Al-La intermediate alloy is added into the aluminum alloy melt, the hydrogen content in the aluminum alloy melt is less than 0.3mL/100g.
Further, the rare earth La content in the conductor aluminum alloy cast ingot is controlled to be 0.04-0.1 wt%.
Further, the temperature of the heating in the step (1) is 800-900 ℃.
Further, the temperature of the heating in the step (2) is 730-760 ℃; the heat preservation time of the rare earth La which is wrapped by aluminum foil and added into the aluminum melt is 10-30min.
Further, the temperature of the Al-Si alloy melt prepared in the step (3) is 700-720 ℃; the temperature of the Al-Si alloy melt after Mg is added is 750-770 ℃.
Further, the heating temperature in the step (5) is 520-550 ℃; the heating temperature in the step (6) is 175-215 ℃.
Compared with the prior art, the invention has the positive and beneficial effects that:
(1) The second phase particles commonly found in Al-Mg-Si alloys are Si and Mg 2 Si phase, mg when contacting corrosive medium 2 The Mg element in the Si particles is preferentially dissolved, and the potential of the Al matrix is higher than that of Mg 2 The potential of Si particles, the potential difference between them accelerating Mg 2 The potential of the Al matrix is lower than that of the Si particles, the Al matrix at the edge of the Si particles is anodically dissolved, the local corrosion of the Al matrix extends to the long flaky Si particles along the grain boundary region to form deep and narrow corrosion pits, and after the Si particles are removed from the corrosion pits, the corrosion continuously develops along the grain boundary due to the self-catalytic effect in the deep and narrow corrosion pits, so that the grain boundary region is severely corroded. Due to the rare earth elements added in the inventionThe atomic radius (0.187 nm) of the element La is larger than that of Al (0.143 nm), si (0.134 nm) and Mg (0.160 nm), and the rare earth element La is arranged between the Al matrix and the Mg 2 The solubility in Si particles is low, so La atoms are repelled in Al matrix and Mg during solidification 2 An La-rich layer is formed in the interface area of Si particles and is wrapped on Mg 2 The surface of Si particles, thereby at Mg 2 The La-rich layer is formed on the surface of the Si particle, and because the potential of rare earth element La is lower, mg 2 The La-rich layer formed on the surface of the Si particles is preferentially dissolved in Mg 2 The local region near the Si particles releases high concentration of La 3+ La as corrosion inhibitor 3+ To react with water solution to generate La with protective effect 2 O 3 /La(OH) 3 Layer coated with Mg 2 Si particle surface, thereby hindering Mg 2 The Si particles are selectively dissolved, and meanwhile, the addition of trace La also prevents the growth of the Si particles, so that the Si particles are changed into a short rod-shaped structure from a long sheet-shaped structure, the continuous distribution of the Si particles at the grain boundary is broken, the fine and dispersed Si particles are formed, the corrosion is prevented from being rapidly expanded along the grain boundary region, and the lasting corrosion resistance of the aluminum alloy is further improved.
(2) According to the invention, when the Al-La intermediate alloy is prepared, the content of impurity oxygen element in the added rare earth element La is controlled to be less than 0.02 wt%, so that the content of harmful impurities in the Al-La intermediate alloy and the final aluminum alloy melt can be controlled, and the corrosion resistance of the final aluminum alloy melt is prevented from weakening due to excessive content of harmful impurities. If the content of the impurity oxygen element in the added rare earth element La is more than 0.02wt.% in the preparation of the Al-La intermediate alloy, on the one hand, a large amount of oxide is contained in the rare earth element La, and when the Al-La intermediate alloy is added into the aluminum alloy melt, the oxide is difficult to float up, impurities are easy to form in the aluminum alloy, and meanwhile, the impurity rare earth oxide La is introduced 2 O 3 So that the reaction is reversible La in (La) 2 O 3 The concentration of the rare earth oxides is increased, so that the reversible reaction moves leftwards, the deslagging effect of La element is reduced, the inclusion caused by the introduction of the rare earth oxides and incomplete deslagging is used as a leakage source, and the inclusion is used as a corrosion starting position in a corrosion medium, so that the occurrence of corrosion is accelerated; on the other hand, the added rare earth La forms rare earth oxide with oxygen element, and is used as modified Si and Mg after the Al-La master alloy is added into the aluminum alloy melt 2 The effective La element of Si particles is reduced, and the corresponding effect of improving the corrosion resistance of the aluminum alloy is also weakened.
(3) The invention is to control the hydrogen content in the aluminum alloy melt to be less than 0.3mL/100g because the hydrogen element reacts with rare earth La to form La+2[H]→LaH 2 The Gibbs standard free energy of the alloy is negative in the smelting temperature range of the aluminum alloy and is more than deslagging reaction When the hydrogen content in the aluminum alloy melt is larger than 0.3mL/100g, the limited rare earth La changes the main effect into dehydrogenation after the Al-La intermediate alloy is added into the aluminum alloy melt, and the metamorphic Si and Mg cannot be exerted 2 The effect of the Si particles, and therefore the effect of the rare earth La on improving the corrosion resistance of the aluminum alloy, is impaired.
(4) The content of the added rare earth element La is controlled to be 0.04-0.1wt.%, because after the content of the added rare earth element La exceeds 0.10wt.%, laAlSi intermetallic compounds with tetragonal structures are formed in the structure after the aluminum alloy is solidified, the pitting potential of the aluminum alloy is reduced, and the corrosion resistance of the aluminum alloy is gradually reduced; when the addition amount of the rare earth element La is less than 0.04wt.%, the rare earth element La mainly plays roles of removing hydrogen and slag in the aluminum alloy melt because the addition amount of the rare earth element La is too small, so that the rare earth element La cannot play roles of deteriorating Si and Mg 2 The effect of the Si particles, and correspondingly the effect of improving the corrosion resistance of the aluminum alloy, is also weakened.
(5) Compared with the rare earth aluminum alloy in the prior art, the rare earth aluminum alloy adopts the rare earth microalloying technology, trace rare earth elements (< 0.1 wt%) are added, the addition amount of rare earth is obviously reduced, and compared with the rare earth element Sc which is frequently added, the rare earth element La is added, so that the preparation cost of the aluminum alloy is reduced.
Drawings
FIG. 1 is a graph of the corrosion profile of an aluminum alloy ingot of the present invention;
FIG. 2 is a cross-sectional corrosion profile of an aluminum alloy ingot of the present invention;
FIG. 3 is a graph showing the corrosion morphology of an aluminum alloy ingot without rare earth element La added in the comparative example of the present invention;
FIG. 4 is a cross-sectional corrosion profile of an aluminum alloy ingot without rare earth element La added in the comparative example of the present invention.
Detailed Description
For a better understanding of the present invention, reference is made to the following examples, which are included within the scope of the present invention, but are not intended to limit the scope of the present invention.
Example 1
A method for improving corrosion damage resistance of a conductor aluminum alloy, comprising the steps of:
(1) Preparing an Al-Si prefabricated alloy: placing an industrial pure aluminum ingot into a graphite clay crucible, heating to melt the aluminum ingot and heating to 850 ℃ to form an aluminum melt, adding Si into the aluminum melt for heat preservation, and then casting the aluminum melt after adding the Si into an iron mold to obtain an Al-12Si prefabricated alloy ingot;
(2) Al-La intermediate alloy preparation: placing an industrial pure aluminum ingot into a graphite clay crucible, heating to melt and raise the temperature to 750 ℃ to form an aluminum melt, wrapping and adding rare earth La with the oxygen content of 0.014wt.% into the aluminum melt by using aluminum foil, preserving heat for 20min, and casting the aluminum melt after adding the rare earth La into an iron mold to obtain an Al-9La intermediate alloy, wherein the preparation of the Al-9La intermediate alloy is carried out in a pure Ar inert gas atmosphere protection smelting furnace;
(3) Placing industrial pure aluminum and an Al-12Si prefabricated alloy cast ingot into a graphite clay crucible according to the component proportion of Al-0.6Si-0.6Mg-0.08La, heating and melting by using a resistance furnace to obtain an Al-12Si alloy melt, adding pure Mg wrapped by an Al foil into the obtained Al-12Si alloy melt by using a bell jar, stirring the melt to fully dissolve Mg, heating to 750 ℃, adding a mixture of NaCl, KCl and Na3AlF6, refining for 10min, standing to form an aluminum alloy melt, removing slag and gas in the melt by using a refining agent, and measuring the hydrogen content in the aluminum alloy melt liquid to be 0.24mL/100g by using an aluminum liquid hydrogen meter;
(4) Adding the Al-9La intermediate alloy obtained in the step (2) into the aluminum alloy melt obtained in the step (3), preserving heat and stirring for 10min, then cooling to 720 ℃, adding 0.3% of refiner Al-5Ti-1B, blowing high-purity Ar gas into the aluminum alloy melt added with the Al-9La intermediate alloy, and finally casting the aluminum alloy melt added with the Al-9La intermediate alloy into an iron mold preheated to 150 ℃ to obtain a cylindrical conductor aluminum alloy cast ingot with the diameter of 20mm and the height of 40 mm;
(5) Heating the conductor aluminum alloy cast ingot obtained in the step (4) to 535 ℃ for heat preservation for 1h, and then carrying out water quenching treatment;
(6) And (3) heating the conductor aluminum alloy cast ingot after water quenching in the step (5) to 200 ℃, and then aging for 4 hours.
Example 2
A method for improving corrosion damage resistance of a conductor aluminum alloy, comprising the steps of:
(1) Preparing an Al-Si prefabricated alloy: placing an industrial pure aluminum ingot into a graphite clay crucible, heating to melt the aluminum ingot and heating to 800 ℃ to form an aluminum melt, adding Si into the aluminum melt for heat preservation, and then casting the aluminum melt after adding the Si into an iron mold to obtain an Al-12Si prefabricated alloy ingot;
(2) Al-La intermediate alloy preparation: placing an industrial pure aluminum ingot into a graphite clay crucible, heating to melt the aluminum ingot and heating the aluminum ingot to 730 ℃ to form an aluminum melt, wrapping and adding rare earth La with the oxygen content of 0.016wt.% into the aluminum melt by using aluminum foil, preserving heat for 30min, and casting the aluminum melt after adding the rare earth La into an iron mold to obtain an Al-9La intermediate alloy, wherein the preparation of the Al-9La intermediate alloy is carried out in a pure Ar inert gas atmosphere protection smelting furnace;
(3) Placing industrial pure aluminum and an Al-12Si prefabricated alloy cast ingot into a graphite clay crucible according to the component proportion of Al-0.6Si-0.6Mg-0.04La, heating and melting by using a resistance furnace to obtain an Al-12Si alloy melt, adding pure Mg wrapped by an Al foil into the obtained Al-12Si alloy melt by using a bell jar, stirring the melt to fully dissolve Mg, heating to 760 ℃, adding a mixture of NaCl, KCl and Na3AlF6, refining for 12min, standing to form an aluminum alloy melt, removing slag and gas in the melt by using a refining agent, and measuring the hydrogen content in the aluminum alloy melt liquid to be 0.25mL/100g by using an aluminum liquid hydrogen meter;
(4) Adding the Al-9La intermediate alloy obtained in the step (2) into the aluminum alloy melt obtained in the step (3), preserving heat and stirring for 8min, then cooling to 700 ℃, adding 0.2% of refiner Al-5Ti-1B, blowing high-purity Ar gas into the aluminum alloy melt added with the Al-9La intermediate alloy, and finally casting the aluminum alloy melt added with the Al-9La intermediate alloy into an iron mold preheated to 150 ℃ to obtain a cylindrical conductor aluminum alloy cast ingot with the diameter of 20mm and the height of 40 mm;
(5) Heating the conductor aluminum alloy cast ingot obtained in the step (4) to 520 ℃ for heat preservation for 2 hours, and then carrying out water quenching treatment;
(6) And (3) heating the conductor aluminum alloy cast ingot after water quenching in the step (5) to 175 ℃, and then aging for 6 hours.
Example 3
A method for improving corrosion damage resistance of a conductor aluminum alloy, comprising the steps of:
(1) Preparing an Al-Si prefabricated alloy: placing an industrial pure aluminum ingot into a graphite clay crucible, heating to melt the aluminum ingot and heating to 870 ℃ to form an aluminum melt, adding Si into the aluminum melt for heat preservation, and then casting the aluminum melt after adding the Si into an iron mold to obtain an Al-12Si prefabricated alloy ingot;
(2) Al-La intermediate alloy preparation: placing an industrial pure aluminum ingot into a graphite clay crucible, heating to melt the aluminum ingot and heating to 740 ℃ to form an aluminum melt, wrapping and adding rare earth La with the oxygen content of 0.018wt.% into the aluminum melt by using aluminum foil, preserving heat for 25min, and casting the aluminum melt after adding the rare earth La into an iron mold to obtain an Al-9La intermediate alloy, wherein the preparation of the Al-9La intermediate alloy is carried out in a pure Ar inert gas atmosphere protection smelting furnace;
(3) Placing industrial pure aluminum and an Al-12Si prefabricated alloy cast ingot into a graphite clay crucible according to the component proportion of Al-0.6Si-0.6Mg-0.06La, heating and melting by using a resistance furnace to obtain an Al-12Si alloy melt, adding pure Mg wrapped by an Al foil into the obtained Al-12Si alloy melt by using a bell jar, stirring the melt to fully dissolve Mg, heating to 770 ℃, adding a mixture of NaCl, KCl and Na3AlF6, refining for 15min, standing to form an aluminum alloy melt, removing slag and gas in the melt by using a refining agent, and measuring the hydrogen content in the aluminum alloy melt liquid to be 0.26mL/100g by using an aluminum liquid hydrogen meter; the method comprises the steps of carrying out a first treatment on the surface of the
(4) Adding the Al-9La intermediate alloy obtained in the step (2) into the aluminum alloy melt obtained in the step (3), preserving heat and stirring for 12min, then cooling to 710 ℃, adding 0.25% of refiner Al-5Ti-1B, blowing high-purity Ar gas into the aluminum alloy melt added with the Al-9La intermediate alloy, and finally casting the aluminum alloy melt added with the Al-9La intermediate alloy into an iron mold preheated to 150 ℃ to obtain a cylindrical conductor aluminum alloy cast ingot with the diameter of 20mm and the height of 40 mm;
(5) Heating the conductor aluminum alloy cast ingot obtained in the step (4) to 540 ℃ for heat preservation for 50min, and then carrying out water quenching treatment;
(6) And (3) heating the conductor aluminum alloy cast ingot after water quenching in the step (5) to 215 ℃, and then aging for 3 hours.
Example 4
A method for improving corrosion damage resistance of a conductor aluminum alloy, comprising the steps of:
(1) Preparing an Al-Si prefabricated alloy: placing an industrial pure aluminum ingot into a graphite clay crucible, heating to melt the aluminum ingot and heating to 900 ℃ to form an aluminum melt, adding Si into the aluminum melt for heat preservation, and then casting the aluminum melt after adding the Si into an iron mold to obtain an Al-12Si prefabricated alloy ingot;
(2) Al-La intermediate alloy preparation: placing an industrial pure aluminum ingot into a graphite clay crucible, heating to melt and raise the temperature to 760 ℃ to form an aluminum melt, wrapping and adding rare earth La with the oxygen content of 0.017wt.% into the aluminum melt by using aluminum foil, preserving the temperature for 10min, and casting the aluminum melt after adding the rare earth La into an iron mold to obtain an Al-9La intermediate alloy, wherein the preparation of the Al-9La intermediate alloy is carried out in a pure Ar inert gas atmosphere protection smelting furnace;
(3) Placing industrial pure aluminum and an Al-12Si prefabricated alloy cast ingot into a graphite clay crucible according to the component proportion of Al-0.6Si-0.6Mg-0.1La, heating and melting by using a resistance furnace to obtain an Al-12Si alloy melt, adding pure Mg wrapped by an Al foil into the obtained Al-12Si alloy melt by using a bell jar, stirring the melt to fully dissolve Mg, heating to 760 ℃, adding a mixture of NaCl, KCl and Na3AlF6, refining for 15min, standing to form an aluminum alloy melt, removing slag and gas in the melt by using a refining agent, and measuring the hydrogen content in the aluminum alloy melt liquid to be 0.28mL/100g by using an aluminum liquid hydrogen meter; the method comprises the steps of carrying out a first treatment on the surface of the
(4) Adding the Al-9La intermediate alloy obtained in the step (2) into the aluminum alloy melt obtained in the step (3), preserving heat and stirring for 15min, then cooling to 715 ℃, adding 0.25% of refiner Al-5Ti-1B, blowing high-purity Ar gas into the aluminum alloy melt added with the Al-9La intermediate alloy, and finally casting the aluminum alloy melt added with the Al-9La intermediate alloy into an iron mold preheated to 150 ℃ to obtain a cylindrical conductor aluminum alloy cast ingot with the diameter of 20mm and the height of 40 mm;
(5) Heating the conductor aluminum alloy cast ingot obtained in the step (4) to 550 ℃ for heat preservation for 30min, and then carrying out water quenching treatment;
(6) And (3) heating the conductor aluminum alloy cast ingot after water quenching in the step (5) to 190 ℃, and then aging for 5 hours.
Comparative example 1
The only difference between comparative example 1 and example 1 is that: a trace of rare earth element La was not added, and the other was exactly the same as in example 1.
Comparative example 2
The only difference between comparative example 2 and example 1 is that: in the step (2), rare earth La having an oxygen content of 0.025wt.% was added to the aluminum melt by wrapping it with aluminum foil and heat-preserving for 20 minutes, and the other steps were exactly the same as in example 1.
Comparative example 3
The only difference between comparative example 3 and example 1 is that: in the step (3), the hydrogen content in the aluminum alloy melt liquid is measured to be 0.32mL/100g by utilizing an aluminum liquid hydrogen meter; the other is exactly the same as in example 1.
Comparative example 4
The only difference between comparative example 4 and example 1 is that: in the step (3), the component proportion of Al-0.6Si-0.6Mg-0.12La is calculated; the other is exactly the same as in example 1.
The chemical compositions of the aluminum alloy ingots were measured by using an inductively coupled plasma emission spectrometer, and the chemical compositions of the aluminum alloy ingots in each example and comparative example and the oxygen and hydrogen element contents in the preparation process are shown in table 1.
Table 1 chemical composition of aluminum alloy ingots and comparative examples and comparative preparation process
The strength, conductivity and corrosion resistance of the aluminum alloy ingots subjected to the aging treatment of examples 1 to 4 and comparative examples 1 to 4 were tested as follows:
the tensile strength of the aluminum alloy ingot in example 1 was 268MPa and the electrical conductivity was 57.9% iacs; the tensile strength of the aluminum alloy ingot in example 2 was 256MPa and the electrical conductivity was 57.4% iacs; the tensile strength of the aluminum alloy ingot in example 3 was 264MPa and the electrical conductivity was 57.7% IACS; the tensile strength of the aluminum alloy ingot in example 4 was 270MPa and the electrical conductivity was 57.9% IACS. After an aluminum alloy ingot is placed in NaCl solution with the concentration of 3.5% for 384 hours, all 4 examples are corroded uniformly, the depth of a corrosion pit is shallower, taking example 1 as an example, the corrosion pit size is smaller as shown in the attached drawing 1, the section corrosion appearance is shown in the attached drawing 2, no obvious corrosion trace exists in a grain boundary area, and the maximum corrosion depth is 30 mu m.
The tensile strength of the aluminum alloy cast ingot in comparative example 1 is 247MPa, and the conductivity is 56.8 percent IACS; the tensile strength of the aluminum alloy cast ingot of comparative example 2 is 240MPa, and the conductivity is 56.6 percent IACS; comparative example 3 aluminum alloy ingot tensile strength 249MPa, electrical conductivity 56.8% iacs; comparative example 4 aluminum alloy ingot had a tensile strength of 252MPa, conductivity 56.6% iacs; after the aluminum alloy ingot is placed in NaCl solution with the concentration of 3.5 percent for 384 hours, the surface of the aluminum alloy ingot is severely corroded. Taking comparative example 1 as an example, the corrosion morphology is shown in fig. 3, the mutual combination size between corrosion pits is large, the grain boundary region is corroded into obvious grooves, the corrosion morphology of the section of the cast ingot is shown in fig. 4, the corrosion of the grain boundary region is obvious, and the maximum corrosion depth is 150 mu m.
From the test results, the invention improves the lasting corrosion resistance of the aluminum alloy cast ingot and also improves the tensile strength and the conductivity of the aluminum alloy cast ingot by reasonably controlling the addition amount of the rare earth element La, the content of the impurity oxygen element in the rare earth element La and the content of hydrogen in the aluminum alloy melt.
The above description should not be taken as limiting the practice of the invention to these descriptions, but it will be understood by those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and the invention is defined by the appended claims.
Claims (6)
1. The method for improving corrosion damage resistance of the conductor aluminum alloy is characterized by comprising the following steps of:
(1) Preparing an Al-Si prefabricated alloy: placing an industrial pure aluminum ingot into a graphite clay crucible, heating to melt and raise the temperature to form an aluminum melt, adding Si into the aluminum melt for heat preservation, and then casting the aluminum melt after adding the Si into an iron mold to obtain an Al-Si prefabricated alloy ingot;
(2) Al-La intermediate alloy preparation: placing an industrial pure aluminum ingot into a graphite clay crucible, heating to melt and raise the temperature to form an aluminum melt, wrapping rare earth element La with aluminum foil, adding the rare earth element La into the aluminum melt, preserving heat, and casting the aluminum melt added with the rare earth element La into an iron mold to obtain an Al-La intermediate alloy;
(3) Placing industrial pure aluminum and Al-Si prefabricated alloy cast ingot into a graphite clay crucible, heating to melt and raise the temperature to obtain Al-Si alloyWrapping pure Mg with aluminum foil, adding into the Al-Si alloy melt, stirring to dissolve Mg completely, heating, and adding NaCl, KCl and Na 3 AlF 6 Refining and standing the mixture for 10-15min to form an aluminum alloy melt;
(4) Adding the Al-La intermediate alloy obtained in the step (2) into the aluminum alloy melt obtained in the step (3), preserving heat and stirring for 8-15min, then cooling to 700-720 ℃, adding 0.2-0.3% of Al-5Ti-1B refiner, blowing high-purity Ar gas into the aluminum alloy melt added with the Al-La intermediate alloy, and finally casting the aluminum alloy melt added with the Al-La intermediate alloy into a preheated iron mold to obtain a conductor aluminum alloy cast ingot;
(5) Heating the conductor aluminum alloy cast ingot obtained in the step (4) to a certain temperature for heat preservation, and then carrying out water quenching treatment;
(6) Heating the conductor aluminum alloy cast ingot subjected to water quenching in the step (5) to a certain temperature for heat preservation, and then performing artificial aging treatment;
the content of impurity oxygen elements in rare earth elements La of the Al-La intermediate alloy is less than 0.02wt.%, and the total content of the rare earth elements La is more than 99.5wt.%;
before the Al-La intermediate alloy is added into an aluminum alloy melt, the hydrogen content in the aluminum alloy melt is less than 0.3mL/100g;
the content of rare earth element La in the conductor aluminum alloy cast ingot is controlled to be 0.04-0.1 wt%.
2. The method for improving corrosion damage resistance of a conductor aluminum alloy according to claim 1, wherein the preparation of the Al-La intermediate alloy is performed in a pure Ar gas inert atmosphere protection smelting furnace.
3. The method for improving corrosion damage resistance of a conductive aluminum alloy according to claim 1, wherein the temperature of the heating in the step (1) is 800-900 ℃.
4. The method for improving corrosion damage resistance of a conductive aluminum alloy according to claim 1, wherein the temperature of the heating in the step (2) is 730-760 ℃; the heat preservation time of the rare earth La which is wrapped by aluminum foil and added into the aluminum melt is 10-30min.
5. The method for improving corrosion damage resistance of a conductor aluminum alloy according to claim 1, wherein the temperature of the Al-Si alloy melt prepared in the step (3) is 700-720 ℃; the temperature of the Al-Si alloy melt after Mg is added is 750-770 ℃.
6. The method of claim 1, wherein the heating in step (5) is performed at a temperature of 520-550 ℃; the heating temperature in the step (6) is 175-215 ℃.
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