CN109865962B - Low-melting-point corrosion-resistant nickel-based eutectic brazing material and application thereof - Google Patents
Low-melting-point corrosion-resistant nickel-based eutectic brazing material and application thereof Download PDFInfo
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Abstract
The invention discloses a low-melting-point corrosion-resistant nickel-based eutectic brazing material and application thereof. The low-melting-point corrosion-resistant nickel-based eutectic brazing material comprises the following components in percentage by mass: 10-14 wt% of chromium, 8-12 wt% of phosphorus, 9-11 wt% of copper, 0.5-2 wt% of tin, 0.08-0.12 wt% of silicon, and the balance of nickel and inevitable impurities. The invention also discloses application of the low-melting-point corrosion-resistant nickel-based eutectic brazing material in the field of stainless steel materials or pure copper welding. The invention utilizes the alloying action of chromium, copper, silicon and phosphorus in nickel to accurately control the contents of chromium, copper, silicon and phosphorus to obtain eutectic compositions, and prepares a nickel-based eutectic brazing material with low melting point, corrosion resistance, high temperature resistance, high welding strength and high wettability, and is particularly suitable for brazing stainless steel electric heating tubes, stainless steel watches, stainless steel jewelry and pure copper parts.
Description
Technical Field
The invention relates to a brazing material, in particular to a low-melting-point corrosion-resistant nickel-based eutectic brazing material and application thereof, and belongs to the technical field of welding.
Background
In the prior art, the brazing of stainless steel parts such as electric heating tubes and the like is usually completed by adopting a continuous brazing mode under a hydrogen protective atmosphere, and in order to obtain excellent welding tightness and long product service life, most of brazing filler metals used are low-temperature eutectic nickel-based solders. The solid phase is directly converted into the liquid phase in the melting process of the eutectic solder, and the phenomenon of solid-liquid coexistence does not exist, so that the eutectic solder has optimal fluidity, gaps can be filled quickly, and the welding tightness of products is ensured. Meanwhile, the low-temperature brazing can avoid the growth phenomenon of crystal grains of the parent metal to the maximum extent, and the service life of stainless steel parts such as an electric heating tube and the like is prolonged. The welding flux with the brand number of BNi-6 in the nickel-based welding flux is the nickel-based eutectic welding flux with the lowest melting point (about 880 ℃), the brazing temperature can be controlled below 950 ℃, but the welding flux only contains nickel and phosphorus and is easy to corrode and oxidize under the corrosive or high-temperature environment. The nickel-based solder with the BNi-7 mark contains a large amount of chromium element, so that the corrosion resistance of the solder is greatly improved, but the melting point is increased to 890 ℃, and the brazing temperature generally needs about 1050 ℃. High brazing temperature brings high energy consumption, the damage to a brazed element is larger, and the growth phenomenon of crystal grains in a weldment is easy to cause, so that the service life of a product is influenced. Therefore, it is desirable to reduce the melting point of solder and the soldering temperature, whether from the viewpoint of soldering process, product quality control, or from the viewpoint of reducing energy consumption and production cost. For example, in patent publication No. CN105189030A, the welding temperature of nickel-based brazing filler metal is reduced to 980-1000 ℃; a low temperature nickel-based braze alloy having a melting point below 1000 c is mentioned in the patent publication CN 101898283A. However, the solder compositions reported in these publications are all non-eutectic compositions, the solder must go through a solid-liquid coexisting region during the melting process, the existence of the solid phase affects the fluidity and the gap filling performance of the solder, and the solder requirements of stainless steel parts with high sealing requirements cannot be met. In addition, the related nickel-based alloy which is publicly reported still has a melting point higher than that of the BNi-7 alloy, and cannot meet the requirement of the low-temperature brazing industry. Therefore, how to develop the low-temperature nickel-based brazing filler metal with eutectic alloy components on the basis of maintaining the chromium content of the material and ensuring that the corrosion resistance is not changed so as to further reduce the melting point and the brazing temperature of the nickel brazing filler metal is a research difficulty in the prior art.
Disclosure of Invention
The invention mainly aims to provide a nickel-based eutectic brazing material with low melting point, corrosion resistance and high temperature resistance, so as to overcome the defects in the prior art.
The invention also aims to provide application of the low-melting-point corrosion-resistant nickel-based eutectic brazing material.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a low-melting-point corrosion-resistant nickel-based eutectic brazing material which comprises the following components in percentage by mass: 10-14 wt% of chromium, 8-12 wt% of phosphorus, 9-11 wt% of copper, 0.5-2 wt% of tin, 0.05-0.15 wt% of silicon, and the balance of nickel.
Further, the remainder contains unavoidable impurities, the content of which is less than 500 ppm.
The embodiment of the invention also provides application of the low-melting-point corrosion-resistant nickel-based eutectic brazing material in the field of stainless steel materials or pure copper welding.
Compared with the prior art, the invention has the beneficial effects that:
1) according to the invention, by controlling the contents of chromium and phosphorus in the traditional BNi-7 brazing material and simultaneously adding a proper amount of copper, tin and silicon elements, the technical effect of obviously reducing the melting point temperature of the nickel brazing filler metal is realized, and the melting point of the alloy is reduced to about 870 ℃ under the condition of ensuring the corrosion resistance and the welding performance of the alloy to be unchanged, so that the nickel-based eutectic brazing material with low melting point, corrosion resistance and high temperature resistance is prepared and obtained, and is particularly suitable for brazing of stainless steel electric heating tubes, stainless steel watches, stainless steel jewelry and pure copper parts;
2) the method utilizes the alloying action of chromium, copper, silicon and phosphorus in nickel to accurately control the contents of chromium, copper, silicon and phosphorus to obtain eutectic compositions; the brazing filler metal has short melting time and good fluidity, thereby fundamentally solving the problem of low-temperature brazing of the nickel-based brazing filler metal in automatic brazing;
3) automatic brazing experiments show that the low-melting-point corrosion-resistant nickel-based eutectic brazing material provided by the invention has excellent joint filling performance in reducing the automatic brazing temperature and improving the wettability of the brazing filler metal, can effectively solve the problems of large base metal grains, high energy consumption, high-temperature damage of brazing equipment and the like caused by overhigh brazing temperature in the brazing process, has the corrosion resistance and high-temperature oxidation performance equivalent to those of BNi-7, and solves the industrial welding problem.
Detailed Description
In view of the deficiencies in the prior art, the present inventors propose a technical solution of the present invention, and further explain the technical solution, the implementation process and the principle thereof, etc. as follows.
The embodiment of the invention provides a low-melting-point corrosion-resistant nickel-based eutectic brazing material which comprises the following components in percentage by mass: 10-14 wt% of chromium, 8-12 wt% of phosphorus, 9-11 wt% of copper, 0.5-2 wt% of tin, 0.05-0.15 wt% of silicon, and the balance of nickel.
In some preferred embodiments, the content of chromium in the low-melting-point corrosion-resistant nickel-based eutectic brazing material is 11.5-12.5 wt%.
Further, the content of copper in the low-melting-point corrosion-resistant nickel-based eutectic brazing material is 9.5-10.5 wt%.
Further, the content of phosphorus in the low-melting-point corrosion-resistant nickel-based eutectic brazing material is 9.5-10.5 wt%.
Further, the content of tin in the low-melting-point corrosion-resistant nickel-based eutectic brazing material is 0.8-1.2 wt%.
Further, the content of silicon in the low-melting-point corrosion-resistant nickel-based eutectic brazing material is 0.08-0.12 wt%.
In some preferred embodiments, the remainder further comprises unavoidable impurities, the content of which is less than 500 ppm.
Further, the content of the impurities is less than 300 ppm.
Furthermore, the low-melting-point corrosion-resistant nickel-based eutectic brazing material is a multi-element eutectic alloy, the melting point is 865-875 ℃ (870 +/-5 ℃), the high temperature of above 800 ℃ can be endured in the air for a long time, and the welding strength and the corrosion resistance are superior to those of BNi-7 solder.
Furthermore, the low-melting-point corrosion-resistant nickel-based eutectic brazing material is in a powdery or amorphous thin strip shape, and the powdery brazing material can be stirred with a proper glue or paste to obtain a paste or slurry-like brazing material which can be applied to stainless steel brazing.
In another aspect, the embodiment of the invention also provides the application of the nickel-based eutectic brazing material with low melting point and corrosion resistance in the field of stainless steel materials or pure copper welding.
Further, the application comprises the brazing of the low-melting-point corrosion-resistant nickel-based eutectic brazing material to a stainless steel electric heating tube, a stainless steel watch, a stainless steel jewelry or a pure copper part.
Furthermore, the brazing temperature is 900-1000 ℃.
In conclusion, the invention develops the chromium-nickel-based eutectic solder, the melting point of the eutectic solder is obviously reduced compared with the melting point of the existing nickel solder, the automatic brazing temperature can be greatly reduced, the brazing temperature is controlled between 900 ℃ and 1000 ℃, the phenomenon of grain growth of the stainless steel base metal is effectively avoided, and the service life of the product is prolonged. Meanwhile, the chromium content of the brazing filler metal is equivalent to that of BNi-7, the corrosion resistance is unchanged, and the brazing filler metal can meet the brazing requirements of industries such as heating tubes and the like.
Further, the design principle of the invention is as follows: the invention utilizes the alloying action of chromium, copper, silicon and phosphorus in nickel, accurately controls the contents of chromium, copper, silicon and phosphorus to obtain eutectic compositions, and the liquidus and solidus of the brazing filler metal are almost coincident; the melting time of the brazing filler metal is short, and the fluidity is good, so that the problems of furnace temperature control, wetting and the like of the nickel-based brazing filler metal in automatic brazing are fundamentally solved; the automatic brazing experiment shows that the low-melting-point corrosion-resistant nickel-based eutectic brazing material provided by the invention has excellent performance in reducing the automatic brazing temperature, improving the wettability of the brazing filler metal and joint filling performance, can effectively solve the problems of large base metal grains, high energy consumption, high-temperature damage of brazing equipment and the like caused by overhigh brazing temperature in the brazing process, and has an important industrial application prospect.
The technical solution of the present invention is further described in detail by the following examples. However, the examples are chosen only for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention. In the examples, the apparatus and methods used are those conventional in the art, unless otherwise specified.
Example 1
The low-melting-point corrosion-resistant nickel-based eutectic brazing material of the embodiment comprises, by mass, 12.5% of chromium, 10.5% of copper, 1.2% of tin, 10.5% of phosphorus, 0.15% of silicon, the balance being nickel, and 267ppm of impurities. The test result of the heat absorption and release reaction shows that the melting point of the low-melting-point corrosion-resistant nickel-based eutectic brazing material is875 ℃ and the bending strength of a welding spot is 710N/mm2The braze diffusion coefficient at 900 ℃ was 20.2.
Example 2
The low-melting-point corrosion-resistant nickel-based eutectic brazing material of the embodiment comprises, by mass, 11.5% of chromium, 9.5% of copper, 0.8% of tin, 9.5% of phosphorus, 0.05% of silicon, and the balance of nickel and 400ppm of impurities. The test result of the heat absorption and release reaction shows that the liquid melting point of the low-melting-point corrosion-resistant nickel-based eutectic brazing material is 874 ℃, and the bending strength of a welding spot is 690N/mm2The braze diffusion coefficient at 900 ℃ was 16.5.
Example 3
The low-melting-point corrosion-resistant nickel-based eutectic brazing material of the embodiment comprises, by mass, 12% of chromium, 10% of copper, 1% of tin, 10% of phosphorus, 0.1% of silicon, the balance of nickel, and 370ppm of impurities. The test result of the heat absorption and release reaction shows that the melting point of the low-melting-point corrosion-resistant nickel-based eutectic brazing material is 870 ℃, and the bending strength of a welding spot is 653N/mm2The braze diffusion coefficient at 900 ℃ was 25.6.
Example 4
The low-melting-point corrosion-resistant nickel-based eutectic brazing material comprises, by mass, 13% of chromium, 9% of copper, 1.2% of tin, 11% of phosphorus, 0.1% of silicon, the balance of nickel, and 300ppm of impurities. The test result of the heat absorption and release reaction shows that the melting point of the low-melting-point corrosion-resistant nickel-based eutectic brazing material is 879 ℃, and the bending strength of a welding spot is 589N/mm2The braze diffusion coefficient at 900 ℃ was 15.8.
Example 5
The low-melting-point corrosion-resistant nickel-based eutectic brazing material of the embodiment comprises, by mass, 14% of chromium, 11% of copper, 0.5% of tin, 12% of phosphorus, 0.12% of silicon, the balance of nickel, and 300ppm of impurities. The test result of the heat absorption and release reaction shows that the melting point of the low-melting-point corrosion-resistant nickel-based eutectic brazing material is 878 ℃, and the bending strength of a welding spot is 592N/mm2The braze diffusion coefficient at 900 ℃ was 15.9.
Example 6
The low-melting-point corrosion-resistant nickel-based eutectic brazing material comprises 10% of chromium by mass,10% of copper, 2% of tin, 8% of phosphorus, 0.08% of silicon, the balance of nickel and 300ppm of impurities. The test result of the heat absorption and release reaction shows that the melting point of the low-melting-point corrosion-resistant nickel-based eutectic brazing material is 876 ℃, and the bending strength of a welding spot is 593N/mm2The braze diffusion coefficient at 900 ℃ was 18.7.
Comparative example 1
The nickel-based brazing material of the comparative example was composed of, by mass, 14% of chromium, 10% of phosphorus, the balance of nickel, and 330ppm of impurities. The test results of the heat absorption and release reaction show that the melting point of the brazing material is 890 ℃, and the bending strength of the welding spot is 673N/mm2The braze diffusion coefficient at 900 ℃ was 5.6.
Comparative example 2
The nickel-based brazing material of the comparative example was composed of, by mass, 14% of chromium, 10% of phosphorus, 10% of copper, the balance of nickel, and 360ppm of impurities. The test result of the heat absorption and release reaction shows that the solidus temperature of the brazing material is 890 ℃, the liquidus temperature is 910 ℃, and the brazing test shows that the solder is not melted at 900 ℃.
Therefore, compared with the comparative example 2, the invention realizes the technical effect of obviously reducing the melting point temperature of the nickel brazing filler metal by controlling the contents of chromium and phosphorus in the traditional BNi-7 brazing material and simultaneously adding a proper amount of copper, tin and silicon elements, reduces the melting point of the alloy to about 870 ℃ under the condition of ensuring the corrosion resistance and the welding performance of the alloy to be unchanged, and prepares the nickel-based eutectic brazing material with low melting point, corrosion resistance and high temperature resistance, which is particularly suitable for brazing stainless steel electric heating tubes, stainless steel watches, stainless steel jewelry and pure copper parts.
In addition, the inventors also conducted experiments with other raw materials and conditions listed in the present specification, and similarly produced a nickel-based eutectic brazing material having a low melting point, corrosion resistance, high temperature resistance, high weld strength, and high weld wettability, in the manner of examples 1 to 6.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (1)
1. The low-melting-point corrosion-resistant nickel-based eutectic brazing material is characterized by comprising the following components in percentage by mass: 12.5 wt% of chromium, 10.5wt% of phosphorus, 10.5wt% of copper, 1.2wt% of tin, 0.15wt% of silicon, impurities with the content of 267ppm and the balance of nickel, wherein the melting point of the low-melting-point corrosion-resistant nickel-based eutectic brazing material is 875 ℃.
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| CN101499601A (en) * | 2009-03-04 | 2009-08-05 | 安固集团有限公司 | Method for welding carbon board and copper substrate in commutator |
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