Method for rapidly preparing multi-element Cu-Mn-Ni-Si foil strip brazing filler metal

Abstract

The invention belongs to the technical field of brazing material preparation, and particularly relates to a method for rapidly preparing multi-element Cu-Mn-Ni-Si foil strip brazing filler metal. The preparation method comprises the following steps: smelting and casting preparation raw materials of the multi-element Cu-Mn-Ni-Si series brazing filler metal to obtain a cast ingot; the upper surface and the lower surface of the cast ingot are cut layer by layer in the direction perpendicular to the thickness direction of the cast ingot, the loose cast ingot center part with thick dendritic crystals is abandoned, and a plurality of block ingots are obtained; and the block ingot is subjected to small deformation rolling and annealing, and the multi-element Cu-Mn-Ni-Si series foil strip brazing filler metal is obtained. The method provided by the invention is simple in process operation and high in efficiency, various types of multi-element Cu-Mn-Ni series foil strip brazing filler metal can be prepared, the obtained brazing filler metal is good in cleanliness, and the rapid production requirements and quality indexes of diversified brazing filler metal can be met.

Description

Technical Field

[0001] The invention belongs to the technical field of brazing material preparation, and in particular relates to a method for rapidly preparing multi-element Cu-Mn-Ni-Si foil strip brazing material. Background Art

[0002] Multi-component Cu-Mn-Ni-Si brazing filler metals have good fluidity, wettability, thermal strength, corrosion resistance and excellent weld mechanical properties. They can be used for brazing of carbon steel, copper alloys, stainless steel and high-temperature alloys, and are widely used in the chemical industry, aerospace and other fields.

[0003] At present, multi-component Cu-Mn-Ni-Si solder is usually used in the form of wire, foil or powder, among which foil is more commonly used, while wire and powder are less commonly used. However, the addition of Si (especially Si mass percentage higher than 1%), B, P and other alloying elements in multi-component Cu-Mn-Ni-Si foil solder improves the welding performance of multi-component Cu-Mn-Ni-Si solder, while significantly reducing the plasticity of the solder; at the same time, the solder is easily affected by temperature to form a brittle phase, which will further reduce the plasticity of the solder, resulting in poor processing performance of the solder, and ultimately leading to a long time-consuming and low production efficiency of multi-component Cu-Mn-Ni-Si foil solder, and it is impossible to achieve rapid preparation. Summary of the invention

[0004] The object of the present invention is to provide a method for rapidly preparing a multi-component Cu-Mn-Ni-Si foil strip solder. The method provided by the present invention solves the problems of long time consumption and low production efficiency of the existing process, has the advantages of high efficiency and simple process operation, and can realize the rapid preparation of a multi-component Cu-Mn-Ni-Si foil strip solder.

[0005] In order to achieve the above object, the present invention provides the following technical solutions:

[0006] The present invention provides a method for rapidly preparing a multi-element Cu-Mn-Ni-Si foil solder, comprising the following steps:

[0007] The raw materials for preparing the multi-component Cu-Mn-Ni-Si brazing alloy are melted and cast to obtain an ingot;

[0008] Cutting the ingot layer by layer from the upper and lower surfaces of the ingot in a direction perpendicular to the thickness of the ingot, discarding the central part of the ingot, and obtaining a plurality of ingot blocks;

[0009] The ingot is subjected to first small deformation rolling and first annealing, wherein the first small deformation rolling and the first annealing are performed cyclically, a single roll gap reduction of the first small deformation rolling is ≤0.15 mm, and a cumulative deformation between two adjacent first anneals is ≤20%, to obtain an initial brazing material;

[0010] The initial solder is subjected to a second small deformation rolling and a second annealing, the second small deformation rolling and the second annealing are cyclically performed, the single roll gap reduction of the second small deformation rolling is ≤0.15mm, and the cumulative deformation between two adjacent second annealings is ≥60%, until the multi-component Cu-Mn-Ni-Si foil solder is obtained.

[0011] Preferably, the thickness of the ingot is 20-30 mm; the width of the ingot is 80-120 mm, and the length is 150-200 mm.

[0012] Preferably, the thickness of the ingot is 2-3 mm; the thickness difference between the upper and lower rolling surfaces of the ingot is ≤0.3 mm;

[0013] The thickness of the central part of the ingot is 0.4 to 0.5 times the thickness of the ingot.

[0014] Preferably, the first small deformation rolling is performed along the length direction of the ingot, the rolling rate is ≤40 mm / s, the single roll gap reduction is 0.05-0.15 mm; and the cumulative deformation between two adjacent first annealings is 15-20%.

[0015] Preferably, the first annealing is performed in an air atmosphere, the temperature of the first annealing is 0.88 to 0.9 times the solidus temperature, the holding time is 5 to 8 minutes, and the cooling method is water cooling.

[0016] Preferably, the thickness of the initial solder is 1.2-1.5 mm.

[0017] Preferably, the second small deformation rolling is performed along the length direction of the initial solder, the rolling rate is ≤40 mm / s, the single roll gap reduction is 0.05-0.15 mm; and the cumulative deformation between two adjacent second annealings is 60-80%.

[0018] Preferably, the second annealing is vacuum annealing, the vacuum degree of the second annealing is ≤10Pa, the temperature is 0.85 to 0.88 times the solidus temperature, the holding time is 8 to 20min, the cooling method is rapid cooling to room temperature, and the rapid cooling rate is ≥30°C / min.

[0019] Preferably, the thickness of the multi-component Cu-Mn-Ni-Si foil solder is 0.05-0.12 mm.

[0020] Preferably, the multi-component Cu-Mn-Ni-Si foil solder includes Cu35NiMnSiCoFeBP, Cu40AgMnNiSiZnBP, CuAgMnNiSi or CuMnNiSi;

[0021] The mass percentage of Si element in the CuAgMnNiSi is 1-3%;

[0022] The mass percentage of Si element in the CuMnNiSi is 1-3%.

[0023] The invention provides a method for rapidly preparing a multi-element Cu-Mn-Ni-Si foil solder, comprising the following steps: smelting and casting raw materials for preparing the multi-element Cu-Mn-Ni-Si solder to obtain an ingot; cutting the ingot layer by layer along a thickness direction perpendicular to the ingot from the upper and lower surfaces, discarding the central part of the ingot, and obtaining a plurality of block ingots; performing first small deformation rolling and first annealing on the block ingot, wherein the first small deformation rolling and the first annealing are performed in a cycle, a single roll gap reduction amount of the first small deformation rolling is ≤0.15 mm, and a cumulative deformation amount between two adjacent first anneals is ≤20%, so as to obtain an initial solder; performing second small deformation rolling and second annealing on the initial solder, wherein the second small deformation rolling and the second annealing are performed in a cycle, a single roll gap reduction amount of the second small deformation rolling is ≤0.15 mm, and a cumulative deformation amount between two adjacent second anneals is ≥60%, until the multi-element Cu-Mn-Ni-Si foil solder is obtained. The present invention removes the loose structure and coarse dendrite part in the center of the ingot by a layer-by-layer slicing method, and obtains a plurality of ingots with dense and fine grain structure, which can not only improve the rolling processability of the solder, but also shorten the rolling time. Compared with the direct rolling ingot, the present invention can significantly improve the solder preparation efficiency. Moreover, the present invention improves the stress distribution of the rolling surface of the ingot by optimizing the single roll gap reduction of the first small deformation rolling to ≤0.15mm, avoids the large stress difference between different positions of the rolling surface and the rolling surface and the center of the ingot due to uneven deformation, and the cumulative deformation between two adjacent first anneals is ≤20%, which can effectively avoid the tearing phenomenon caused by excessive deformation of the ingot. The present invention optimizes the single roll gap reduction of the second small deformation rolling to ≤0.15mm, and the cumulative deformation between two adjacent second anneals is ≥60%. On the basis that the first small deformation rolling has achieved dense structure, crystal crushing or formed equiaxed crystals, the present invention increases the cumulative deformation between two adjacent second anneals, which can further shorten the processing time while ensuring the plasticity of the solder. In summary, compared with the spray forming and atomization methods in the prior art, the present invention has the advantages of simple operation, low cost and rapid preparation; at the same time, it can effectively solve the current problems of easy opening and tearing of multi-element Cu-Mn-Ni-Si foil solder during rolling and poor applicability of the solder state, and obtain products that meet the solder quality index requirements.

[0024] Furthermore, in the present invention, the first annealing is performed in an air atmosphere, the temperature of the first annealing is 0.88 to 0.9 times the solidus temperature, the holding time is 5 to 8 minutes, and the cooling method is water cooling. By optimizing the operating parameters of the first annealing, the present invention can suppress the generation of brittle phases in the ingot during the first annealing cooling process and ensure the plasticity of the ingot. At the same time, the first annealing does not need to be performed under vacuum conditions, but can be performed directly in an air atmosphere, which can also further shorten the preparation time and improve production efficiency.

[0025] Furthermore, in the present invention, the second annealing is vacuum annealing, the vacuum degree of the second annealing is ≤10Pa, the temperature is 0.85 to 0.88 times the solidus temperature, the holding time is 8 to 20 minutes, the cooling method is rapid cooling to room temperature, and the rapid cooling rate is ≥30°C / min. The present invention controls the second annealing to be vacuum annealing, and the purpose of vacuum annealing is to ensure the surface quality of the solder, without oxidation and other phenomena, and thus the cleanliness requirements of the solder can be met without surface treatment; the through hole of the present invention controls the rapid cooling rate, which can avoid the brittle phases such as Ni-Si generated during the slow cooling process, which deteriorates the processability of the solder. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 It is a schematic diagram of the process of the method of the present invention;

[0027] Figure 2 It is a schematic diagram of cutting the ingot layer by layer in the present invention. DETAILED DESCRIPTION

[0028] The present invention provides a method for rapidly preparing a multi-element Cu-Mn-Ni-Si foil solder, comprising the following steps:

[0029] The raw materials for preparing the multi-component Cu-Mn-Ni-Si brazing alloy are melted and cast to obtain an ingot;

[0030] Cutting the ingot layer by layer from the upper and lower surfaces of the ingot in a direction perpendicular to the thickness of the ingot, discarding the central part of the ingot, and obtaining a plurality of ingot blocks;

[0031] The ingot is subjected to first small deformation rolling and first annealing, wherein the first small deformation rolling and the first annealing are performed cyclically, a single roll gap reduction of the first small deformation rolling is ≤0.15 mm, and a cumulative deformation between two adjacent first anneals is ≤20%, to obtain an initial brazing material;

[0032] The initial solder is subjected to a second small deformation rolling and a second annealing, the second small deformation rolling and the second annealing are cyclically performed, the single roll gap reduction of the second small deformation rolling is ≤0.15mm, and the cumulative deformation between two adjacent second annealings is ≥60%, until the multi-component Cu-Mn-Ni-Si foil solder is obtained.

[0033] In the present invention, unless otherwise specified, all preparation raw materials / components are commercially available products well known to those skilled in the art.

[0034] The present invention melts and casts the raw materials for preparing the multi-component Cu-Mn-Ni-Si solder to obtain an ingot. In the present invention, the multi-component Cu-Mn-Ni-Si foil solder preferably includes Cu35NiMnSiCoFeBP, Cu40AgMnNiSiZnBP, CuAgMnNiSi or CuMnNiSi. The mass percentage of Si element in the CuAgMnNiSi is preferably 1-3%. The mass percentage of Si element in the CuMnNiSi is preferably 1-3%. In a specific embodiment of the present invention, the Cu35NiMnSiCoFeBP is preferably Cu34.3-Ni29-Mn29-Co5-Fe1.2-Si1.1-B0.2-P0.2 in terms of mass percentage. The Cu40AgMnNiSiZnBP is preferably Cu42-Ag23-Mn21.5-Ni11.5-Si0.3-Zn1.3-B0.2-P0.2 in terms of mass percentage. The CuMnNiSi is preferably Cu55-Mn37.5-Ni5-Si1.5 in terms of mass percentage.

[0035] In the present invention, the raw materials for preparing the multi-element Cu-Mn-Ni-Si solder preferably include single-element raw materials, or include single-element raw materials and intermediate alloy raw materials. In the present invention, the single-element raw materials preferably include at least four of Cu, Ni, Mn, Co, Fe and Si. The purity of the Cu single substance is preferably >99.9% or preferably electrolytic Cu. The purity of the Ni single substance is preferably >99.9% or preferably electrolytic Ni. The purity of the Mn single substance is preferably >99.9% or preferably electrolytic Mn. Therefore, the purity of the Co single substance is preferably >99.9% or preferably electrolytic Co. The Fe single substance is preferably industrial pure Fe. The purity of the Si single substance is preferably >99.9%. The intermediate alloy raw material preferably includes NiB intermediate alloy and / or CuP intermediate alloy.

[0036] In the present invention, the raw materials are preferably prepared according to the mass percentage of each element in the multi-element Cu-Mn-Ni-Si foil solder, and then the smelting is performed.

[0037] In the present invention, the smelting is preferably carried out in a vacuum medium frequency induction furnace. The present invention has no special requirements for the specific implementation process of the smelting. The mold used for casting is preferably a graphite mold. The present invention controls the ingot size and cooling rate through a graphite mold, improves the surface quality of the ingot, reduces the brittle phase of the ingot, excessive dendrite growth, etc., and the resulting ingot has a smooth surface and a uniform crystal structure, which is convenient for subsequent layer-by-layer cutting, rolling and annealing.

[0038] In the present invention, the thickness of the ingot is preferably 20 to 30 mm, and in the embodiment, it can be 30 mm or 20 mm. The width of the ingot is preferably 80 to 120 mm, and in the embodiment, it can be 80 mm, 90 mm or 88 mm. The length of the ingot is preferably 150 to 200 mm.

[0039] The invention ensures that the ingot quality meets the requirements of cutting by limiting the ingot size: the casting defects of the ingot are minimized, and the ingot surface grains are fine, the center part is loose and the dendrites are less.

[0040] After obtaining the ingot, the present invention preferably pre-treats the ingot and then Figure 2 The schematic diagram of layer-by-layer slicing is shown in FIG. 1 and the block ingot is obtained by slicing layer by layer. The pretreatment preferably includes: removing shrinkage cavities of the ingot, and then milling the surface of the ingot after the shrinkage cavities are removed. The milling is preferably performed using a milling machine, and the milling is used to remove impurity defects of the ingot.

[0041] like Figure 2 As shown, the present invention performs layer-by-layer slicing from the upper and lower surfaces of the ingot in a direction perpendicular to the thickness of the ingot, discards the loose and coarse dendrite center portion of the ingot, and obtains a plurality of ingot blocks. In the present invention, the layer-by-layer slicing is preferably performed by wire cutting or electric spark cutting. The center portion of the ingot is preferably remelted.

[0042] In the present invention, the functions of the layer-by-layer cutting are: 1) reducing the initial rolling thickness and greatly improving the processing efficiency; 2) removing the loose central part with coarse dendrites after cutting, and retaining the ingot structure with fine and uniform grains, thereby improving the ingot additivity and processing efficiency.

[0043] In the present invention, the central part of the ingot is the loose structure and coarse dendrite part in the center of the ingot. The thickness of the central part of the ingot is preferably 0.4 to 0.5 times the thickness of the ingot, and in the embodiment it can be 13 mm or 8 mm. In the present invention, the thickness of the block ingot is preferably 2 to 3 mm, and in the embodiment it can be 3 mm or 2.5 mm. The present invention adopts a layer-by-layer cutting method to discard the central part of the ingot to obtain a plurality of block ingots located on the surface of the ingot, which can obtain block ingots with improved plasticity and uniform and fine grains, improve processing efficiency, and avoid openings due to looseness and other reasons during rolling of the block ingot.

[0044] In the present invention, the thickness difference between the upper and lower rolling surfaces of the ingot is preferably ≤0.3 mm. The present invention can effectively avoid tearing of the ingot due to uneven deformation by controlling the thickness difference between the upper and lower rolling surfaces to preferably ≤0.3 mm.

[0045] After obtaining the ingot, the present invention subjects the ingot to a first small deformation rolling and a first annealing, wherein the first small deformation rolling and the first annealing are performed in a cycle, wherein a single roll gap reduction of the first small deformation rolling is ≤0.15 mm, and the cumulative deformation between two adjacent first anneals is ≤20%, to obtain an initial solder.

[0046] In the present invention, by way of example, the first small deformation rolling and the first annealing cycle are specifically performed as follows: first small deformation rolling, first annealing, first small deformation rolling, first annealing, ..., first small deformation rolling, first annealing.

[0047] In the present invention, the first small deformation rolling is preferably carried out by a two-roll rolling mill. The first small deformation rolling is carried out along the length direction of the ingot, and the rolling rate is preferably ≤40mm / s, more preferably 25-35mm / s, and in the embodiment it can be 30mm / s or 35mm / s; the single roll gap reduction is preferably 0.05-0.15mm, and in the embodiment it can be 0.1mm or 0.15mm. The cumulative deformation between the two adjacent first annealings is preferably 15-20%. The present invention controls the cumulative deformation between the two adjacent first annealings to be preferably 15-20%, so as to avoid problems such as ingot tearing derived from work hardening due to excessive deformation.

[0048] The present invention preferably controls the rolling rate and the single roll gap reduction of the first small deformation rolling, so as to avoid the phenomenon that when the ingot is deformed, the deformation amount of different positions of the rolling surface, the rolling surface and the center of the ingot are greatly different, resulting in local stress concentration on the rolling surface and tearing. In the present invention, the first annealing is preferably carried out in an air atmosphere. The temperature of the first annealing is preferably 0.88 to 0.9 times the solidus temperature, for example, in the embodiment, it can be 840°C (the multi-component Cu-Mn-Ni-Si foil brazing alloy is Cu35NiMnCoFeSiBP), 680°C (the multi-component Cu-Mn-Ni-Si foil brazing alloy is Cu40AgMnNiSiZnBP) or 760°C (the multi-component Cu-Mn-Ni-Si foil brazing alloy is Cu55-Mn37.5-Ni5-Si1.5); the holding time is preferably 5 to 8 minutes, and in the embodiment, it can be 8 minutes or 6 minutes; the cooling method is water cooling. The first annealing can be performed in an air atmosphere. In the present invention, the first annealing is performed in an air atmosphere, which can further ensure the purpose of rapid preparation.

[0049] In the present invention, the thickness of the initial brazing material is preferably 1.2-1.5 mm, and in the embodiment, it can be 1 mm or 1.2 mm. The present invention can avoid excessive deformation and tearing of the ingot by controlling the parameters of the first small deformation rolling and the first annealing, and at the same time inhibit the formation of brittle phases during the cooling process of the ingot, thereby ensuring the plasticity of the ingot.

[0050] After obtaining the initial solder, the present invention preferably cuts off 2 to 2.5 mm of the edge of each side (long side and wide side) of the initial solder before performing the second small deformation rolling and the second annealing.

[0051] After obtaining the initial solder, the present invention subjects the initial solder to a second small deformation rolling and a second annealing, wherein the second small deformation rolling and the second annealing are performed in a cycle, and only the second small deformation rolling is performed in the last cycle, the single roll gap reduction of the second small deformation rolling is ≤0.15 mm, and the cumulative deformation between two adjacent second anneals is ≥60%, until the multi-component Cu-Mn-Ni-Si foil solder is obtained.

[0052] In the present invention, by way of example, the second small deformation rolling and the second annealing cycle are specifically performed as follows: second small deformation rolling, second annealing, second small deformation rolling, second annealing, ..., second small deformation rolling, second annealing, second small deformation rolling.

[0053] In the present invention, the second small deformation rolling is preferably carried out using a four-roll gate machine. The second small deformation rolling is rolled along the length direction of the initial solder, and the rolling rate is preferably ≤40mm / s, more preferably 20-35mm / s, and in the embodiment it can be 30mm / s, 20mm / s, 25mm / s or 35mm / s; the single roll gap reduction is preferably 0.05-0.15mm, and in the embodiment it can be 0.1mm, 0.15mm or 0.05mm. The cumulative deformation between two adjacent second annealings is preferably 60-80%. The present invention controls the cumulative deformation between two adjacent second annealings to preferably 60-80%, which can avoid solder tearing, etc., while reducing the number of annealing times, improving processing efficiency, and achieving the purpose of rapid preparation.

[0054] In the present invention, the second annealing is preferably vacuum annealing, and the vacuum degree of the second annealing is preferably ≤10Pa, and can be 5Pa in the embodiment; the temperature is preferably 0.85 to 0.88 times the solidus temperature, for example, it can be 660 to 830°C, and in the embodiment it can be 830°C (the multi-component Cu-Mn-Ni-Si foil brazing filler metal is Cu35NiMnCoFeSiBP), 660°C (the multi-component Cu-Mn-Ni-Si foil brazing filler metal is Cu40AgMnNiSiZnBP) or 750°C (the multi-component Cu-Mn-Ni-Si foil brazing filler metal is Cu55-Mn37.5-Ni5-Si1.5); the holding time is preferably 8 to 20 minutes, and can be 15 minutes or 20 minutes in the embodiment, and the cooling method is preferably rapid cooling to room temperature, and the rapid cooling rate is preferably ≥30°C / min, more preferably 30 to 35°C / min, and can be 35°C / min or 30°C / min in the embodiment. The present invention can effectively eliminate the internal stress of the solder, soften the solder, and cool it quickly to avoid the formation of a brittle phase, thereby ensuring the plasticity of the solder by controlling the parameters of the second small deformation rolling and the second annealing.

[0055] In the present invention, the multi-component Cu-Mn-Ni-Si foil brazing filler metal is specifically a multi-component Cu-Mn-Ni-Si foil brazing filler metal.

[0056] In the present invention, the thickness of the multi-component Cu-Mn-Ni-Si foil solder is 0.05-0.12 mm, and in the embodiment, it can be 0.1 mm or 0.05 mm.

[0057] In the present invention, the width of the multi-component Cu-Mn-Ni-Si foil solder is 80 mm, 60 mm or 64 mm.

[0058] In the present invention, the oxygen content of the multi-component Cu-Mn-Ni-Si foil solder is lower than 180ppm, the solder composition is uniform, the quality is stable, and the deviation between the actual composition Si, B, P and the nominal composition Si, B, P does not exceed 0.06% (mass percentage).

[0059] In order to further illustrate the present invention, the technical solutions provided by the present invention are described in detail below in conjunction with embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0060] The following examples are based on Figure 1 The schematic flow chart shown is for preparing multi-component Cu-Mn-Ni-Si foil solder, specifically multi-component Cu-Mn-Ni-Si foil solder.

[0061] Example 1

[0062] This embodiment prepares a Cu35NiMnCoFeSiBP foil strip solder with a width of 80 mm and a thickness of 0.1 mm, specifically comprising the following steps:

[0063] (1) According to the nominal composition of Cu35NiMnCoFeSiBP (in mass percentage, Cu34.3-Ni29-Mn29-Co5-Fe1.2-Si1.1-B0.2-P0.2) and a total weight of 2.6 kg, electrolytic copper Cu, electrolytic copper Ni, electrolytic copper Mn, electrolytic Co, industrial pure Fe, and pure Si with a purity greater than 99.9% are weighed respectively, wherein B and P elements are added in the form of NiB and CuP master alloys, respectively, the raw materials are placed in a medium frequency furnace for smelting and cast into an ingot with a width of 90 mm and a thickness of 30 mm using a high-purity graphite mold;

[0064] (2) After the shrinkage cavity of the ingot is removed, the surface of the ingot is milled by a milling machine to remove impurities and defects, thereby obtaining an ingot with a thickness of 28 mm;

[0065] (3) cutting the milled ingot into blocks by wire cutting or electric spark cutting to obtain five blocks with a thickness of 3 mm and a thickness difference of ≤0.3 mm, wherein the middle portion of the ingot with a thickness of 13 mm is recycled;

[0066] (4) rolling the ingot along the length direction with a two-roll mill, controlling the rolling rate to be 30 mm / s, rolling to a thickness of 2.4 mm with a single roll gap reduction of 0.1 mm, and directly water-cooling at 840°C for 8 min, then rolling to a thickness of 2.0 mm with a single roll gap reduction of 0.1 mm, and directly water-cooling at 840°C for 8 min, then rolling to a thickness of 1.7 mm with a single roll gap reduction of 0.15 mm, and directly water-cooling at 840°C for 8 min, then rolling to a thickness of 1.4 mm with a single roll gap reduction of 0.15 mm, and directly water-cooling at 840°C for 6 min, then rolling to a thickness of 1.2 mm with a single roll gap reduction of 0.15 mm, and directly water-cooling at 840°C for 6 min;

[0067] (5) After cutting off 2 mm of the edge of each side of the product of step (4), the product was rolled along the length direction using a four-roller gate mill, with the rolling rate controlled to be 30 mm / s, and the thickness was rolled to 0.4 mm with a single roll gap reduction of 0.15 mm, and then the product was kept at 830° C. for 15 min at a vacuum degree of 5 Pa, and then cooled to room temperature at a cooling rate of 35° C. / min;

[0068] (6) A four-roll mill is used with a rolling rate of 25 mm / s, and the solder is rolled to a thickness of 0.1 mm with a single roll gap reduction of 0.05 mm. The solder is cut off at the edge to obtain a foil strip solder with a width of 80 mm and a thickness of 0.1 mm.

[0069] The Cu35NiMnCoFeSiBP foil solder obtained in this embodiment has an oxygen content of less than 180ppm, a uniform solder composition, and stable quality. The deviation between the actual composition Si, B, and P and the nominal composition Si, B, and P does not exceed 0.06% (mass percentage). Compared with direct rolling ingots, the time required to prepare the solder product of the same weight can be shortened by 50%.

[0070] Example 2

[0071] This embodiment prepares a Cu40AgMnNiSiZnBP foil solder with a width of 80 mm and a thickness of 0.05 mm, specifically comprising the following steps:

[0072] (1) According to the nominal composition of Cu40AgMnNiSiZnBP (in mass percentage, Cu42-Ag23-Mn21.5-Ni11.5-Si0.3-Zn1.3-B0.2-P0.2) and a total weight of 2.2 kg, Ag, Cu, Ni, Mn, Zn, and Si with a purity greater than 99.9% are weighed, wherein B and P elements are added in the form of NiB and CuP master alloys, and the raw materials are placed in a medium frequency furnace for smelting and cast into an ingot with a width of 88 mm and a thickness of 20 mm using a high-purity graphite mold;

[0073] (2) After the shrinkage cavity of the ingot is removed, the surface of the ingot is milled by a milling machine to remove impurities and defects, thereby obtaining an ingot with a thickness of 18 mm;

[0074] (3) cutting the milled ingot into blocks by wire cutting or electric spark cutting to obtain four blocks with a thickness of 2.5 mm and a thickness difference of ≤0.3 mm, wherein the middle portion of the ingot with a thickness of 8 mm is recycled;

[0075] (4) rolling the ingot along the length direction by a two-roll mill, controlling the rolling rate to be 35 mm / s, rolling to a thickness of 2.1 mm with a single roll gap reduction of 0.15 mm, then directly water-cooling at 680°C for 8 min, then rolling to a thickness of 1.7 mm with a single roll gap reduction of 0.15 mm, then directly water-cooling at 680°C for 8 min, then rolling to a thickness of 1.4 mm with a single roll gap reduction of 0.15 mm, then directly water-cooling at 680°C for 6 min, then rolling to a thickness of 1.2 mm with a single roll gap reduction of 0.15 mm, then directly water-cooling at 680°C for 6 min;

[0076] (5) After cutting off 2.5 mm of the edge of each side of the product of step (4), the product was rolled along the length direction using a four-roll gate mill, with the rolling rate controlled to be 35 mm / s, and the thickness was rolled to 0.4 mm with a single roll gap reduction of 0.1 mm, and then the product was kept at 660° C. for 15 min at a vacuum degree of 5 Pa, and then cooled to room temperature at a cooling rate of 30° C. / min;

[0077] (6) using a four-roll mill, controlling the rolling rate to 25 mm / s, rolling to a thickness of 0.1 mm with a single roll gap reduction of 0.05 mm, then keeping at 660°C for 15 min at a vacuum degree of 5 Pa, and cooling to room temperature at a cooling rate of 30°C / min;

[0078] (7) A four-roll mill is used with a rolling rate of 20 mm / s, and the solder is rolled to a thickness of 0.05 mm with a single roll gap reduction of 0.05 mm. The solder is then cut off at the edge to obtain a foil strip solder with a width of 80 mm and a thickness of 0.05 mm.

[0079] The Cu40AgMnNiSiZnBP solder foil obtained in this embodiment has an oxygen content of less than 180ppm, a uniform solder composition, stable quality, and a deviation of the actual composition Si, B, P from the nominal composition Si, B, P of no more than 0.06% (mass percentage). Compared with the direct rolling ingot, the Cu40AgMnNiSiZnBP solder obtained in this embodiment can shorten the time required for preparing the solder product of the same weight by 60%.

[0080] Example 3

[0081] This embodiment prepares a Cu55-Mn37.5-Ni5-Si1.5 foil solder with a width of 74 mm and a thickness of 0.1 mm, specifically comprising the following steps:

[0082] (1) Cu, Ni, Mn and Si with a purity greater than 99.9% were weighed according to the nominal composition of Cu55-Mn37.5-Ni5-Si1.5 and a total weight of 2.4 kg, the raw materials were placed in a medium frequency furnace for smelting and cast into an ingot with a width of 80 mm and a thickness of 20 mm using a high-purity graphite mold;

[0083] (2) After the shrinkage cavity of the ingot is removed, the surface of the ingot is milled by a milling machine to remove impurities and defects, thereby obtaining an ingot with a thickness of 17 mm;

[0084] (3) cutting the milled ingot into blocks by wire cutting or electric spark cutting to obtain three blocks with a thickness of 3 mm and a thickness difference of ≤0.3 mm, wherein the middle portion of the ingot with a thickness of 8 mm is recycled;

[0085] (4) rolling the ingot along the length direction with a two-roll mill, controlling the rolling rate to be 35 mm / s, rolling to a thickness of 2.5 mm with a single roll gap reduction of 0.15 mm, keeping at 760°C for 8 min and then directly water cooling, then rolling to a thickness of 2.1 mm with a single roll gap reduction of 0.15 mm, keeping at 760°C for 8 min and then directly water cooling, then rolling to a thickness of 1.7 mm with a single roll gap reduction of 0.15 mm, keeping at 760°C for 8 min and then directly water cooling, then rolling to a thickness of 1.4 mm with a single roll gap reduction of 0.15 mm and keeping at 760°C for 6 min and then directly water cooling, then rolling to a thickness of 1.2 mm with a single roll gap reduction of 0.15 mm and keeping at 760°C for 6 min and then directly water cooling;

[0086] (5) After cutting off 2 mm of the edge of each side of the product of step (4), the product was rolled along the length direction using a four-roll gate mill, with the rolling rate controlled to be 30 mm / s, and the thickness was rolled to 0.4 mm with a single roll gap reduction of 0.1 mm, and then the product was kept at 750° C. for 20 min under a vacuum degree of 5 Pa, and then cooled to room temperature at a cooling rate of 30° C. / min;

[0087] (6) A four-roll mill is used with a rolling rate of 30 mm / s, and the solder is rolled to a thickness of 0.1 mm with a single roll gap reduction of 0.15 mm. The solder is then cut off at the edge to obtain a foil solder with a width of 74 mm and a thickness of 0.1 mm.

[0088] The Cu55-Mn37.5-Ni5-Si1.5 foil solder obtained in this embodiment has an oxygen content of less than 180ppm, a uniform solder composition, stable quality, and a deviation of the actual composition Si, B, P from the nominal composition Si, B, P of no more than 0.06% (mass percentage). The Cu55-Mn37.5-Ni5-Si1.5 foil solder obtained in this embodiment has good cleanliness and stable quality. Compared with directly rolling ingots, the time required to prepare the solder product of the same weight can be shortened by 65%.

[0089] It can be seen from the above embodiments that the method provided by the present invention has simple process operation and high efficiency, and can prepare various types of multi-component Cu-Mn-Ni-Si foil solders. The obtained solder has good cleanliness and can meet the production requirements and quality indicators of diversified solders.

[0090] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A method for rapidly preparing a multi-element Cu-Mn-Ni-Si foil solder, characterized in that: The following steps are involved: The raw materials for preparing the multi-component Cu-Mn-Ni-Si brazing alloy are melted and cast to obtain an ingot; Cutting the ingot layer by layer from the upper and lower surfaces of the ingot in a direction perpendicular to the thickness of the ingot, discarding the central part of the ingot, and obtaining a plurality of ingot blocks; The ingot is subjected to first small deformation rolling and first annealing, wherein the first small deformation rolling and the first annealing are performed cyclically, a single roll gap reduction of the first small deformation rolling is ≤0.15 mm, and a cumulative deformation between two adjacent first anneals is ≤20%, to obtain an initial brazing material; The initial solder is subjected to a second small deformation rolling and a second annealing, the second small deformation rolling and the second annealing are cyclically performed, the single roll gap reduction of the second small deformation rolling is ≤0.15mm, and the cumulative deformation between two adjacent second annealings is ≥60%, until the multi-component Cu-Mn-Ni-Si foil solder is obtained.

2. The method for rapidly preparing multi-element Cu-Mn-Ni-Si foil solder according to claim 1, characterized in that: The thickness of the ingot is 20-30 mm; the width of the ingot is 80-120 mm, and the length is 150-200 mm.

3. The method for rapidly preparing multi-element Cu-Mn-Ni-Si foil solder according to claim 1 or 2, characterized in that: The thickness of the ingot is 2-3 mm; the thickness difference between the upper and lower rolling surfaces of the ingot is ≤0.3 mm; The thickness of the central part of the ingot is 0.4 to 0.5 times the thickness of the ingot.

4. The method for rapidly preparing multi-element Cu-Mn-Ni-Si foil solder according to claim 1, characterized in that: The first small deformation rolling is performed along the length direction of the ingot, with a rolling rate of ≤40 mm / s and a single roll gap reduction of 0.05-0.15 mm; the cumulative deformation between two adjacent first annealings is 15-20%.

5. The method for rapidly preparing multi-element Cu-Mn-Ni-Si foil solder according to claim 1 or 4, characterized in that: The first annealing is performed in an air atmosphere, the temperature of the first annealing is 0.88 to 0.9 times the solidus temperature, the holding time is 5 to 8 minutes, and the cooling method is water cooling.

6. The method for rapidly preparing multi-element Cu-Mn-Ni-Si foil solder according to claim 1, characterized in that: The thickness of the initial solder is 1.2-1.5 mm.

7. The method for rapidly preparing multi-element Cu-Mn-Ni-Si foil solder according to claim 1 or 6, characterized in that: The second small deformation rolling is carried out along the length direction of the initial solder, with a rolling rate of ≤40 mm / s and a single roll gap reduction of 0.05-0.15 mm; the cumulative deformation between two adjacent second annealings is 60-80%.

8. The method for rapidly preparing multi-element Cu-Mn-Ni-Si foil solder according to claim 1 or 7, characterized in that: The second annealing is vacuum annealing, the vacuum degree of the second annealing is ≤10Pa, the temperature is 0.85 to 0.88 times the solidus temperature, the holding time is 8 to 20min, the cooling method is rapid cooling to room temperature, and the rapid cooling rate is ≥30°C / min.

9. The method for rapidly preparing multi-element Cu-Mn-Ni-Si foil solder according to claim 1, characterized in that: The thickness of the multi-component Cu-Mn-Ni-Si foil solder is 0.05-0.12 mm.

10. The method for rapidly preparing multi-element Cu-Mn-Ni-Si foil solder according to claim 1 or 9, characterized in that: The multi-component Cu-Mn-Ni-Si foil solder includes Cu35NiMnSiCoFeBP, Cu40AgMnNiSiZnBP, CuAgMnNiSi or CuMnNiSi; The mass percentage of Si element in the CuAgMnNiSi is 1-3%; The mass percentage of Si element in the CuMnNiSi is 1-3%.

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