Large-size antioxidative amorphous alloy ribbon, and preparation method and application thereof

Abstract

The application relates to the field of non-gold alloys, and discloses a large-size oxidation-resistant amorphous alloy ribbon as well as a preparation method and application thereof. The large-size oxidation-resistant amorphous alloy ribbon comprises P 5-8%, Sn 4-16%, Ni 4-14%, Ge 0.05-0.15%, Mo 0.01-0.03%, R 0.05-0.1% and Cu in a residual amount, wherein R is one or more of Sc, Er and Y. The amorphous alloy ribbon has excellent amorphous forming capability under a larger width size, is high in toughness and oxidation resistance, and is excellent in brazing performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of amorphous alloys, in particular to a large-size oxidation-resistant amorphous alloy ribbon and a preparation method and application thereof. BACKGROUND

[0002] Amorphous alloy is a kind of disordered metastable material formed by rapidly cooling high-temperature alloy melt to room temperature, which has excellent properties such as high strength, toughness, corrosion resistance and high elastic limit. At present, one of the main industrial production processes of amorphous alloy ribbon is single-roll ribbon casting. The amorphous ribbon prepared by this method has good formability, good toughness and uniform composition, which can effectively solve the problem of difficult forming of traditional alloy strips.

[0003] In recent years, silver-free solder Cu-P-Sn has made considerable progress in replacing silver-based solder due to its low melting point, good self-soldering property, low price and high strength of soldered joints. However, due to the existence of brittle compound Cu3P in silver-free solder Cu-P-Sn, the alloy is brittle at room temperature, which not only makes it difficult to produce large-size (width ≥ 30 mm) thin strips, but also greatly reduces the processing performance of the strip in the later stage and the joint strength after soldering.

[0004] Studies have shown that the amorphous forming ability of Cu-P-Ni-Sn quaternary system (for example CN105033500A) is higher than that of Cu-P-Ni ternary system, while Cu-P binary alloy has almost no amorphous forming ability. The composition ratio of each element in copper alloy directly affects the forming ability of amorphous ribbon. In addition, since the single-roll ribbon casting production of copper-based amorphous ribbon is carried out in the whole process under atmospheric environment, copper alloy strip will inevitably be oxidized during the forming process. If the strip is exposed to air for a long time during the later storage and transportation, the oxidation of the strip will be further intensified, thereby affecting the soldering performance.

[0005] Therefore, it is urgent to develop a new copper-based amorphous alloy ribbon which has large-size (width ≥ 30 mm) amorphous forming ability and also has good toughness and oxidation resistance. SUMMARY

[0006] In order to solve the above technical problems, the present application provides a large-size oxidation-resistant amorphous alloy ribbon and a preparation method and application thereof. The amorphous alloy ribbon of the present application still has excellent amorphous forming ability at a larger width size, and also has high toughness and high oxidation resistance, thereby having excellent soldering performance.

[0007] The specific technical scheme of the present application is as follows:

[0008] In a first aspect, the present application provides a large-size antioxidative amorphous alloy ribbon, which comprises the following elements in mass percentage: P 5-8%, Sn 4-16%, Ni 4-14%, Ge 0.02-0.3%, Mo 0.01-0.04%, R 0.05-0.1%, Cu balance, wherein R is one or more of Sc, Er and Y.

[0009] The present application dopes other elements on the basis of the Cu-P-Ni-Sn quaternary system. Among them: (1) adding trace element Ge is conducive to improving the surface activity of the material, thereby improving the brazing wettability of the brazing filler metal; (2) adding trace element Mo, Mo as a high-melting-point transition metal, can form interstitial solid solution to improve the strength and hardness of the brazing filler metal, and can also form a composite oxide layer with R elements to improve the oxidation resistance of the system; (3) appropriate Sc, Er and Y elements have significant atomic size difference with the base Cu element, which can increase the atomic stacking disorder during rapid solidification, thereby improving the amorphous forming ability; Furthermore, Sc, Er and Y elements can form pinning points for shear band extension in amorphous, promoting the bifurcation of single main shear band into multiple micro shear bands, dispersing local stress concentration, thereby improving the toughness of the material; In addition, Sc, Er and Y elements have a very high affinity for oxygen, which preferentially diffuses to the surface of the melt in a high-temperature environment to form a dense oxide layer, which can effectively hinder the diffusion of oxygen atoms into the interior of the substrate, thereby improving the oxidation resistance of the material.

[0010] Further, the content of each of the above-mentioned doping elements is also crucial, for example: the present application finds that when the content of Ge is less than 0.02%, the improvement of the brazing wettability is not significant, and when the content is higher than 0.3%, it is easy to induce metastable phase precipitation; when the content of Mo exceeds 0.04%, it will cause the viscosity of the melt to abnormally increase, increasing the difficulty of preparing amorphous ribbons by the ribbon casting process; and excessive R elements are easy to segregate at the grain boundaries and combine with the base Cu to form some brittle phases, which will damage the mechanical properties of the ribbon. Finally, the content of the above-mentioned elements in the present application is strictly controlled within the above-mentioned range.

[0011] As a preferred, the amorphous alloy ribbon comprises the following elements in mass percentage: P 6-8%, Sn 4-16%, Ni 4-14%, Ge 0.05-0.15%, Mo 0.01-0.03%, R 0.05-0.1%, Cu balance, wherein R is one or more of Sc, Er and Y.

[0012] As a preferred, the width of the amorphous alloy ribbon is ≥30 mm.

[0013] In a second aspect, the present application provides a preparation method of an amorphous alloy ribbon, which comprises the following steps:

[0014] S1: mix and melt the raw materials to obtain high-purity and uniform alloy ingot.

[0015] S2: re-melt the alloy ingot, spray it through a nozzle onto a rotating copper roller, and obtain large-size strip after cooling.

[0016] S3: heat treat the strip under a protective gas to obtain amorphous alloy ribbon. After heat treatment, the amorphous alloy ribbon can maintain excellent toughness while also improving certain strength.

[0017] S4: acid wash the amorphous alloy ribbon. After acid washing pretreatment, the surface reactivity of the amorphous alloy ribbon can be activated, and the adhesion of the passivation film in S5 passivation treatment can be enhanced.

[0018] S5: passivate the amorphous alloy ribbon. Passivation treatment can make the copper-based amorphous alloy ribbon have high oxidation resistance, and it can remain clean and bright even after long-term exposure to air.

[0019] Preferably, in S2, the re-melting temperature is 680-750 ℃, and the holding time is 5-10 min.

[0020] Preferably, in S2, the length of the slit of the nozzle is 30-50 mm (the width of the amorphous alloy ribbon is equivalent to the length of the nozzle slit), and the width is 0.5-1 mm.

[0021] Preferably, in S2, the diameter of the copper roller is 0.6-0.8 m, and the rotating speed of the copper roller is 25-35 m / s (linear speed).

[0022] The present application finds that the rotating speed of the copper roller also has a relatively important influence on the performance of the material. If the rotating speed is too low, the cooling rate of the melt after contacting the copper roller is insufficient, the spun strip is severely crystallized, and it is almost brittle and breaks upon impact; and if the rotating speed is too high, the melt does not spread sufficiently after contacting the copper roller, resulting in a very thin strip with too many holes and substandard quality.

[0023] Preferably, in S3, the heat treatment is: heating to 120-160 ℃ at a heating rate of 3-5 ℃ / min, holding for 20-40 min; then heating to 200-230 ℃ at a heating rate of 3-5 ℃ / min, holding for 40-80 min, and cooling with the furnace.

[0024] In order to further improve the performance of the material, the heat treatment is designed into two stages: the first stage (120~160 ℃) is slow heating, which is mainly to promote structural relaxation and eliminate the internal stress of the quenched amorphous strip, because the temperature is lower than the glass transition temperature (Tg) of the amorphous alloy; the second stage (200-230 ℃) is close to or slightly higher than the initial crystallization temperature (Tx) of the amorphous alloy, and the crystallization process can be controlled by slow heating in stages, so that the rapid growth of the crystal grains is inhibited, and the fine (<50 nm) and dispersed nanocrystalline phase is formed, which is embedded in the amorphous matrix to improve the toughness-strength synergy: the amorphous matrix maintains the toughness, and the nanocrystalline phase provides the strength (Hall-Petch effect). If only one step of heat treatment is performed, the crystallization of the amorphous strip is not controlled, and the crystal grains may grow rapidly, which destroys the toughness of the strip.

[0025] Preferably, in S3, the protective gas is helium, nitrogen or argon.

[0026] Preferably, in S4, the pickling uses dilute hydrochloric acid, dilute sulfuric acid or dilute nitric acid; the concentration of the acid is 10-20wt%, and the pickling time is 10-20 s.

[0027] Preferably, in S5, the passivation agent used in the passivation is a chromium-free and environmentally friendly passivation agent, which includes benzotriazole as a corrosion inhibitor, a complexing agent, a surface active agent and a solvent. The mass fraction of benzotriazole in the total system is 0.3-1.5%; the mass of the complexing agent is 3-5 times that of benzotriazole; and the mass fraction of the surface active agent in the complexing agent is 40-60%.

[0028] It is found that the content of each component in the passivation agent is important to the passivation effect. First, the mass of the complexing agent needs to be controlled to be 3-5 times that of benzotriazole, because the complexing agent in this proportion can not only ensure the complexation of free metal ions but also will not destroy the corrosion inhibition effect of benzotriazole (excessive complexing agent will compete with benzotriazole for the active sites of the metal, resulting in a decrease in the coverage rate of the passivation film); second, the mass of the surface active agent accounts for 40-60% of the mass of the complexing agent, because the surface active agent in this proportion can not only play the role of dispersion, wetting and enhancement of the adhesion of the passivation film, but also will not affect the stability of the system and the passivation film due to excessive amount (excessive surface active agent will block the contact between the benzotriazole molecules and the surface of the strip, which will destroy the integrity of the passivation film); in addition, the mass fraction of benzotriazole in the total system is 0.3-1.5%, because the corrosion inhibitor in this proportion can play the best anti-oxidation effect.

[0029] Preferably, in S5, the complexing agent includes at least one of phytic acid, citric acid and tartaric acid.

[0030] Preferably, in S5, the surface active agent includes at least one of oil-based hydroxyethyl imidazoline, butyne diol and triethanolamine.

[0031] Preferably, in S5, the solvent comprises at least one of water and ethanol.

[0032] Preferably, in S5, the time of the passivation treatment is 5-20 min.

[0033] In a third aspect, the application provides a use of the large-size antioxidative amorphous alloy ribbon in preparing silver-free brazing filler.

[0034] Compared with the prior art, the application has the following beneficial effects:

[0035] (1) The application dopes other elements on the basis of the Cu-P-Ni-Sn quaternary system. Among them: Ge is conducive to improving the wettability of the brazing filler; Mo can form an interstitial solid solution to improve the strength and hardness of the brazing filler, and can also form a composite oxide layer with R elements to improve the oxidation resistance of the system; Sc, Er and Y elements can improve the amorphous forming ability and improve the toughness of the material. In addition, Sc, Er and Y elements can combine with oxygen and preferentially diffuse to the surface of the melt in a high-temperature environment, forming a dense oxide layer that can effectively hinder the diffusion of oxygen atoms into the interior of the substrate, thereby improving the oxidation resistance of the material.

[0036] (2) The amorphous alloy ribbon prepared by the single-roller spinning method in the application maintains excellent toughness while improving certain strength after heat treatment. At the same time, the pickling and passivation treatment makes the copper-based amorphous alloy ribbon have high oxidation resistance, and it remains clean and bright even after being exposed to air for a long time.

[0037] (3) The large-size amorphous ribbon of the application applied in the brazing field has good toughness and can be arbitrarily cut and processed without breaking, and is suitable for different welding conditions while maintaining excellent wettability and joint strength. BRIEF DESCRIPTION OF DRAWINGS

[0038] Figure 1 The comparison chart of the samples of Example 1 and Comparative Example 3 after being placed in air for one month;

[0039] Figure 2 The final shape of the amorphous alloy sample in each embodiment of the application is shown in the schematic diagram.

[0040] Figure 3 The schematic diagram of the flat plate bending experiment device. DETAILED DESCRIPTION

[0041] The embodiments of the present application, the technical effects produced, will be clearly and detailed described below in conjunction with the embodiments. Obviously, the described embodiments are only part of the embodiments of the present application, not all embodiments, based on the embodiments of the present application, other embodiments obtained by those skilled in the art without creative labor, all belong to the scope of protection of the present application, the following examples are only used to illustrate the present application, and should not be regarded as limiting the scope of the present application.

[0042] Total examples

[0043] In a first aspect, a large-size oxidation-resistant amorphous alloy ribbon comprises the following elements by mass percentage: P 5-8%, Sn 4-16%, Ni 4-14%, Ge 0.02-0.3%, Mo 0.01-0.04%, R 0.05-0.1%, Cu balance, wherein R is one or more of Sc, Er and Y.

[0044] Preferably, the amorphous alloy ribbon comprises the following elements by mass percentage: P 6-8%, Sn 4-16%, Ni 4-14%, Ge 0.05-0.15%, Mo 0.01-0.03%, R 0.05-0.1%, Cu balance, wherein R is one or more of Sc, Er and Y.

[0045] Preferably, the width of the amorphous alloy ribbon is ≥30 mm.

[0046] In a second aspect, a method for preparing an amorphous alloy ribbon comprises the following steps:

[0047] S1: mixing and melting each raw material to obtain a high-purity, uniform alloy ingot.

[0048] In some preferred embodiments, in S1, the melting uses one or more of a vacuum induction furnace, a vacuum arc furnace, and a vacuum floating melting furnace.

[0049] S2: remelting the alloy ingot and spraying it through a nozzle onto a rotating copper roller to obtain a large-size ribbon after cooling.

[0050] In some preferred embodiments, in S2, the remelting temperature is 680-750 ℃, and the holding time is 5-10 min.

[0051] In some preferred embodiments, in S2, the length of the gap of the nozzle is 30-50 mm (the width of the amorphous alloy ribbon is equivalent to the length of the nozzle gap), and the width is 0.5-1 mm; the diameter of the copper roller is 0.6-0.8 m, and the rotating speed of the copper roller is 25-35 m / s.

[0052] S3: heat-treating the ribbon under protective gas to obtain amorphous alloy ribbon.

[0053] In some preferred embodiments, in S3, the heat-treating is: heating to 120-160 ℃ at a heating rate of 3-5 ℃ / min, holding for 20-40 min; then heating to 200-230 ℃ at a heating rate of 3-5 ℃ / min, holding for 40-80 min, and cooling with the furnace.

[0054] In some preferred embodiments, in S3, the protective gas is helium, nitrogen or argon.

[0055] S4: pickling the amorphous alloy ribbon.

[0056] In some preferred embodiments, in S4, the pickling uses dilute hydrochloric acid, dilute sulfuric acid or dilute nitric acid; the concentration of the acid is 10-20 wt%, and the pickling time is 10-20 s.

[0057] S5: passivating the amorphous alloy ribbon.

[0058] In some preferred embodiments, in S5, the passivation uses a chromium-free environmentally friendly passivation agent, which includes: benzotriazole as a corrosion inhibitor, a complexing agent, a surface active agent and a solvent. The benzotriazole accounts for 0.3-1.5% of the total mass; the mass of the complexing agent is 3-5 times that of the benzotriazole; and the mass of the surface active agent accounts for 40-60% of the mass of the complexing agent.

[0059] In some more preferred embodiments, in S5, the complexing agent includes at least one of phytic acid, citric acid and tartaric acid.

[0060] In some more preferred embodiments, in S5, the surface active agent includes at least one of oil-based hydroxyethyl imidazoline, butyne diol and triethanolamine.

[0061] In some more preferred embodiments, in S5, the solvent includes at least one of water and ethanol.

[0062] In some preferred embodiments, in S5, the passivation time is 5-20 min.

[0063] S6: winding and collecting the amorphous alloy ribbon, and further processing and cutting into a desired shape.

[0064] In some preferred embodiments, in S6, winding is performed using a full-automatic ribbon winding machine.

[0065] In some preferred embodiments, in S6, cutting is performed using a punching machine, and a customized mold is selected according to the preset shape to punch the ribbon into an amorphous sheet of the preset shape.

[0066] In some preferred embodiments, in S6, the preset shape includes any different size of a circle, a circular ring, a rectangle, a rectangular ring, and other conventional and unconventional shapes.

[0067] In a third aspect, the application provides a use of the large-size oxidation-resistant amorphous alloy ribbon in preparing a silver-free solder.

[0068] Specific embodiments and comparative examples

[0069] Table 1: Raw material ratio of each example

[0070]

[0071] Table 2: Specific process parameters of step S2 in each example

[0072]

[0073] Example 1

[0074] S1: According to the composition ratio of the raw materials in Example 1 in Table 1, a vacuum induction melting furnace was used for melting to obtain a high-purity and uniform alloy ingot.

[0075] S2: The alloy ingot obtained in S1 was remelted and sprayed through a customized nozzle onto a rotating copper roller to rapidly cool to obtain a large-size ribbon. The specific process parameters of this step are recorded in Table 2.

[0076] S3: The product obtained in S2 was annealed under nitrogen at a heating rate of 3 ℃ / min to 120 ℃, and then kept for 40 min. The temperature was further increased to 200 ℃ at a heating rate of 3 ℃ / min, and then kept for 80 min. The amorphous alloy ribbon was obtained by furnace cooling.

[0077] S4: The amorphous alloy ribbon obtained in S3 was pickled with 10% dilute nitric acid for 10 s to obtain the amorphous alloy ribbon.

[0078] S5: 0.3% benzotriazole, 1.5% complexing agent (tartaric acid + citric acid, 1:1 ratio), 0.6% surfactant (triethanolamine), and the rest of ethanol were thoroughly mixed to prepare a 1L passivation solution. The amorphous alloy ribbon obtained in S4 was passivated for 5 min.

[0079] S6: A full-automatic ribbon winding machine was used to automatically wind and collect the large-size oxidation-resistant amorphous alloy ribbon obtained in S5, and a circular ring die was further selected to punch and cut the ribbon into a circular ring shape to obtain an amorphous welding ring (as shown in Figure 2 ).

[0080] Example 2

[0081] S1: The components of each raw material were proportioned according to Example 2 in Table 1, and a vacuum induction melting furnace was used for melting to obtain high-purity and uniform alloy ingots.

[0082] S2: The alloy ingots obtained in S1 were remelted and sprayed through a customized nozzle onto a rotating copper roller to rapidly cool to obtain large-size strips, and the specific process parameters of this step are recorded in Table 2.

[0083] S3: The product obtained in S2 was annealed and heat-treated under nitrogen, heated to 130°C at a heating rate of 3°C / min, kept for 30 min, and then heated to 210°C at a heating rate of 3°C / min, kept for 70 min, and then cooled in the furnace to obtain amorphous alloy ribbons.

[0084] S4: The amorphous alloy ribbons of S3 were pickled with 15% dilute nitric acid for 15 s to obtain amorphous alloy ribbons.

[0085] S5: 0.5% benzotriazole, 2.0% complexing agent (phytic acid + tartaric acid, 1:1 ratio), 0.8% surfactant (oil-based hydroxyethyl imidazoline, butynediol, 2:1 ratio), and the balance of deionized water were thoroughly mixed to form a 1L passivation solution, and the amorphous alloy ribbons obtained in S4 were passivated for 10 min.

[0086] S6: The large-size oxidation-resistant amorphous alloy ribbons obtained in S5 were automatically wound and collected using a full-automatic ribbon winding machine, and further selected rectangular ring-shaped molds were used to punch and cut the ribbons into rectangular rings to obtain amorphous welding pieces (as shown in Figure 2 ).

[0087] Example 3

[0088] S1: The components of each raw material were proportioned according to Example 3 in Table 1, and a vacuum arc melting furnace was used for melting to obtain high-purity and uniform alloy ingots.

[0089] S2: The alloy ingots obtained in S1 were remelted and sprayed through a customized nozzle onto a rotating copper roller to rapidly cool to obtain large-size strips, and the specific process parameters of this step are recorded in Table 2.

[0090] S3: The product obtained in S2 was annealed and heat-treated under argon, heated to 140°C at a heating rate of 4°C / min, kept for 30 min, and then heated to 220°C at a heating rate of 4°C / min, kept for 60 min, and then cooled in the furnace to obtain amorphous alloy ribbons.

[0091] S4: The amorphous alloy ribbons of S3 were pickled with 15% dilute sulfuric acid for 15 s to obtain amorphous alloy ribbons.

[0092] S5: Take 0.8% benzotriazole, 4.0% complexing agent (phytic acid + tartaric acid + citric acid, 3:1:1 ratio), 2.0% surfactant (oil-based hydroxyethyl imidazoline, butynediol, 1:1 ratio), and the rest of the deionized water to mix thoroughly to make 1L of passivation solution. The amorphous alloy ribbon obtained in S4 is passivated for 10 minutes.

[0093] S6: Use a full-automatic ribbon winding machine to automatically wind and collect the large-size oxidation-resistant amorphous alloy ribbon obtained in S5, and further select a circular mold to punch and cut the ribbon into small circular pieces to obtain amorphous welding pieces (as shown in Figure 2 ).

[0094] Example 4

[0095] S1: According to Table 1, the components of each raw material are proportioned, and a vacuum arc melting furnace is used for melting to obtain high-purity and uniform alloy ingots.

[0096] S2: The alloy ingot obtained in S1 is remelted and sprayed through a customized nozzle onto a rotating copper roller to rapidly cool to obtain a large-size ribbon. The specific process parameters are recorded in Table 2.

[0097] S3: The product obtained in S2 is annealed under argon at a heating rate of 4 ℃ / min to 150 ℃, and then held for 30 min. The temperature is further increased to 220 ℃ at a heating rate of 4 ℃ / min, and then held for 50 min. The amorphous alloy ribbon is obtained by furnace cooling.

[0098] S4: The amorphous alloy ribbon obtained in S3 is pickled with 20% dilute sulfuric acid for 20 s to obtain an amorphous alloy ribbon.

[0099] S5: Take 1.0% benzotriazole, 3.0% complexing agent (phytic acid + tartaric acid + citric acid, 3:1:1 ratio), 1.8% surfactant (oil-based hydroxyethyl imidazoline, butynediol, triethanolamine, 2:2:1 ratio), and the rest of the deionized water to mix thoroughly to make 1L of passivation solution. The amorphous alloy ribbon obtained in S4 is passivated for 15 minutes.

[0100] S6: Use a full-automatic ribbon winding machine to automatically wind and collect the large-size oxidation-resistant amorphous alloy ribbon obtained in S5, and further select a circular mold to punch and cut the ribbon into a square ring to obtain an amorphous welding ring (as shown in Figure 2 ).

[0101] Example 5

[0102] S1: The ingredients of each raw material were proportioned according to Example 5 in Table 1, and a vacuum suspension melting furnace was used for melting to obtain high-purity and uniform alloy ingots.

[0103] S2: The alloy ingots obtained in S1 were remelted and sprayed through a customized nozzle onto a rotating copper roller to rapidly cool to obtain large-size strips, and the specific process parameters of this step are recorded in Table 2.

[0104] S3: The product obtained in S2 was annealed under helium, heated to 160°C at a rate of 5°C / min, kept for 20 min, and then heated to 230°C at a rate of 5°C / min, kept for 40 min, and then cooled in the furnace to obtain amorphous alloy ribbons.

[0105] S4: The amorphous alloy ribbons of S3 were pickled with 10% dilute hydrochloric acid for 10 s to obtain amorphous alloy ribbons.

[0106] S5: 1.5% benzotriazole, 4.5% complexing agent (phytic acid + tartaric acid + citric acid, 3:1:1 ratio), 1.8% surfactant (oil-based hydroxyethyl imidazoline, butynediol, triethanolamine, 2:2:1 ratio), and the balance of deionized water were thoroughly mixed to make 1L of passivation solution, and the amorphous alloy ribbons obtained in S4 were passivated for 20 min.

[0107] S6: The large-size oxidation-resistant amorphous alloy ribbons obtained in S5 were automatically wound and collected using a full-automatic ribbon winding machine, and further selected circular molds were used to punch and cut the ribbons into five-star pieces to obtain amorphous welding pieces.

[0108] Comparative Example 1 (without adding Ge and Mo elements)

[0109] Compared with Example 1, the raw material ratio in S1 step did not contain Ge and Mo elements, and the raw material ratio was: Cu 79.9%, P 6%, Sn 8%, Ni 6%, and Er 0.1%. The other preparation steps and parameters were the same.

[0110] Comparative Example 2 (adding Ge but not adding Mo elements)

[0111] Compared with Example 1, the raw material ratio in S1 step contained Ge but not Mo elements, and the raw material ratio was: Cu 79.85%, P 6%, Sn 8%, Ni 6%, Ge 0.05%, and Er 0.1%. The other preparation steps and parameters were the same.

[0112] Comparative Example 3 (without adding R elements)

[0113] Compared with Example 1, the raw material ratio in S1 step does not contain Er element, and the raw material ratio is: Cu 79.84%, P 6%, Sn 8%, Ni 6%, Ge 0.05%, Mo 0.01%. Other preparation steps and parameters are the same.

[0114] Comparative Example 4 (without heat treatment)

[0115] Compared with Example 1, the S3 step does not perform annealing heat treatment. Other preparation steps and parameters are the same.

[0116] Comparative Example 5 (one-step heat treatment)

[0117] Compared with Example 1, the S3 step heat treatment process is: heating to 220 ℃ at a heating rate of 3-5 ℃, and holding for 80 min. Other preparation steps and parameters are the same.

[0118] Comparative Example 6 (without passivation treatment)

[0119] Compared with Example 1, the S4 step does not perform passivation treatment after pickling. Other preparation steps and parameters are the same.

[0120] Comparative Example 7 (excessive complexing agent in passivation agent):

[0121] Compared with Example 1, the S5 step passivation agent composition ratio is: 0.3% benzotriazole, 2.0% complexing agent (tartaric acid + citric acid, 1:1 ratio), 1.0% surfactant (triethanolamine), and the rest is ethanol. Other preparation steps and parameters are the same.

[0122] Comparative Example 8 (excessive surfactant in passivation agent):

[0123] Compared with Example 1, the S5 step passivation agent composition ratio is: 0.3% benzotriazole, 1.5% complexing agent (tartaric acid + citric acid, 1:1 ratio), 1.5% surfactant (triethanolamine), and the rest is ethanol. Other preparation steps and parameters are the same.

[0124] Performance test

[0125] The performance of the amorphous alloy strip of each example and each comparative example was tested, and the test method was:

[0126] Strip toughness test: bend the strip into a u shape between two plates, slowly reduce the plate spacing at a constant rate (v=0.1 mm / s) until the strip breaks or is bent to 180°, record the distance D between the two plates when the breakage occurs, and calculate the corresponding breakage strain (as shown in Figure 3 ).

[0127] Belt oxidation resistance test: take each example and each comparative example of the strip sample placed in a 50 ℃ air oven for 2 h, and then placed in an 80 ℃ oven for 2 h, and then placed in air for 1 month to observe the color change of the strip surface. Color difference instrument (CIELab*) was used to quantify the color change, and the oxidation degree was characterized by yellowness (b value) and color difference (ΔE), wherein the greater the positive value of the yellowness b value, the more obvious the yellow tendency, and ΔE: total color difference (ΔE = √(ΔL² + Δa² + Δb*²), taking the sample after passivation in example 1 as the reference.

[0128] Belt brazing strength test: take each example and each comparative example of the strip sample and the base material for brazing, the brazing temperature is 700 ℃, the holding time is 10 min, use the tensile testing machine to apply tensile force to the tensile sample at room temperature at a speed of 10 −4 m / s, after breaking, the breaking force is divided by the actual use area, and the average value is taken to obtain the joint tensile strength.

[0129] Belt wettability test: accurately weigh and cut each example and each comparative example of the strip to ensure the same mass, square shape 6 mm × 6 mm of amorphous strip. Place the strip on the wetting sample surface, vacuum brazing with red copper at 700 ℃ for 5 min, the vacuum degree is 1 × 10 −3 Pa, the flow area is calculated in millimeter, and the results are shown in Table 3.

[0130] Table 3: test results of each example and each comparative example

[0131]

[0132] From the above table data comparison, it can be seen that:

[0133] From example 1 and comparative example 1, it can be seen that adding appropriate amount of Ge and Mo elements in the alloy composition formula can significantly improve the wettability of the material during brazing, and also helps to improve the joint strength. In comparative example 1, the absence of Ge and Mo elements reduces the alloy amorphous forming ability, and partial strip surface crystallization occurs during the strip preparation process, because the fracture strain and toughness decrease.

[0134] From example 1 and comparative example 2, it can be seen that adding appropriate amount of Ge elements and Mo elements in the alloy composition is more beneficial to improve the toughness and wettability of the material during brazing than adding only Ge elements without Mo elements, and also helps to improve the joint strength.

[0135] From example 1 and comparative example 3, it can be seen that adding appropriate amount of Er elements in the alloy composition formula is beneficial to improve the toughness and wettability of the material during brazing, and also helps to improve the joint strength.

[0136] From example 1 and comparative example 4, comparative example 5, it can be seen that comparative example 5 only uses one step of heat treatment, which can improve the joint strength of the strip during brazing to a certain extent, but has a negative impact on the toughness of the strip; example 1 further designs the heat treatment into two stages, which not only improves the joint strength of the strip during brazing, but also improves the toughness of the strip itself.

[0137] From example 1 and comparative example 6, it can be seen that after the passivation process of the strip, Figure 1 It can be seen by comparison that the passivation treatment can significantly improve the oxidation resistance of the strip, so that the strip can maintain a bright and clean surface when exposed to air for a long time.

[0138] From example 1 and comparative example 7, it can be seen that adding an excess of complexing agent in the passivation agent will destroy the corrosion inhibition effect of benzotriazole (BTA), because the excess of complexing agent will compete with benzotriazole for metal active sites, resulting in a decrease in the coverage of the passivation film.

[0139] From example 1 and comparative example 8, it can be seen that adding an excess of surfactant in the passivation agent will also affect the passivation effect, because the excess of surfactant blocks the contact between benzotriazole molecules and the surface of the strip, and destroys the integrity of the passivation film.

[0140] In summary, the preparation and post-treatment process of a large-size oxidation-resistant amorphous alloy strip provided by the present application is simple and convenient to operate, has good toughness and oxidation resistance, and has excellent wettability and joint strength when used as a brazing material.

[0141] The raw materials and equipment used in the present application are conventional raw materials and equipment in the art unless otherwise specified; the methods used in the present application are conventional methods in the art unless otherwise specified.

[0142] The above is only a preferred embodiment of the present application, and does not limit the present application in any way. Any simple modification, change and equivalent transformation of the above embodiment based on the technical essence of the present application still falls within the protection scope of the technical solution of the present application.

Claims

1. An antioxidant amorphous alloy thin strip, characterized in that... The elements include the following mass percentages: P 5-8%, Sn 4-16%, Ni 4-14%, Ge 0.02-0.3%, Mo 0.01-0.04%, R 0.05-0.1%, Cu balance, where R is one or more of Sc, Er and Y.

2. The amorphous alloy thin strip according to claim 1, characterized in that: The elements include the following mass percentages: P 6-8%, Sn 4-16%, Ni 4-14%, Ge 0.05-0.15%, Mo 0.01-0.03%, R 0.05-0.1%, Cu balance, where R is one or more of Sc, Er and Y.

3. The amorphous alloy thin strip according to claim 1 or 2, characterized in that: The width of the amorphous alloy strip is ≥30 mm.

4. A method for preparing an amorphous alloy thin strip according to any one of claims 1-3, characterized in that... include: S1: Mix and melt the raw materials to obtain an alloy ingot; S2: The alloy ingot is remelted and sprayed onto a rotating copper roller through a nozzle. After cooling, a strip is obtained. S3: Heat treatment under a protective gas to obtain amorphous alloy strips; S4: Pickling treatment; S5: Passivation treatment.

5. The preparation method according to claim 4, characterized in that: In S2, The remelting temperature is 680-750 ℃, and the holding time is 5-10 min; The nozzle slit has a length of 30-50 mm and a width of 0.5-1 mm; the copper roller has a diameter of 0.6-0.8 m and a rotational speed of 25-35 m / s.

6. The preparation method according to claim 4, characterized in that: In S3, the heat treatment is as follows: heating to 120-160 ℃ at a heating rate of 3-5 ℃ / min, holding at that temperature for 20-40 min; then heating to 200-230 ℃ at a heating rate of 3-5 ℃ / min, holding at that temperature for 40-80 min, and then cooling with the furnace.

7. The preparation method according to claim 4, characterized in that: In S5, the passivating agent used for passivation includes: benzotriazole, complexing agent, surfactant and solvent; Benzotriazole accounts for 0.3-1.5% of the total mass; the complexing agent accounts for 3-5 times the mass of benzotriazole; and the surfactant accounts for 40-60% of the mass of the complexing agent.

8. The preparation method according to claim 7, characterized in that: In S5, The complexing agent includes at least one of phytic acid, citric acid and tartaric acid; The surfactant includes at least one of oil-based hydroxyethyl imidazoline, butynediol, and triethanolamine; The solvent includes at least one of water and ethanol.

9. The preparation method according to claim 4, characterized in that: In S5, the passivation treatment time is 5-20 minutes.

10. The application of the antioxidant amorphous alloy thin strip according to any one of claims 1-3 or the antioxidant amorphous alloy thin strip obtained by the preparation method according to any one of claims 4-9 in the preparation of silver-free solder.

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