A heat treatment method for forming an ultra-thin corrosion-resistant oxide layer on the surface of an Au alloy

Abstract

The application discloses a heat treatment method for generating an ultrathin corrosion-resistant oxide layer on the surface of an Au alloy, and comprises the following steps: loading the gold alloy into a closed container, repeatedly washing the inside of the closed container with inert gas, making the oxygen partial pressure in the closed container 20-500 Pa, and introducing inert gas as protective gas; annealing the closed container containing the gold alloy, the annealing temperature is 500-600 DEG C, and the annealing time is 3-10 h; other elements in the gold alloy can form a dense oxide layer and can form a single-phase intermetallic compound with Au. The composition ratio of the Au-containing alloy itself is not changed, and the corrosion resistance is improved only by controlling the annealing conditions, so that the application has strong applicability in the field of energy storage equipment and other fields where noble metals are used more.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of Au-containing alloy corrosion resistance, and particularly relates to a heat treatment method for generating an ultrathin corrosion-resistant oxide layer on the surface of an Au alloy. BACKGROUND

[0002] The statements herein only provide background technology related to the present application, and do not necessarily constitute the prior art.

[0003] A gold alloy is a noble metal material composed of gold as a main component and other elements. The addition of other elements can improve the performance of pure gold, such as increasing the strength and wear resistance of gold, and improving the electrical properties of gold. Gold alloys are widely used as conductor materials in electronic devices, semiconductor equipment and microcircuits.

[0004] Au is an inert metal that is difficult to corrode under normal conditions. However, after Au is alloyed with a reactive metal element, the corrosion resistance of the alloy mainly depends on the properties of the reactive element. For example, in an HCl solution (concentration > 0.01 M), the Al element is selectively corroded, and the Au element is rearranged to form nanoporous gold, causing the alloy to lose its original alloy luster (Al2Au is powder purple) and turn into the dark yellow color of porous gold (the finer the pore size, the darker the yellow color). Although adding other corrosion-resistant elements or increasing the content of Au element is an effective measure to inhibit the corrosion of Au-containing alloys, it will affect the original color of the alloy and there are problems such as excessive cost.

[0005] In addition, the existing alloy corrosion prevention process often uses annealing process, but the inventors have found through experiments that if a conventional annealing process is used to heat treat the gold alloy, a micron-level thick corrosion-resistant oxide layer is formed on the surface of the gold alloy. Although this oxide layer can improve the corrosion resistance of the gold alloy to some extent, it will significantly reduce the electrical conductivity of the gold alloy due to its large thickness, thereby making it difficult to take advantage of the excellent electrical conductivity of the gold alloy. SUMMARY

[0006] In view of the deficiencies of the prior art, the present application aims to provide a heat treatment method for generating an ultrathin corrosion-resistant oxide layer on the surface of an Au alloy.

[0007] In order to achieve the above-mentioned purpose, the present application is realized by the following technical solution:

[0008] In a first aspect, the present application provides a heat treatment method for generating an ultrathin corrosion-resistant oxide layer on the surface of an Au alloy, comprising the following steps:

[0009] The gold alloy is loaded into a closed container, and the inside of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 20-500 Pa, and inert gas is introduced as a protective gas;

[0010] The closed container containing the gold alloy is annealed at a temperature of 500-600℃ for 3-10h.

[0011] In the gold alloy, the elements other than gold can form a dense oxide layer and can form a single-phase intermetallic compound with Au.

[0012] Due to the low oxygen partial pressure atmosphere created during annealing, the oxidation process of Al2Au is very slow, and only a nanoscale oxide film is formed on the surface of the alloy after annealing. The heat treatment method in the present application is based on controlling the form of gold atoms in the oxide layer, and is more inclined to a surface modification method. It has a strict temperature range, and beyond this temperature range, it no longer has this excellent corrosion resistance.

[0013] During the oxidation process, the original lattice structure of the gold alloy is destroyed, and nanoscale phase separation of gold and other elements occurs. Under a low oxygen partial pressure environment, the oxidation rate of the alloy is slow, greatly reducing the degree of phase separation of gold and other elements. Au atoms remain in the dense oxide layer formed by the oxidation of other elements in the form of nanoscale clusters, with a nanoscale spacing. This greatly increases the density of the aluminum oxide layer and effectively prevents the intrusion of corrosive elements in the external environment. This greatly increases the density of the oxidation layer of other elements and effectively prevents the intrusion of corrosive substances in the external environment, thereby effectively improving the corrosion resistance of the gold alloy.

[0014] In addition, the corrosion-resistant oxide film prepared by the method of the present application has a nanoscale thickness, which is 2-3 orders of magnitude lower than the thickness of the oxide layer prepared by traditional annealing processes. This can effectively reduce the problem of significant conductivity reduction caused by an excessively thick oxide layer, and is more conducive to the application of gold alloys as conductive materials.

[0015] In some embodiments, the gold alloy contains Al or Ti in addition to gold.

[0016] Preferably, the gold content in the gold alloy is greater than 30%, which is the mass percentage.

[0017] In some embodiments, the inert gas is nitrogen or argon.

[0018] Preferably, the inert gas is introduced as a protective gas to make the pressure in the closed container equal to or lower than atmospheric pressure.

[0019] In some embodiments, the closed container is a quartz tube.

[0020] In some embodiments, the annealing temperature is 550-600℃, and the annealing time is 3-8h. In some embodiments, the annealing temperature is 550-600℃, and the annealing time is 3-8h.

[0021] In some embodiments, when the gold alloy is an Al2Au alloy, the annealing temperature is 540-560°C and the annealing time is 4-6 hours.

[0022] In some embodiments, the oxygen partial pressure during annealing is less than 200 Pa;

[0023] Preferably, the oxygen partial pressure during annealing is below 150 Pa;

[0024] Preferably, the oxygen partial pressure during annealing is less than 100 Pa;

[0025] Preferably, the oxygen partial pressure during annealing is below 40 Pa.

[0026] Preferably, the oxygen partial pressure during annealing is 20-30 Pa.

[0027] Secondly, the present invention provides a corrosion-resistant Au alloy, prepared by the aforementioned heat treatment method.

[0028] The beneficial effects achieved by one or more embodiments of the present invention described above are as follows:

[0029] Regarding the issue of improving the corrosion resistance of Au-containing alloys, many solutions exist, such as increasing the Au content or adding other corrosion-resistant elements like Ni and Cr, all of which can improve the alloy's corrosion resistance. The advantage of this invention is that it achieves improved corrosion resistance solely through controlling the annealing conditions without altering the composition of the Au-containing alloy itself, making it highly applicable in fields such as energy storage equipment where precious metals are frequently used. Attached Figure Description

[0030] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0031] Figure 1 The corrosion morphology of Al2Au alloy without special annealing treatment after 1h of etching with 1M HCl;

[0032] Figure 2 The corrosion morphology of the Al2Au alloy annealed according to Example 1 of the present invention after 1h corrosion with 1M HCl;

[0033] Figure 3 This refers to the special oxide layer structure on the surface of the Al2Au alloy after annealing treatment according to Example 1 of the present invention;

[0034] Figure 4 This is a crystal structure diagram of the Al2Au alloy after annealing in Example 1 of the present invention;

[0035] Figure 5Figure 2 is a surface morphology diagram of the Al2Au alloy after annealing treatment in Example 2 of the present application before corrosion in 1M HCl solution;

[0036] Figure 6 Figure 3 is a surface morphology diagram of the Al2Au alloy after annealing treatment in Example 2 of the present application after corrosion in 1M HCl solution;

[0037] Figure 7 Figure 4 is a surface morphology diagram of the Al2Au alloy after annealing treatment in Comparative Example 1 of the present application before corrosion in 1M HCl solution;

[0038] Figure 8 Figure 5 is a surface morphology diagram of the Al2Au alloy after annealing treatment in Comparative Example 1 of the present application after corrosion in 1M HCl solution;

[0039] Figure 9 Figure 6 is a surface morphology diagram of the Al2Au alloy after annealing treatment in Comparative Example 2 of the present application before corrosion in 1M HCl solution;

[0040] Figure 10 Figure 7 is a surface morphology diagram of the Al2Au alloy after annealing treatment in Comparative Example 2 of the present application after corrosion in 1M HCl solution;

[0041] Figure 11 Figure 8 is a surface morphology diagram of the Al2Au alloy after annealing treatment in Comparative Example 3 of the present application before corrosion in 1M HCl solution;

[0042] Figure 12 Figure 9 is a surface morphology diagram of the Al2Au alloy after annealing treatment in Comparative Example 3 of the present application after corrosion in 1M HCl solution. DETAILED DESCRIPTION

[0043] It should be noted that the following detailed description is illustrative only and is not intended to limit the application in any way. Except where otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.

[0044] Example 1

[0045] A heat treatment method for generating an ultra-thin corrosion-resistant oxide layer on the surface of an Al2Au alloy, comprising the following steps:

[0046] The Al2Au alloy is loaded into a closed container, and the interior of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 30 Pa, and nitrogen gas is introduced as a protective gas;

[0047] The closed container containing the gold alloy is annealed at a temperature of 550 DEG C for 5 hours to obtain an Al2Au alloy with enhanced corrosion resistance.

[0048] Corrosion resistance test:

[0049] The Al2Au alloy before and after annealing is respectively corroded using 1M HCl solution for 1 hour.

[0050] It can be found that the Al2Au alloy without special annealing treatment is seriously dealloyed corrosion Figure 1 ), and the Al element is corroded and dissolved, and the Au element forms a nano-porous structure.

[0051] The Al2Au alloy after special annealing treatment is not corroded on the surface Figure 2 ) in 1M HCl for 1 hour.

[0052] In a high temperature environment, the Al element of Al2Au will be oxidized, and the Au element will not. Due to the low oxygen partial pressure atmosphere created during annealing, the oxidation process of Al2Au is very slow, and only about 40nm of oxide film is generated on the surface of the alloy after 5h of annealing (such as Figure 3 )。

[0053] In the oxidation process, the original lattice structure of Al2Au is destroyed, and nanoscale phase separation of Al and Au occurs (such as Figure 4 ), in a low oxygen partial pressure environment, the oxidation speed of the alloy is slow, the degree of phase separation of Al and Au is greatly reduced, the Au atoms remain in the form of nanoscale clusters in the aluminum oxide Al2O3, and the distance between them is also nanoscale, greatly increasing the density of the aluminum oxide layer, effectively preventing the invasion of corrosive elements in the external environment, and greatly enhancing the corrosion resistance (the Al2O3 generated on the surface of pure Al will be corroded by HCl).

[0054] Compared with other annealing treatment methods for enhancing the corrosion resistance of alloys, the thickness of the oxide layer prepared by the present application is reduced by 2-3 orders of magnitude, effectively reducing the conductivity loss caused by the over-thickness of the oxide layer.

[0055] Example 2

[0056] A heat treatment method for generating an ultra-thin corrosion-resistant oxide layer on the surface of an Al2Au alloy, comprising the following steps:

[0057] The Al2Au alloy is loaded into a closed container, and inert gas is repeatedly washed inside the closed container to make the oxygen partial pressure in the closed container 35Pa, and nitrogen gas is introduced as a protective gas;

[0058] The Al2Au alloy was annealed in a closed container at a temperature of 575°C for 5 hours to obtain an Al2Au alloy with enhanced corrosion resistance.

[0059] Figure 5 Figure 2 is a surface morphology diagram of the Al2Au alloy of Example 2 before corrosion in 1M HCl solution, and Figure 3 is a surface morphology diagram of the Al2Au alloy of Example 2 after corrosion in 1M HCl solution. Figure 5 As can be seen, after annealing, a dense oxide layer is formed on the surface of the Al2Au alloy, and the gold enhances the dense aluminum oxide layer.

[0060] The Al2Au alloy before and after annealing was respectively corroded using 1M HCl solution for 1 hour. Figure 6 Figure 2 is a surface morphology diagram of the Al2Au alloy of Example 2 before corrosion in 1M HCl solution, and Figure 3 is a surface morphology diagram of the Al2Au alloy of Example 2 after corrosion in 1M HCl solution.

[0061] Comparative Example 1

[0062] The heat treatment method for the Al2Au alloy includes the following steps:

[0063] The Al2Au alloy was placed in a closed container, and the inside of the closed container was repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 35 Pa, and nitrogen gas was introduced as a protective gas.

[0064] The Al2Au alloy was annealed in a closed container at a temperature of 800°C for 5 hours to obtain the treated Al2Au alloy.

[0065] Figure 7 Figure 4 is a surface morphology diagram of the Al2Au alloy of Comparative Example 1 before corrosion in 1M HCl solution, and Figure 5 is a surface morphology diagram of the Al2Au alloy of Comparative Example 1 after corrosion in 1M HCl solution.

[0066] The Al2Au alloy before and after annealing was respectively corroded using 1M HCl solution for 1 hour. Figure 8 Figure 4 is a surface morphology diagram of the Al2Au alloy of Comparative Example 1 before corrosion in 1M HCl solution, and Figure 5 is a surface morphology diagram of the Al2Au alloy of Comparative Example 1 after corrosion in 1M HCl solution.

[0067] Comparative Example 2

[0068] The heat treatment method for the Al2Au alloy includes the following steps:

[0069] The Al2Au alloy was placed in a sealed container, and the inside of the sealed container was repeatedly purged with an inert gas to make the oxygen partial pressure inside the sealed container 35 Pa. Nitrogen gas was then introduced as a protective gas.

[0070] The sealed container containing the gold alloy was annealed at a temperature of 400℃ for 5 hours to obtain the treated Al2Au alloy.

[0071] Figure 9 The image shows the surface morphology of the Al2Au alloy after annealing at 400℃ before corrosion in 1M HCl solution in Comparative Example 2. It can be seen that although no aluminum oxide segregation occurred on the surface of the Al2Au alloy, the oxide layer was too thin and could not effectively protect the substrate.

[0072] Figure 10 The image shows the surface morphology of the Al2Au alloy annealed at 400℃ after corrosion in 1M HCl solution for 1 hour in Comparative Example 2. It can be seen that the corrosion is quite severe, forming a porous structure. This is because aluminum oxide and elemental aluminum are dissolved and leached out by the acid.

[0073] Comparative Example 3

[0074] The heat treatment method for Al2Au alloy includes the following steps:

[0075] The gold alloy was placed in a sealed container, and the inside of the sealed container was repeatedly purged with an inert gas to make the oxygen partial pressure inside the sealed container 35 Pa. Nitrogen gas was then introduced as a protective gas.

[0076] The sealed container containing the gold alloy was annealed at a temperature of 700℃ for 5 hours to obtain the treated Al2Au alloy.

[0077] Figure 11 The image shows the surface morphology of the Al2Au alloy after annealing at 700℃ before corrosion in 1M HCl solution in Comparative Example 3. An alumina protective layer with corrosion resistance is formed on the surface of the Al2Au alloy. However, it can be seen that after annealing at 700℃, the grains in the alumina protective layer grow significantly, resulting in Al segregation at the grain boundaries. The oxide layer composition at the grain boundaries is uneven, which easily leads to preferential corrosion at the grain boundaries.

[0078] Figure 12 The image shows the surface morphology of the Al2Au alloy after annealing at 700℃ in Comparative Example 3 of this invention, after being corroded in 1M HCl solution for 1 hour. It can be seen that the surface of the Al2Au alloy was corroded to a certain extent.

[0079] Example 3

[0080] A heat treatment method for generating an ultra-thin corrosion-resistant oxide layer on the surface of an Al2Au alloy, comprising the following steps:

[0081] The Al2Au alloy is placed in a closed container, the interior of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 450 Pa, and nitrogen gas is introduced as a protective gas;

[0082] The closed container containing the gold alloy is subjected to annealing treatment, the annealing temperature is 500 DEG C, the annealing time is 5 h, and an Al2Au alloy with enhanced corrosion resistance is obtained.

[0083] Example 4

[0084] A heat treatment method for generating an ultra-thin corrosion-resistant oxide layer on the surface of an Al2Au alloy, comprising the following steps:

[0085] The Al2Au alloy is placed in a closed container, the interior of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 400 Pa, and nitrogen gas is introduced as a protective gas;

[0086] The closed container containing the gold alloy is subjected to annealing treatment, the annealing temperature is 500 DEG C, the annealing time is 5 h, and an Al2Au alloy with enhanced corrosion resistance is obtained.

[0087] Example 5

[0088] A heat treatment method for generating an ultra-thin corrosion-resistant oxide layer on the surface of an Al2Au alloy, comprising the following steps:

[0089] The Al2Au alloy is placed in a closed container, the interior of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 350 Pa, and nitrogen gas is introduced as a protective gas;

[0090] The closed container containing the gold alloy is subjected to annealing treatment, the annealing temperature is 550 DEG C, the annealing time is 3 h, and an Al2Au alloy with enhanced corrosion resistance is obtained.

[0091] Example 6

[0092] A heat treatment method for generating an ultra-thin corrosion-resistant oxide layer on the surface of an Al2Au alloy, comprising the following steps:

[0093] The Al2Au alloy is placed in a closed container, the interior of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 300 Pa, and nitrogen gas is introduced as a protective gas;

[0094] The closed container containing the gold alloy is subjected to annealing treatment, the annealing temperature is 510 DEG C, the annealing time is 4 h, and an Al2Au alloy with enhanced corrosion resistance is obtained.

[0095] Example 7

[0096] A heat treatment method for generating an ultra-thin corrosion-resistant oxide layer on the surface of an Al2Au alloy, comprising the following steps:

[0097] The Al2Au alloy is loaded into a closed container, the interior of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 200 Pa, and nitrogen gas is introduced as a protective gas;

[0098] The closed container containing the gold alloy is subjected to annealing treatment, the annealing temperature is 600 ℃, the annealing time is 10 h, and an Al2Au alloy with enhanced corrosion resistance is obtained.

[0099] Example 8

[0100] A heat treatment method for generating an ultra-thin corrosion-resistant oxide layer on the surface of an Al2Au alloy, comprising the following steps:

[0101] The Al2Au alloy is loaded into a closed container, the interior of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 250 Pa, and nitrogen gas is introduced as a protective gas;

[0102] The closed container containing the gold alloy is subjected to annealing treatment, the annealing temperature is 570 ℃, the annealing time is 7 h, and an Al2Au alloy with enhanced corrosion resistance is obtained.

[0103] Example 9

[0104] A heat treatment method for generating an ultra-thin corrosion-resistant oxide layer on the surface of an Al2Au alloy, comprising the following steps:

[0105] The Al2Au alloy is loaded into a closed container, the interior of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 150 Pa, and nitrogen gas is introduced as a protective gas;

[0106] The closed container containing the gold alloy is subjected to annealing treatment, the annealing temperature is 560 ℃, the annealing time is 7 h, and an Al2Au alloy with enhanced corrosion resistance is obtained.

[0107] Example 10

[0108] A heat treatment method for generating an ultra-thin corrosion-resistant oxide layer on the surface of an Al2Au alloy, comprising the following steps:

[0109] The Al2Au alloy is loaded into a closed container, the interior of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 100 Pa, and nitrogen gas is introduced as a protective gas;

[0110] The closed container containing the gold alloy is annealed at a temperature of 550 DEG C for 4 hours to obtain an Al2Au alloy with enhanced corrosion resistance.

[0111] Example 11

[0112] A heat treatment method for forming a super-thin corrosion-resistant oxide layer on the surface of an Al2Au alloy includes the following steps:

[0113] The Al2Au alloy is placed in a closed container, the interior of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 60 Pa, and nitrogen gas is introduced as a protective gas;

[0114] The closed container containing the gold alloy is annealed at a temperature of 590 DEG C for 8 hours to obtain an Al2Au alloy with enhanced corrosion resistance.

[0115] Example 12

[0116] A heat treatment method for forming a super-thin corrosion-resistant oxide layer on the surface of an Al2Au alloy includes the following steps:

[0117] The Al2Au alloy is placed in a closed container, the interior of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 20 Pa, and nitrogen gas is introduced as a protective gas;

[0118] The closed container containing the gold alloy is annealed at a temperature of 500 DEG C for 4 hours to obtain an Al2Au alloy with enhanced corrosion resistance.

[0119] Example 13

[0120] A heat treatment method for forming a super-thin corrosion-resistant oxide layer on the surface of a titanium-gold alloy includes the following steps:

[0121] The titanium-gold alloy with a mass percentage of gold of 40% is placed in a closed container, the interior of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 20 Pa, and nitrogen gas is introduced as a protective gas;

[0122] The closed container containing the titanium-gold alloy is annealed at a temperature of 510 DEG C for 6 hours to obtain a titanium-gold alloy with enhanced corrosion resistance.

[0123] Example 14

[0124] A heat treatment method for forming a super-thin corrosion-resistant oxide layer on the surface of a titanium-gold alloy includes the following steps:

[0125] The titanium-gold alloy with 50% of gold by mass is put into a closed container, the inside of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 30 Pa, and nitrogen gas is introduced as a protective gas;

[0126] The closed container containing the titanium-gold alloy is annealed at a temperature of 510 ℃ for 6 h to obtain the titanium-gold alloy with enhanced corrosion resistance.

[0127] Example 15

[0128] A heat treatment method for generating an ultra-thin corrosion-resistant oxide layer on the surface of a titanium-gold alloy, comprising the following steps:

[0129] The titanium-gold alloy with 50% of gold by mass is put into a closed container, the inside of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 30 Pa, and nitrogen gas is introduced as a protective gas;

[0130] The closed container containing the titanium-gold alloy is annealed at a temperature of 510 ℃ for 6 h to obtain the titanium-gold alloy with enhanced corrosion resistance.

[0131] Example 16

[0132] A heat treatment method for generating an ultra-thin corrosion-resistant oxide layer on the surface of a titanium-gold alloy, comprising the following steps:

[0133] The titanium-gold alloy with 50% of gold by mass is put into a closed container, the inside of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 30 Pa, and nitrogen gas is introduced as a protective gas;

[0134] The closed container containing the titanium-gold alloy is annealed at a temperature of 510 ℃ for 6 h to obtain the titanium-gold alloy with enhanced corrosion resistance.

[0135] Example 17

[0136] A heat treatment method for generating an ultra-thin corrosion-resistant oxide layer on the surface of a titanium-gold alloy, comprising the following steps:

[0137] The titanium-gold alloy with 50% of gold by mass is put into a closed container, the inside of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 30 Pa, and nitrogen gas is introduced as a protective gas;

[0138] The closed container containing the titanium-gold alloy is annealed at a temperature of 510 ℃ for 6 h to obtain the titanium-gold alloy with enhanced corrosion resistance.

[0139] Example 18

[0140] A heat treatment method for generating an ultra-thin corrosion-resistant oxide layer on the surface of a titanium-gold alloy, comprising the following steps:

[0141] A titanium-gold alloy with a mass percentage of gold of 45% is placed in a closed container, the interior of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 150 Pa, and nitrogen gas is introduced as a protective gas;

[0142] The closed container containing the titanium-gold alloy is subjected to annealing treatment, the annealing temperature is 560℃, and the annealing time is 7h, thereby obtaining a titanium-gold alloy with enhanced corrosion resistance.

[0143] Example 19

[0144] A heat treatment method for generating an ultra-thin corrosion-resistant oxide layer on the surface of a titanium-gold alloy, comprising the following steps:

[0145] A titanium-gold alloy with a mass percentage of gold of 35% is placed in a closed container, the interior of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 200 Pa, and nitrogen gas is introduced as a protective gas;

[0146] The closed container containing the titanium-gold alloy is subjected to annealing treatment, the annealing temperature is 510℃, and the annealing time is 4h, thereby obtaining a titanium-gold alloy with enhanced corrosion resistance.

[0147] Example 20

[0148] A heat treatment method for generating an ultra-thin corrosion-resistant oxide layer on the surface of a titanium-gold alloy, comprising the following steps:

[0149] A titanium-gold alloy with a mass percentage of gold of 40% is placed in a closed container, the interior of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 250 Pa, and nitrogen gas is introduced as a protective gas;

[0150] The closed container containing the titanium-gold alloy is subjected to annealing treatment, the annealing temperature is 580℃, and the annealing time is 8h, thereby obtaining a titanium-gold alloy with enhanced corrosion resistance.

[0151] Example 21

[0152] A heat treatment method for generating an ultra-thin corrosion-resistant oxide layer on the surface of a titanium-gold alloy, comprising the following steps:

[0153] A titanium-gold alloy with a mass percentage of gold of 45% is placed in a closed container, the interior of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 300 Pa, and nitrogen gas is introduced as a protective gas;

[0154] The closed container containing the titanium-gold alloy is annealed at a temperature of 560℃ for 6 hours to obtain a titanium-gold alloy with enhanced corrosion resistance.

[0155] Example 22

[0156] A heat treatment method for generating an ultra-thin corrosion-resistant oxide layer on the surface of a titanium-gold alloy, comprising the following steps:

[0157] The titanium-gold alloy with a mass percentage of gold of 50% is placed in a closed container, the inside of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 350 Pa, and nitrogen gas is introduced as protective gas;

[0158] The closed container containing the titanium-gold alloy is annealed at a temperature of 570℃ for 5 hours to obtain a titanium-gold alloy with enhanced corrosion resistance.

[0159] Example 23

[0160] A heat treatment method for generating an ultra-thin corrosion-resistant oxide layer on the surface of a titanium-gold alloy, comprising the following steps:

[0161] The titanium-gold alloy with a mass percentage of gold of 40% is placed in a closed container, the inside of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 400 Pa, and nitrogen gas is introduced as protective gas;

[0162] The closed container containing the titanium-gold alloy is annealed at a temperature of 510℃ for 3 hours to obtain a titanium-gold alloy with enhanced corrosion resistance.

[0163] Example 24

[0164] A heat treatment method for generating an ultra-thin corrosion-resistant oxide layer on the surface of a titanium-gold alloy, comprising the following steps:

[0165] The titanium-gold alloy with a mass percentage of gold of 55% is placed in a closed container, the inside of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 450 Pa, and nitrogen gas is introduced as protective gas;

[0166] The closed container containing the titanium-gold alloy is annealed at a temperature of 570℃ for 7 hours to obtain a titanium-gold alloy with enhanced corrosion resistance.

[0167] Example 25

[0168] A heat treatment method for generating an ultra-thin corrosion-resistant oxide layer on the surface of a titanium-gold alloy, comprising the following steps:

[0169] A titanium alloy with a gold content of 60% by mass is placed in a sealed container. The inside of the sealed container is repeatedly purged with an inert gas to make the oxygen partial pressure inside the sealed container 450 Pa. Nitrogen gas is then introduced as a protective gas.

[0170] The sealed container containing the titanium alloy was annealed at a temperature of 530°C for 5 hours to obtain a titanium alloy with enhanced corrosion resistance.

[0171] Example 26

[0172] A heat treatment method for forming an ultrathin corrosion-resistant oxide layer on the surface of a titanium alloy includes the following steps:

[0173] A titanium-gold alloy with a gold content of 60% by mass is placed in a sealed container. The inside of the sealed container is repeatedly purged with an inert gas to make the oxygen partial pressure inside the sealed container 500 Pa. Nitrogen gas is then introduced as a protective gas.

[0174] The sealed container containing the titanium alloy was annealed at a temperature of 550°C for 6 hours to obtain a titanium alloy with enhanced corrosion resistance.

[0175] Example 27

[0176] A heat treatment method for forming an ultrathin corrosion-resistant oxide layer on the surface of a gold alloy includes the following steps:

[0177] A gold alloy with a gold mass percentage of 35% was placed in a sealed container. The inside of the sealed container was repeatedly purged with an inert gas to make the oxygen partial pressure inside the sealed container 30 Pa. Nitrogen gas was then introduced as a protective gas.

[0178] The sealed container containing the gold alloy was annealed at a temperature of 550°C for 8 hours to obtain a gold alloy with enhanced corrosion resistance.

[0179] Example 27

[0180] A heat treatment method for forming an ultrathin corrosion-resistant oxide layer on the surface of a gold alloy includes the following steps:

[0181] A gold alloy with a gold mass percentage of 40% was placed in a sealed container. The inside of the sealed container was repeatedly purged with an inert gas to make the oxygen partial pressure inside the sealed container 40 Pa. Nitrogen gas was then introduced as a protective gas.

[0182] The sealed container containing the gold alloy was annealed at a temperature of 560°C for 8 hours to obtain a gold alloy with enhanced corrosion resistance.

[0183] Example 28

[0184] A heat treatment method for generating an ultra-thin corrosion-resistant oxide layer on the surface of a gold alloy, comprising the following steps:

[0185] A gold alloy with a mass percentage of 45% gold is loaded into a closed container, the interior of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 100 Pa, and nitrogen gas is introduced as a protective gas;

[0186] The closed container containing the gold alloy is subjected to annealing treatment, the annealing temperature is 570°C, and the annealing time is 7h, to obtain a gold alloy with enhanced corrosion resistance.

[0187] Example 29

[0188] A heat treatment method for generating an ultra-thin corrosion-resistant oxide layer on the surface of a gold alloy, comprising the following steps:

[0189] A gold alloy with a mass percentage of 50% gold is loaded into a closed container, the interior of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 30 Pa, and nitrogen gas is introduced as a protective gas;

[0190] The closed container containing the gold alloy is subjected to annealing treatment, the annealing temperature is 560°C, and the annealing time is 4h, to obtain a gold alloy with enhanced corrosion resistance.

[0191] Example 30

[0192] A heat treatment method for generating an ultra-thin corrosion-resistant oxide layer on the surface of a gold alloy, comprising the following steps:

[0193] A gold alloy with a mass percentage of 55% gold is loaded into a closed container, the interior of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 25 Pa, and nitrogen gas is introduced as a protective gas;

[0194] The closed container containing the gold alloy is subjected to annealing treatment, the annealing temperature is 570°C, and the annealing time is 5h, to obtain a gold alloy with enhanced corrosion resistance.

[0195] Example 31

[0196] A heat treatment method for generating an ultra-thin corrosion-resistant oxide layer on the surface of a gold alloy, comprising the following steps:

[0197] A gold alloy with a mass percentage of 60% gold is loaded into a closed container, the interior of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 35 Pa, and nitrogen gas is introduced as a protective gas;

[0198] The closed container containing the gold alloy is subjected to annealing treatment, the annealing temperature is 550°C, and the annealing time is 5h, to obtain a gold alloy with enhanced corrosion resistance.

[0199] Example 32

[0200] A heat treatment method for forming an ultra-thin corrosion-resistant oxide layer on the surface of a gold alloy, comprising the following steps:

[0201] A gold alloy with a mass percentage of 55% gold is placed in a closed container, the interior of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 200 Pa, and nitrogen gas is introduced as a protective gas;

[0202] The closed container containing the gold alloy is subjected to annealing treatment, the annealing temperature is 560℃, and the annealing time is 5h, to obtain a gold alloy with enhanced corrosion resistance.

[0203] Example 33

[0204] A heat treatment method for forming an ultra-thin corrosion-resistant oxide layer on the surface of a gold alloy, comprising the following steps:

[0205] A gold alloy with a mass percentage of 65% gold is placed in a closed container, the interior of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 300 Pa, and nitrogen gas is introduced as a protective gas;

[0206] The closed container containing the gold alloy is subjected to annealing treatment, the annealing temperature is 570℃, and the annealing time is 4h, to obtain a gold alloy with enhanced corrosion resistance.

[0207] Example 34

[0208] A heat treatment method for forming an ultra-thin corrosion-resistant oxide layer on the surface of a gold alloy, comprising the following steps:

[0209] A gold alloy with a mass percentage of 65% gold is placed in a closed container, the interior of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 350 Pa, and nitrogen gas is introduced as a protective gas;

[0210] The closed container containing the gold alloy is subjected to annealing treatment, the annealing temperature is 555℃, and the annealing time is 5h, to obtain a gold alloy with enhanced corrosion resistance.

[0211] Example 35

[0212] A heat treatment method for forming an ultra-thin corrosion-resistant oxide layer on the surface of a gold alloy, comprising the following steps:

[0213] A gold alloy with a mass percentage of 60% gold is placed in a closed container, the interior of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 400 Pa, and nitrogen gas is introduced as a protective gas;

[0214] The closed container containing the gold alloy is annealed at a temperature of 580 DEG C for 6 hours to obtain a gold alloy with enhanced corrosion resistance.

[0215] Example 36

[0216] A heat treatment method for forming a super-thin corrosion-resistant oxide layer on the surface of a gold alloy includes the following steps:

[0217] A gold alloy with a mass percentage of 55% gold is placed in a closed container, the interior of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 500 Pa, and nitrogen gas is introduced as a protective gas;

[0218] The closed container containing the gold alloy is annealed at a temperature of 590 DEG C for 7 hours to obtain a gold alloy with enhanced corrosion resistance.

[0219] Example 37

[0220] A heat treatment method for forming a super-thin corrosion-resistant oxide layer on the surface of a gold alloy includes the following steps:

[0221] A gold alloy with a mass percentage of 65% gold is placed in a closed container, the interior of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 455 Pa, and nitrogen gas is introduced as a protective gas;

[0222] The closed container containing the gold alloy is annealed at a temperature of 600 DEG C for 3 hours to obtain a gold alloy with enhanced corrosion resistance.

[0223] Example 38

[0224] A heat treatment method for forming a super-thin corrosion-resistant oxide layer on the surface of a gold alloy includes the following steps:

[0225] A gold alloy with a mass percentage of 50% gold is placed in a closed container, the interior of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 23 Pa, and nitrogen gas is introduced as a protective gas;

[0226] The closed container containing the gold alloy is annealed at a temperature of 595 DEG C for 6 hours to obtain a gold alloy with enhanced corrosion resistance.

[0227] Example 39

[0228] A heat treatment method for forming a super-thin corrosion-resistant oxide layer on the surface of a gold alloy includes the following steps:

[0229] A gold alloy with a mass percentage of gold of 40% is loaded into a closed container, the inside of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 35 Pa, and nitrogen gas is introduced as a protective gas;

[0230] The closed container containing the gold alloy is annealed at a temperature of 575 °C for 6 h to obtain a gold alloy with enhanced corrosion resistance.

[0231] Example 40

[0232] A heat treatment method for generating an ultra-thin corrosion-resistant oxide layer on the surface of a titanium-gold alloy, comprising the following steps:

[0233] A titanium-gold alloy with a mass percentage of gold of 45% is loaded into a closed container, the inside of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 27 Pa, and nitrogen gas is introduced as a protective gas;

[0234] The closed container containing the titanium-gold alloy is annealed at a temperature of 535 °C for 5.5 h to obtain a titanium-gold alloy with enhanced corrosion resistance.

[0235] Example 41

[0236] A heat treatment method for generating an ultra-thin corrosion-resistant oxide layer on the surface of a titanium-gold alloy, comprising the following steps:

[0237] A titanium-gold alloy with a mass percentage of gold of 48% is loaded into a closed container, the inside of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 38 Pa, and nitrogen gas is introduced as a protective gas;

[0238] The closed container containing the titanium-gold alloy is annealed at a temperature of 575 °C for 4.5 h to obtain a titanium-gold alloy with enhanced corrosion resistance.

[0239] Example 42

[0240] A heat treatment method for generating an ultra-thin corrosion-resistant oxide layer on the surface of a titanium-gold alloy, comprising the following steps:

[0241] A titanium-gold alloy with a mass percentage of gold of 53% is loaded into a closed container, the inside of the closed container is repeatedly washed with inert gas to make the oxygen partial pressure in the closed container 42 Pa, and nitrogen gas is introduced as a protective gas;

[0242] The closed container containing the titanium-gold alloy is annealed at a temperature of 580 °C for 6.5 h to obtain a titanium-gold alloy with enhanced corrosion resistance.

[0243] The above merely provides the preferred embodiments of the present application, and is not used to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modifications, equivalent replacements, improvements, etc. made within the principles and technical scope of the present application shall fall into the scope of the present application.

Claims

1. A heat treatment method for forming an ultrathin corrosion-resistant oxide layer on the surface of an Au alloy, characterized in that: Includes the following steps: The gold alloy is placed in a sealed container, and the inside of the sealed container is repeatedly purged with inert gas to make the oxygen partial pressure inside the sealed container 20-450 Pa. Inert gas is then introduced as a protective gas. The sealed container containing the gold alloy is annealed at a temperature of 500-600℃ for 3-10 hours. In the gold alloy, elements other than gold can form a dense oxide layer and can form a single-phase intermetallic compound with Au; The other elements in the gold alloy are Al or Ti.

2. The heat treatment method for forming an ultrathin corrosion-resistant oxide layer on the surface of Au alloy according to claim 1, characterized in that: In the gold alloy, the gold content is greater than 30%, where % is a mass percentage.

3. The heat treatment method for forming an ultrathin corrosion-resistant oxide layer on the surface of Au alloy according to claim 1, characterized in that: The inert gas is nitrogen or argon.

4. The heat treatment method for forming an ultrathin corrosion-resistant oxide layer on the surface of an Au alloy according to claim 3, characterized in that: An inert gas is introduced as a protective gas to make the pressure in the closed container equal to or lower than atmospheric pressure.

5. The heat treatment method for forming an ultrathin corrosion-resistant oxide layer on the surface of an Au alloy according to claim 1, characterized in that: The sealed container is a quartz tube.

6. The heat treatment method for forming an ultrathin corrosion-resistant oxide layer on the surface of an Au alloy according to claim 1, characterized in that: The annealing temperature is 550-600℃, and the annealing time is 3-8 hours.

7. The heat treatment method for forming an ultrathin corrosion-resistant oxide layer on the surface of an Au alloy according to claim 1, characterized in that: When the gold alloy is an Al2Au alloy, the annealing temperature is 540-560℃ and the annealing time is 4-6h.

8. The heat treatment method for forming an ultrathin corrosion-resistant oxide layer on the surface of an Au alloy according to claim 1, characterized in that: The oxygen partial pressure during annealing is below 200 Pa.

9. The heat treatment method for forming an ultrathin corrosion-resistant oxide layer on the surface of an Au alloy according to claim 8, characterized in that: The oxygen partial pressure during annealing is below 150 Pa.

10. The heat treatment method for forming an ultrathin corrosion-resistant oxide layer on the surface of an Au alloy according to claim 9, characterized in that: The oxygen partial pressure during annealing is less than 100 Pa.

11. The heat treatment method for forming an ultrathin corrosion-resistant oxide layer on the surface of an Au alloy according to claim 10, characterized in that: The oxygen partial pressure during annealing is below 40 Pa.

12. The heat treatment method for forming an ultrathin corrosion-resistant oxide layer on the surface of an Au alloy according to claim 11, characterized in that: The oxygen partial pressure during annealing is 20-30 Pa.

13. A corrosion-resistant Au alloy, prepared by any one of the heat treatment methods described in claims 1-12.

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