Low-melting-point nickel-manganese-silicon-based brazed metal for heat exchanger applications

Abstract

Ni-Mn-Si-based brazing filler alloys or metals, which can be nickel-rich, manganese-rich, or silicon-rich, have unexpectedly narrow melting temperature ranges, low solidus and liquidus temperatures, as determined by differential scanning calorimetry (DSC), and can be brazed at low temperatures while exhibiting good wettability and diffusivity without significant boride formation that would be detrimental to the base metal. The nickel-rich alloys contain 58% to 70% nickel by weight, the manganese-rich alloys contain 55% to 62% manganese by weight, and the silicon-rich alloys contain 25% to 29% silicon by weight. Copper, with or without boron, can be used to partially replace the nickel without substantially increasing or lowering the melting point. The brazing filler alloys have sufficient brazeability to withstand the high-temperature conditions of thin-walled aviation and other heat exchangers.

Description

Technical Field

[0001] The present invention relates to a low melting point nickel-manganese-silicon-based brazing Money alloy. The brazing money alloy or alloy can be in the form of powder, amorphous foil, atomized powder, paste, tape, or sintered preform, and can be used in powder spray coating with a binder for spray applications and in screen printing paste. The brazing Money alloy can be used for brazing heat exchangers or for manufacturing heat exchangers such as thin-walled heat exchangers used in the aerospace industry and heat exchangers for air conditioners.

Background Art

[0002] Nickel-based soldering metals have been used to braze base metals such as stainless steel, alloy steel, carbon steel, and nickel-based superalloys. Ni-Cu-Mn-Si brazing alloys are widely used in the manufacture of heat exchangers for the aerospace industry.

[0003] The most well-known soldering metal for this purpose is defined as BNi-8 by the American Welding Society (AWS). According to Non-Patent Document 1, BNi-8 has a composition of 62.5 wt% - 68.5 wt% Ni, 21.5 wt% - 24.5 wt% Mn, 6.0 wt% - 8.0 wt% Si, and 4.0 wt% - 5.0 wt% Cu, and the total of the weight percentages is 100%. Conventional AWS specification BNi-8 type soldering metals such as Oerlikon Metco AMDRY 930 are widely used in the aerospace industry for brazing thin-walled plate heat exchangers. The nominal composition of Amdry 930 is 24 wt% Mn, 7.0 wt% Si, 5 wt% Cu, and the balance is Ni, and the total of the weight percentages is 100%. Amdry 930 does not contain boron, and the solidus is 1033 °C and the liquidus is 1049 °C.

[0004] Several other soldering products containing a large amount of boron (in the range of 2.75-3.5% by weight) money The genus BNi-1, 1a, 2, 3, 9, and 13 have desirable melting points comparable to Amdry 930, but are unsuitable for brazing thin-walled heat exchangers due to potential erosion problems and strength reduction due to boron diffusion into the base metal. For example, according to Non-Patent Literature 1, the composition of BNi-2 is 62.5 wt% to 68.5 wt% Ni, 6.0 wt% to 8.0 wt% Cr, 4.0 wt% to 5.0 wt% Si, 2.5 wt% to 3.5 wt% Fe, and 2.75 wt% to 3.5 wt% B, with the total weight percentages totaling 100%. Therefore, from the standpoint of strength, a large amount of boron (more than 1 wt%) is undesirable.

[0005] Commercially available nickel-rich brazing alloys that do not contain boron include AMDRY 930 (24 wt% Mn, 7.0 wt% Si, 5 wt% Cu, and the remainder Ni), AMDRY 9301 (23 wt% Mn, 7.0 wt% Si, 4.5 wt% Cu, and the remainder Ni), and AMDRY 9300B (22.5 wt% Mn, 7.0 wt% Si, 4.75 wt% Cu, and the remainder Ni).

[0006] Commercially available manganese-rich brazing alloys that do not contain boron include AT-MN70NiCr from Advanced Technology & Materials Co., Ltd. (AT&M), which has a composition of 24.0% to 26.0% by weight of Ni, 4.5% to 5.5% by weight of Cr, and 68.5% to 71.5% by weight of Mn (http: / / www.atmcn.com / index.php-a=shows&catid=838&id=2555) and a melting point range of 1035°C to 1080°C. A commercially available manganese-rich brazing alloy containing boron is SAE MOBILUS AMS 4780, which has a composition of 66 wt% Mn, 16 wt% Ni, 16 wt% Co, and 0.80 wt% B (https: / / www.sae.org / standards / content / ams4780) and a solidus-liquidus temperature range of 966°C to 1024°C.

[0007] Despite the above, it has a lower melting point compared to BNi-8 type compositions within the Ni-Cu-Mn-Si alloy system. Therefore It can be used for brazing thin-walled heat exchangers. ru soldering Money Identifying the genus is highly desired.

[0008] In contrast, to overcome the above problems, the present invention provides compositions around the true eutectic point in the Ni-Mn-Si ternary system, with further improvements through controlled copper addition and microalloying with small amounts of boron. Since the compositions of the present invention have significantly lower melting points compared to the BNi-8 type, heat exchangers with thin sheet metal, such as those manufactured for the aerospace industry, can be brazed at significantly lower temperatures. Ni-Mn-Si base brazing of the present invention keai Gold or metals exhibit good wettability and diffusivity without the adverse effects of boron diffusion into the base metal, and have an unexpectedly narrow melting point range, low solidus temperature, and low liquidus temperature, even when two phases or peaks are present in the melting profile as determined by differential scanning calorimetry (DSC). To avoid the disadvantages of boron or boride formation, boron is either not used or used in very small amounts. hair Metals or alloys can be in the form of powders, amorphous foils, atomized powders, pastes, tapes, or sintered preforms, and can be used in powder spray coatings with binders for spray applications, and in screen printing pastes. Money The genus can be used for brazing heat exchangers, or for manufacturing heat exchangers, such as thin-walled aircraft heat exchangers and air conditioner heat exchangers, and for use in heat exchangers. Furthermore, brazing can be applied to the base metal. soldering This method allows for the rapid melting of metals while being carried out at low temperatures. [Prior art documents] [Non-patent literature]

[0009] [Non-Patent Document 1] The AWS Brazing Handbook, 5th edition, 2007, Chapter 3, page 86. [Overview of the Initiative] [Problems that the invention aims to solve]

[0010] According to the present invention, Ni-Mn-Si base brazing keai Gold or metals are soldered to be rich in nickel, manganese, or silicon. keai It can be made of gold or metal. Ni-Mn-Si base soldering. keai Gold or metals offer an unexpectedly low melting point with a liquidus temperature below 1060°C and a narrow melting point range below 85°C, with little to no boron. The Ni-Mn-Si base brazing of the present invention keai Gold or metals include nickel, manganese, and silicon, and preferably copper. Optionally, microalloying with very small amounts of boron can be used to further improve solderability and lower the melting point without harmful embrittlement and erosion caused by boron diffusion into the base metal. [Means for solving the problem]

[0011] In embodiments of the present invention, Ni-Mn-Si base brazing keai Gold or metals, A) Nickel-rich soldering keai It is gold, a) Nickel in an amount of 58% to 70% by weight, b) Manganese in an amount of 26% to 29% by weight, c) Silicon in an amount of 6% to 8% by weight, d) Copper in an amount of 0% to 7% by weight, e) Contains boron in an amount of 0% to 1% by weight, The percentages from a) to e) add up to 100% by weight. Nickel-rich soldering keai Gold is A nickel-rich spelter having a solidus temperature of 1040 °C or lower, a liquidus temperature of 1060 °C or lower, or at least one of melting point ranges in which the difference between the solidus temperature and the liquidus temperature is 100 °C or lower, keai or B) An alloy rich in manganese, a) nickel in an amount of 30 wt% to 45 wt%, b) manganese in an amount of 55 wt% to 65 wt%, c) silicon in an amount of 1 wt% to 5 wt%, d) copper in an amount of 0 wt% to 7 wt%, e) boron in an amount of 0 wt% to 1 wt%, where the percentages of a) to e) total 100 wt%, and the manganese-rich spelter keai is a solidus temperature of 990 °C or lower, a liquidus temperature of 1000 °C or lower, or at least one of melting point ranges in which the difference between the solidus temperature and the liquidus temperature is 50 °C or lower, keai or C) An alloy rich in silicon, a) nickel in an amount of 50 wt% to 65 wt%, b) manganese in an amount of 8 wt% to 15 wt%, c) silicon in an amount of 25 wt% to 29 wt%, d) copper in an amount of 0 wt% to 8 wt%, e) boron in an amount of 0 wt% to 1 wt%, where the percentages of a) to e) total 100 wt%, and the silicon-rich spelter keai is a solidus temperature of 930 °C or lower, a liquidus temperature of 960 °C or lower, or at least one of melting point ranges in which the difference between the solidus temperature and the liquidus temperature is 85 °C or lower, keai and can be the silicon-rich spelter.

[0012] In aspects of the present invention, Ni-Mn-Si base brazing keai Gold or metals are a ternary system of nickel, manganese, and silicon. Ni-Mn-Si base soldering. keai Gold or metal is a) nickel-rich ternary solder. keai Gold or metallic Ni-Mn-Si, or (b) manganese-rich ternary soldering keai Gold or metallic Ni-Mn-Si, or (c) silicon-rich soldering keai It can be gold or metallic Ni-Mn-Si. The ternary Ni-Mn-Si alloy or metal has a very narrow melting point range (e.g., below 25°C) and approaches the melting behavior of a eutectic composition where the solidus temperature and liquidus temperature are the same.

[0013] In aspects of the present invention, soldering Money The material or alloy may be in the form of powder, amorphous foil, atomized powder, paste, tape, or sintered preform.

[0014] soldering Money The material or alloy can be used in powder spray coatings with binders for spray applications, and in screen printing pastes.

[0015] In aspects of the present invention, soldering money The metal or alloy is used to repair heat exchangers or to solder heat exchangers with a Ni-Mn-Si base. Money It can be used in the manufacture of heat exchangers by soldering with metal or alloy. keai Gold or metal can be used in the soldering or manufacture of heat exchangers, such as thin-walled aviation heat exchangers and air conditioning heat exchangers.

[0016] The present invention is further illustrated by the accompanying drawings. [Brief explanation of the drawing]

[0017] [Figure 1]This differential scanning calorimetry curve for a nickel-rich ternary 66.6Ni26.6Mn6.8Si brazing alloy of Example 1 of the present invention shows a narrow melting point range of 18°C, along with solidus and liquidus temperatures, exhibiting nearly true eutectic melting behavior and a single peak during heating and cooling cycles. [Figure 2] This is a differential scanning calorimetry curve showing a single peak during heating and cooling cycles for 60.9Ni26.5Mn6.8Si5.9Cu, an nickel-rich Ni-Mn-Si brazing alloy of Example 2 of the present invention, which contains copper but does not contain boron. [Figure 3] This differential scanning calorimetry curve for a manganese-rich ternary 39.5Ni58.0Mn2.5Si brazing alloy of Example 6 of the present invention shows a narrow melting point range of 16°C, along with solidus and liquidus temperatures, exhibiting nearly true eutectic melting behavior and a single peak during heating and cooling cycles. [Figure 4] This is a differential scanning calorimetry curve showing a single peak during heating and cooling cycles for 34.0Ni57.7Mn2.5Si5.8Cu, a manganese-rich Ni-Mn-Si brazing alloy of Example 7 of the present invention, which contains copper but does not contain boron. [Figure 5] This differential scanning calorimetry curve for the silicon-rich ternary 62.3Ni11.0Mn26.7Si brazing alloy of Example 9 of the present invention shows a narrow melting point range of 19°C, along with solidus and liquidus temperatures, exhibiting nearly true eutectic melting behavior and exhibiting a single peak during heating and cooling cycles. [Modes for carrying out the invention]

[0018] Alloys begin to melt at a certain temperature called the solidus and do not completely melt until they reach a second, higher temperature called the liquidus. As used herein, the solidus is the highest temperature at which the alloy is solid and melting begins. As used herein, the liquidus is the temperature at which the alloy is completely melted. Between the solidus and liquidus temperatures, the alloy is partially solid and partially liquid. As used herein, the difference between the solidus and liquidus is called the melting point range. As used herein, the brazing temperature is for Ni-Mn-Si base brazing. keai This is the temperature at which gold is used to form the solder joint. It is preferably above the liquidus, but lower than the melting point of the base metal to which it is applied. The soldering temperature is preferably Ni-Mn-Si base soldering temperature. keai Its temperature is 25°C to 50°C higher than the liquidus temperature of gold.

[0019] The melting point range is a useful gauge of how quickly an alloy melts. Alloys with a narrow melting point range flow faster, and melting at lower temperatures results in faster soldering times and increased yield. Alloys with a narrow melting point range can generally be fitted with fairly tight clearances to base metal parts, for example, 0.002 inches (50.8 μm).

[0020] soldering Metals have a wide melting point range between the solidus and liquidus, where they are partially liquid and partially solid. soldering Alloys can be suitable for filling wider clearances or "capping" finished joints. However, while they are useful for filling gaps, slowly heating alloys with a wide melting point range can lead to an event called liquefaction. Longer heating cycles can cause separation of certain elements, where the lower melting point components separate and flow out first, leaving the higher melting point components behind. Liquefaction is often a problem in furnace brazing because longer heating times required to bring parts to the brazing temperature can accelerate liquefaction. For this application, alloys with a narrow melting point range are preferable. soldering Metal is preferred.

[0021] Ni-Mn-Si based brazing keai The solidus temperature, liquidus temperature, and melting point range of gold are determined herein by differential scanning calorimetry (DSC) in accordance with the NIST practice guide, Boettinger, WJ et al., "DTA and Heat-flux DSC Measurements of Alloy Melting and Freezing," National Institute of Standards and Technology, Special Publication 960-15, November 2006, the disclosure thereof is incorporated herein by reference in its entirety. In making the determination, individual metallic materials are mixed and melted to form an alloy, the resulting alloy is solidified, the solidified alloy is pulverized to form a powder alloy, and then the powder alloy is subjected to DSC analysis. The liquidus and solidus temperatures are determined by the profile of the second heating, which allows the alloy to better conform to the crucible shape and provides a more accurate determination, as shown, for example, on page 12 of the NIST practice guide. DSC analysis is performed using Netzsch (Proteus software) STA-449 DSC at a heating rate of 10°C / min from 700°C to 1100°C, or higher as needed to exceed the liquidus temperature. From room temperature to 700°C, the differential scanning calorimeter is heated at a faster programmed speed, typically taking about 20 minutes, or at about 35°C / min. The cooling rate used for DSC analysis from above the liquidus temperature back to room temperature is also 10°C / min, although other cooling rates may be used.

[0022] The present invention relates to a Ni-Mn-Si base brazing having a low melting point and a liquidus temperature of less than 1060°C, preferably less than 1040°C. Money Provides metals or alloys. They do not contain large amounts of boron that could cause significant erosion of the base metal. Money The metal or alloy can be used for brazing heat exchangers and other devices that require brazing of thin base metals, such as thin-walled aircraft heat exchangers and air conditioner heat exchangers.

[0023] In embodiments of the present invention, a Ni-Mn-Si base solder is present at or very close to the true eutectic point of the Ni-Mn-Si ternary system, which is the temperature at which melting and solidification occur for a pure element or compound at a single temperature, rather than over a range. Money A group or alloy is provided. The Ni-Mn-Si ternary system is thought to have three true eutectic points: a Ni-rich Ni-Mn-Si ternary system, a Mn-rich Ni-Mn-Si ternary system, and a Si-rich Ni-Mn-Si ternary system. Determining the true ternary eutectic point of the Ni-Mn-Si system is difficult because it requires determining the true ternary eutectic point using equilibrium conditions that may require several days of testing to reach. In one aspect of the present invention, after determining the lowest melting point or a reasonably close ternary eutectic point for each of the Ni-rich Ni-Mn-Si ternary systems, the Mn-rich Ni-Mn-Si ternary system, and the Si-rich Ni-Mn-Si ternary system, as evidenced, for example, by a single peak in the DSC curve or a very narrow melting point range, compositional adjustments are made by controlling the addition of copper with or without boron and partially replacing nickel, so as not to substantially raise or lower the melting point.

[0024] Silicon lowers the melting point and does not readily diffuse into the base metal like boron. However, too much silicon can increase brittleness and raise the melting point. Nickel improves both mechanical strength and corrosion resistance. Copper improves wettability and the flow properties of the molten metal. Manganese acts as a melting point inhibitor. Microalloying with small amounts of boron allows for further improvements in brazing properties and melting point without the adverse effects of significant boride formation in the base metal.

[0025] Lowering the solidus and liquidus temperatures allows for Ni-Mn-Si substrate brazing. MoneyBy narrowing the melting point range of a compound or alloy, a composition that behaves more like a eutectic composition with the smallest difference between the solidus temperature and the liquidus temperature can be obtained. The narrowed melting point range, along with excellent wettability and diffusion ability, provides an alloy having a liquidus temperature of 1060°C or less, preferably 1040°C or less, more preferably 1020°C or less, and most preferably 1000°C or less, in embodiments of the present invention.

[0026] In embodiments of the present invention, Ni-Mn-Si base brazing Money The group or alloy is determined by differential scanning calorimetry (DSC), even if there are two phases or two peaks in the melting profile. 1. A narrow melting point temperature range of 100°C or less, for example, 85°C or less, preferably 50°C or less, more preferably 25°C or less, and / or 2. A low solidus temperature of 1040°C or lower, preferably 1030°C or lower, more preferably 1000°C or lower, most preferably 950°C or lower, and / or 3. It exhibits a low liquidus temperature of 1060°C or lower, preferably 1040°C or lower, more preferably 1020°C or lower, and most preferably 1000°C or lower.

[0027] Nickel-rich soldering alloy In embodiments of the present invention, the Ni-Mn-Si base brazed alloy or metal is a) Nickel in an amount of 58% to 70% by weight, b) Manganese in an amount of 26% to 29% by weight, c) Silicon in an amount of 6% to 8% by weight, d) Copper in an amount of 0% to 7% by weight, e) Contains boron in an amount of 0% to 1% by weight, The percentages of a) to e) add up to 100% by weight, resulting in nickel-rich soldering. keai It is gold.

[0028] Nickel-rich soldering keai Gold is A solidus temperature of 1040°C or lower, Liquidus temperature below 1060℃, or The difference between the solidus temperature and the liquidus temperature is at least one of the melting point ranges of 100°C or less.

[0029] In one aspect of the present invention, Ni-Mn-Si soldering keai The gold is nickel-rich ternary solder. keai Gold is Ni-Mn-Si, and a) the amount of nickel is 64% to 70% by weight, preferably 66% to 68% by weight, more preferably 66% to 67% by weight; b) the amount of manganese is 26% to 29% by weight, preferably 26% to 27% by weight, more preferably 26.3% to 26.9% by weight; and c) the amount of silicon is 6% to 8% by weight, preferably 6.5% to 7.5% by weight, more preferably 6.6% to 6.9% by weight, and the percentages of [a) + b) + c)] add up to 100% by weight. Also, nickel-rich ternary soldering keai Gold Ni-Mn-Si is, 1. Solidus temperature of 1040℃ or lower, 2. Liquidus temperature of 1060℃ or lower, 3. The difference between the solidus temperature and the liquidus temperature is 40°C or less, preferably 20°C or less, and the melting point range has at least one of these values.

[0030] In another aspect of the present invention, a nickel-rich soldering method is used, in which copper containing or not containing boron may be included together with nickel, manganese, and silicon. keai Gold is a) Nickel in an amount of 58% to 70% by weight, preferably 58% to 62% by weight, more preferably 58% to 61.5% by weight, b) Manganese in an amount of 26% to 29% by weight, preferably 26.5% to 27.5% by weight, c) Silicon in an amount of 6% to 8% by weight, preferably 6.6% to 7.2% by weight, d) A copper in an amount of 0% to 7% by weight, preferably more than 0% but 7% or less by weight, preferably 4% to 6% by weight, more preferably 4.3% to 5.9% by weight, e) A boron comprising an amount of 0% to 1% by weight, preferably more than 0% but less than 1% by weight, preferably 0.1% to 0.7% by weight, more preferably 0.1% to 0.5% by weight, The percentages from a) to e) add up to 100% by weight.

[0031] Nickel-rich solder containing copper and no boron keai Gold can have a liquidus temperature of less than 1060°C, preferably less than 1040°C. 1. A solidus temperature of 1040°C or lower, preferably 1030°C or lower, more preferably 1025°C or lower, 2. A liquidus temperature of 1060°C or lower, preferably 1045°C or lower, more preferably 1040°C or lower, 3. The difference between the solidus temperature and the liquidus temperature is 40°C or less, preferably 20°C or less, and the melting point range has at least one of these values.

[0032] Nickel-rich solder containing copper and boron keai Gold is 1. A solidus temperature of 1000°C or less, preferably 950°C or less, most preferably 920°C or less, 2. A liquidus temperature of 1030°C or lower, preferably 1010°C or lower, more preferably 1000°C or lower, most preferably 980°C or lower, or 3. The material may have at least one melting point range in which the difference between the solidus temperature and the liquidus temperature is 85°C or less, preferably 65°C or less, and more preferably 35°C or less.

[0033] Manganese-rich soldering alloy In embodiments of the present invention, Ni-Mn-Si base brazing keai Gold or metal, manganese-rich soldering keai It is gold, a) Nickel in an amount of 30% to 45% by weight, preferably 32% to 41% by weight, b) Manganese in an amount of 55% to 62% by weight, preferably 57% to 60% by weight, c) Silicon in an amount of 1% to 5% by weight, preferably 2% to 4% by weight, d) Copper in an amount of 0% to 7% by weight, preferably more than 0% but 7% or less by weight, preferably 4% to 6.5% by weight, e) A mixture containing boron in an amount of 0% to 1% by weight, preferably greater than 0% by weight and less than 1% by weight, preferably 0.1% to 0.7% by weight. The percentages of a) to e) add up to 100% by weight, indicating a manganese-rich solder. keai It is gold.

[0034] Manganese-rich solder keai Gold is 1. Solidus temperature of 990°C or lower, preferably 980°C or lower, more preferably 950°C or lower, most preferably 925°C or lower. 2. A liquidus temperature of 1000°C or less, preferably 980°C or less, more preferably 950°C or less, 3. It may have at least one melting point range in which the difference between the solidus temperature and the liquidus temperature is 35°C or less, preferably 20°C or less.

[0035] In one aspect of the present invention, Ni-Mn-Si soldering keai The gold is coated with manganese-rich ternary solder. keai Gold Ni-Mn-Si, wherein a) the amount of nickel is 36% to 42% by weight, b) the amount of manganese is 56% to 62% by weight, and c) the amount of silicon is 1% to 4% by weight, preferably 2% to 4% by weight, and the total percentage of [a) + b) + c) is 100% by weight, and is rich in manganese. keai It is gold (Ni-Mn-Si).

[0036] Also, manganese-rich ternary soldering keai Gold Ni-Mn-Si is, 1. Solidus temperature of 990°C or lower, preferably 980°C or lower. 2. A liquidus temperature of 1000°C or less, preferably 995°C or less, 3. It has at least one melting point range in which the difference between the solidus temperature and the liquidus temperature is 30°C or less, preferably 20°C or less.

[0037] Silicon-rich soldering alloy In embodiments of the present invention, Ni-Mn-Si base brazing keai Gold or metals are soldered with silicon-rich solder. keai It is gold, a) Nickel in an amount of 50% to 65% by weight, preferably 53% to 63% by weight, more preferably 55% to 63% by weight, b) Manganese in an amount of 8% to 15% by weight, preferably 10% to 12% by weight, c) Silicon in an amount of 25% to 29% by weight, preferably 25% to 28% by weight, d) Copper in an amount of 0% to 8% by weight, preferably more than 0% by weight but 8% or less by weight, preferably 2% to 8% by weight, more preferably 3% to 7% by weight, e) A mixture containing boron in an amount of 0% to 1% by weight, preferably more than 0% but less than 1%, preferably 0.1% to 0.7% by weight, The percentages of a) to e) add up to 100% by weight, resulting in silicon-rich soldering. keai It is gold.

[0038] Silicon-rich solder keai Gold is 1. Solidus temperature of 930°C or lower, preferably 920°C or lower, more preferably 900°C or lower. 2. A liquidus temperature of 960°C or lower, preferably 940°C or lower, more preferably 925°C or lower, 3. It may have at least one melting point range in which the difference between the solidus temperature and the liquidus temperature is 85°C or less, preferably 50°C or less.

[0039] In one aspect of the present invention, Ni-Mn-Si soldering keai Gold is silicon-rich ternary solder. keaiGold Ni-Mn-Si, where a) the amount of nickel is 59% to 65% by weight, b) the amount of manganese is 8% to 14% by weight, and c) the amount of silicon is 25% to 29% by weight, and the sum of the percentages of [a) + b) + c)] is 100% by weight, a silicon-rich ternary solder. keai It is gold (Ni-Mn-Si).

[0040] Also, silicon-rich ternary soldering keai Gold Ni-Mn-Si is, 1. Solidus temperature of 930°C or lower, preferably 920°C or lower. 2. A liquidus temperature of 960°C or lower, preferably 940°C or lower, 3. It has at least one melting point range in which the difference between the solidus temperature and the liquidus temperature is 40°C or less, preferably 20°C or less.

[0041] In embodiments of the present invention, Ni-Mn-Si base brazing keai Gold or metals can be manufactured in the form of powder, amorphous foil, atomized powder, powder-based paste, powder-based tape, sintered preform, powder spray coating with binder, or screen printing paste. Ni-Mn-Si base soldering keai Gold or metal can be applied by spraying or screen printing.

[0042] In an additional aspect of the present invention, Ni-Mn-Si base brazing having liquidus temperatures of 1060, 1040, 1020, and less than 1000°C keai A method is provided for manufacturing or repairing a heat exchanger by soldering it with gold or metal.

[0043] Ni-Mn-Si based brazing keai Gold or metal is soldered. keaiIt can be manufactured using conventional methods for producing gold or metals. For example, as is conventional in the art, all elements or metals in the correct proportions can be mixed and melted together to form a chemically homogeneous alloy which is atomized into a chemically homogeneous alloy powder. Ni-Mn-Si base soldering keai The particle size of gold or metal may depend on the soldering method used. Conventional particle size distributions used in a given soldering method are as follows: Ni-Mn-Si base soldering of the present invention keai It can be used with gold or metal.

[0044] Ni-Mn-Si based brazing keai The base metal to be soldered with gold or metal can be any known or conventional material or article requiring soldering. Non-limiting examples of base metals include alloys or superalloys used in the manufacture of heat exchangers and other devices requiring soldering of thin base metals, such as thin-walled aircraft heat exchangers and air conditioning heat exchangers. Ni-Mn-Si base soldering according to the present invention keai Other non-limiting examples of known and conventional base metals that can be soldered with gold or metal include carbon steel and low-alloy steel, nickel and nickel-based superalloys, stainless steel, and tool steel.

[0045] The present invention is further illustrated by the following non-limiting embodiments, where all parts, percentages, ratios, and proportions are by weight, all temperatures are in °C, and all pressures are atmospheric pressure unless otherwise specified. [Examples]

[0046] Examples 1-11 describe the Ni-Mn-Si base brazing of the present invention based on a ternary Ni-Mn-Si system, with the addition of Cu alone and Cu and B alone. keai This relates to gold or metal. Examples 1-5 are nickel-rich soldering. keai In relation to gold, Examples 6-8 are manganese-rich soldering keai In relation to gold, Examples 9-11 are silicon-rich soldering keaiThis relates to gold. Comparative Example 1 is a BNi-8 type nickel-based brazing alloy, which is a Ni-Mn-Si-Cu nickel-based brazing alloy that does not contain B. keai This relates to Amdry930, which is gold. Comparative Examples 2 and 3 are manganese-rich solders that do not contain silicon or copper, but contain Cr, or contain Co and B. keai This relates to gold. The Ni-Mn-Si base soldering method of this invention. keai Gold or metal (Examples 1-11) and comparative Ni and Mn base soldering keai Table 1 shows the composition of gold or metals (Comparative Examples 1-3), their solidus temperature, liquidus temperature, and melting point range, all determined by DSC using Netzsch STA 449 (DSC) in the same manner with heating and cooling rates of 10°C / min. [Table 1]

[0047] Example 1 is a nickel-rich soldering of the ternary 66.6Ni26.6Mn6.8Si6.8 of the present invention. keai It is gold. As shown in Figure 1, the differential scanning calorimetry curve of the ternary alloy of Example 1 shows a single peak in the heating and cooling cycles, exhibiting nearly true eutectic melting behavior with a narrow melting point range of 18°C ​​and solidus temperatures of 1038°C and liquidus temperatures of 1056°C. The data listed in Table 1 are for the nickel-rich brazing of the ternary 66.6Ni26.6Mn6.8Si of the present invention, which does not contain copper or boron. keai This shows that gold has only slightly higher solidus and liquidus temperatures, as well as a slightly higher melting point range, compared to the copper-containing nickel-based brazed alloy Amdry 930 of Comparative Example 1, which had a solidus temperature of 1033°C, a liquidus temperature of 1049°C, and a melting point range of 16°C.

[0048] In Example 2, the copper was soldered using the ternary nickel-rich soldering method from Example 1. keai By substituting a portion of the nickel in the gold, the present invention provides a nickel-rich solder of 60.9Ni26.5Mn6.8Si5.9Cu that does not contain boron. keai Gold is provided. As shown in Figure 2, the differential scanning calorimetry curve is shown for the nickel-rich Ni-Mn-Si solder of Example 2 of the present invention, which contains copper but does not contain boron. keai Gold, 60.9Ni26.5Mn6.8Si5.9Cu, shows a single peak in the heating and cooling cycles. Nickel-rich brazing of Example 2 of the present invention is shown in Figure 2 and Table 1. keai Gold exhibits a narrow melting point range of 14°C, and solidus temperatures of 1025°C and liquidus temperatures of 1039°C, each of which is unexpectedly lower than the solidus temperature of 1033°C, the liquidus temperature of 1049°C, and the melting point range of 16°C of Amdry 930 in Comparative Example 1.

[0049] In Examples 3-5, copper and a very small amount of boron were used in the ternary nickel-rich soldering of Example 1. keai By substituting a portion of the nickel in the gold, the nickel-rich soldering of the present invention keai As the melting point range of gold increases, the solidus and liquidus temperatures are substantially reduced. The data in Table 1 are for nickel-rich soldering in Examples 3-5. keai This shows that gold exhibits a) an unexpectedly low solidus temperature below 975°C, ranging from 906°C to 975°C, and b) an unexpectedly low liquidus temperature below 1009°C, ranging from 978°C to 1009°C.

[0050] As shown in Figure 3, the differential scanning calorimetry curve of the ternary manganese-rich alloy of Example 6 shows a single peak in the heating and cooling cycles, indicating nearly true eutectic melting behavior, along with a narrow melting point range of 16°C and solidus temperatures of 977°C and liquidus temperatures of 993°C. In Example 7, copper is used in the ternary manganese-rich soldering of Example 6. keai By substituting a portion of the nickel in the gold, a boron-free manganese-rich solder of 34.0Ni57.7Mn2.5Si5.8Cu according to Example 7 of the present invention is achieved. keaiGold is provided. As shown in Figure 4, the differential scanning calorimetry curve of the manganese-rich alloy of Example 7 shows a single peak in the heating and cooling cycles, along with a narrow melting point range of 18°C, a solidus temperature of 948°C, and a liquidus temperature of 966°C, each of which is lower than that of the ternary manganese-rich alloy of Example 6. In Example 8, copper and a small amount of boron are added to the ternary manganese-rich alloy of Example 6. keai By substituting a portion of the nickel in gold, the manganese-rich soldering of the present invention keai The melting point range of gold is raised by only 5°C, while the solidus temperature is substantially lowered to 910°C and the liquidus temperature is substantially lowered to 931°C.

[0051] The data listed in Table 1 pertains to the manganese-rich soldering of the present invention. keai Examples 6-8 of gold exhibit: a) an unexpectedly low solidus temperature of 977°C or less, ranging from 910°C to 977°C; b) an unexpectedly low liquidus temperature of 993°C or less, ranging from 931°C to 993°C; and c) an unexpectedly low melting point range of 21°C or less, ranging from 16°C in Example 6 to 21°C in Example 8. Comparative Examples 2 and 3, which are rich in manganese, have solidus temperatures of 966°C to 1035°C, liquidus temperatures of 1024°C to 1080°C, and a melting point range of 45°C to 58°C. In the case of Comparative Example 2, which does not contain boron, the manganese-rich soldering of Examples 6 and 7, which do not contain boron, is shown to be different. keai Compared to gold, the solidus temperature is 58°C to 87°C higher, the liquidus temperature is 87°C to 114°C higher, and the melting point range is 27°C to 29°C higher. In the case of Comparative Example 3 containing boron, the manganese-rich soldering of Example 8 containing boron... keai Compared to gold, its solidus temperature is 56°C higher, its liquidus temperature is 93°C higher, and its melting point range is 37°C higher.

[0052] Example 9 is a silicon-rich soldering of ternary 62.3Ni11.0Mn26.7Si according to the present invention. keaiIt is gold. As shown in Figure 5, the differential scanning calorimetry curve of the ternary alloy of Example 9 shows a single peak in the heating and cooling cycles, indicating nearly true eutectic melting behavior, along with a narrow melting point range of 19°C and solidus temperatures of 915°C and liquidus temperatures of 934°C. In Example 10, copper is used in the silicon-rich soldering of the ternary alloy of Example 9. keai By substituting a portion of the nickel in gold, the present invention provides a silicon-rich soldering of 55.6Ni10.9Mn26.6Si7.0Cu that does not contain boron. keai Gold is provided, and the silicon-rich soldering of the present invention keai Compared to gold, the solidus temperature is substantially lowered to 880°C, but the liquidus temperature is raised to 947°C, and the melting point range is raised to 67°C. In Example 11, copper and a very small amount of boron are used in the ternary silicon-rich soldering of Example 9. keai By substituting a portion of the nickel in gold, the silicon-rich soldering of the present invention keai With a 17°C increase in the melting point range of gold, the solidus temperature is substantially lowered to 870°C and the liquidus temperature is substantially lowered to 906°C.

[0053] Furthermore, the present invention is disclosed herein in a manner that enables the implementation and use of the invention, at least by disclosing certain exemplary embodiments such as simplification or efficiency improvements, so that, for example, the invention can be implemented without any steps, additional elements, or additional structures not specifically disclosed herein.

[0054] It should be noted that the embodiments described herein are provided solely for illustrative purposes and are not intended to be construed as limiting the invention. Although the invention has been described with reference to exemplary embodiments, it should be understood that the words used herein are descriptive and illustrative, not limiting. Modifications can be made in the embodiments described herein, as are now stated and amended, without departing from the scope and spirit of the invention, within the scope of the appended claims. Although the invention is described herein with reference to specific means, materials, and embodiments, the invention is not intended to be limited to the details disclosed herein, but rather extends to all functionally equivalent structures, methods, and uses, such as those within the scope of the appended claims.

Claims

1. A nickel-rich brazing alloy, a Ni-Mn-Si based brazing alloy, a) The amount of nickel is 58% by weight to 63.5% by weight, b) The amount of manganese is 26% to 29% by weight, c) The amount of silicon is 6% to 8% by weight, d) The amount of copper is 4% to 6% by weight, e) The amount of boron is greater than 0% by weight and less than 1% by weight, The percentages from a) to e) add up to 100% by weight. The aforementioned nickel-rich soldering alloy is The solidus temperature is 1030°C or lower. The liquidus temperature is 1040°C or lower, and The difference between the solidus temperature and the liquidus temperature is 85°C or less. This is a Ni-Mn-Si brazed alloy.

2. The nickel-rich brazing alloy is the Ni-Mn-Si-based brazing alloy according to claim 1, a) The amount of nickel is 58% by weight to 63.5% by weight, b) The amount of manganese is 26% to 29% by weight, c) The amount of silicon is 6% to 8% by weight, d) The amount of copper is 4% to 6% by weight, e) The amount of boron is greater than 0% by weight and less than 1% by weight, The percentages from a) to e) add up to 100% by weight. The aforementioned nickel-rich soldering alloy is The solidus temperature is 1000°C or less, A Ni-Mn-Si-based brazed alloy having a liquidus temperature of 1030°C or lower.

3. The nickel-rich brazing alloy is the Ni-Mn-Si-based brazing alloy according to claim 2, A Ni-Mn-Si brazed alloy in which the amount of boron is 0.1% to 0.7% by weight, and the percentages of a) to e) sum up to 100% by weight.

4. The nickel-rich brazing alloy is the Ni-Mn-Si-based brazing filler alloy according to claim 3, The amount of boron is 0.1% by weight to 0.5% by weight, and the percentages a) to e) add up to 100% by weight. The aforementioned nickel-rich soldering alloy is The solidus temperature is 950°C or lower, or A Ni-Mn-Si brazed alloy having a liquidus temperature of 10¹°C or lower.

5. The nickel-rich brazing alloy is the Ni-Mn-Si-based brazing alloy according to claim 3, a) The amount of nickel is 58% to 62% by weight, b) The amount of manganese is 26.5% by weight to 27.5% by weight, c) The amount of silicon is 6.6% by weight to 7.2% by weight, d) The amount of copper is 4% to 6% by weight, e) The amount of boron is 0.1% by weight to 0.5% by weight, A Ni-Mn-Si brazed alloy in which the percentages of a) to e) add up to 100% by weight.

6. The nickel-rich brazing alloy is the Ni-Mn-Si-based brazing alloy according to claim 5, A Ni-Mn-Si brazed alloy having a solidus temperature of 920°C or lower.

7. The nickel-rich brazing alloy is the Ni-Mn-Si-based brazing alloy according to claim 5, A Ni-Mn-Si-based brazed alloy having a liquidus temperature of 980°C or lower.

8. The Ni-Mn-Si brazed alloy according to claim 1, wherein the solidus temperature is 975°C or less, and / or the liquidus temperature is 1000°C or less.

9. The Ni-Mn-Si brazed alloy according to claim 1, wherein the solidus temperature is 950°C or lower.

10. A Ni-Mn-Si-based brazing alloy according to any one of claims 1 to 9, in the form of a powder, amorphous foil, paste, tape, or sintered preform.

11. A powder spray coating comprising a Ni-Mn-Si base brazed alloy according to any one of claims 1 to 10 and a binder.

12. A heat exchanger comprising a Ni-Mn-Si brazed alloy according to any one of claims 1 to 10.

13. The heat exchanger according to claim 12, which is an aircraft heat exchanger or an air conditioner heat exchanger.

14. A method for manufacturing or repairing a heat exchanger, A method comprising soldering the heat exchanger with the Ni-Mn-Si-based brazing alloy described in any one of claims 1 to 10.

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