CN111331278B - High-corrosion-resistance Zn-Al solder powder, solder paste and preparation method - Google Patents
High-corrosion-resistance Zn-Al solder powder, solder paste and preparation method Download PDFInfo
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- CN111331278B CN111331278B CN202010224941.9A CN202010224941A CN111331278B CN 111331278 B CN111331278 B CN 111331278B CN 202010224941 A CN202010224941 A CN 202010224941A CN 111331278 B CN111331278 B CN 111331278B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
- B23K35/262—Sn as the principal constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/40—Making wire or rods for soldering or welding
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Abstract
A high corrosion resistance Zn-Al solder powder, a solder paste and a preparation method thereof, wherein the Zn-Al solder powder comprises the following components, by mass, 0.01-0.5% of Mo, 0.01-0.3% of Mn, 25-30% of Al, and the balance of Zn; the brazing filler metal paste is prepared from Zn-Al brazing filler metal powder, cesium fluoroaluminate brazing filler metal powder and triethanolamine, wherein the mass percentages of the components are 5-12% of cesium fluoroaluminate brazing filler metal, 8-15% of triethanolamine and the balance of Zn-Al brazing filler metal powder; according to the invention, the Al element content in the Zn-Al solder is increased, and the Mo element is added, so that the melting point of the Zn-Al solder is increased to 445-500 ℃, the matching degree with the active temperature (480-500 ℃) of the cesium fluoroaluminate soldering flux is high, the mechanical property of a soldered joint is good, the mixed potential of a solder paste solder joint alloy is increased, and the corrosion resistance of the soldered joint is enhanced.
Description
Technical Field
The invention relates to the field of brazing of aluminum honeycomb plates, in particular to high-corrosion-resistance Zn-Al brazing filler metal powder, brazing filler metal paste and a preparation method.
Background
The aluminum honeycomb plate has the advantages of good structural stability and good impact resistance and buffering performance, and is widely used in the fields of aerospace, airplanes, trains, ships, buildings and the like.
At present, the preparation method of the aluminum honeycomb plate is generally to weld an aluminum honeycomb core obtained by stretching and aluminum plates on two sides, and the commonly used brazing filler metal is mainly Al-Si brazing filler metal and Zn-Al brazing filler metal. The melting temperature of the existing Al-Si brazing filler metal is 570-6430 ℃, and when high-strength aluminum alloys (particularly 500 series, 6000 series, 7000 series and 2000 series aluminum alloys) are brazed, the melting point of the brazing filler metal is close to that of a base metal due to the fact that the brazing filler metal contains Mg, the solidus temperature is low, excessive burning, corrosion or grain growth of the base metal is easily caused, and the mechanical property of a joint is seriously influenced.
The common Zn-Al solder paste on the market is Zn-2Al solder paste, the melting point of the Zn-2Al solder paste is lower (382-430 ℃), and the Zn-Al solder paste is an ideal solder for the current aluminum alloy brazing. However, the Zn-2Al solder paste has the following problems:
1) the corrosion resistance of the Zn-2Al solder paste is far inferior to that of the Al-Si solder paste, and the service life of the aluminum alloy honeycomb plate is seriously influenced;
2) the brazing flux matched with the Zn-2Al brazing filler metal is commercially available cesium fluoroaluminate, the active temperature of the cesium fluoroaluminate is 480-500 ℃, the activation temperature is far higher than the melting temperature of the brazing filler metal (the brazing filler metal is melted, and the brazing flux is not melted yet), the matching degree of the cesium fluoroaluminate and the melting temperature is low, and the brazing performance of the brazing filler metal is poor.
In order to solve the problems, the development of the Zn-Al brazing paste with strong corrosion resistance, high brazing flux matching degree and good brazing performance is urgently needed.
Disclosure of Invention
The invention aims to provide high-corrosion-resistance Zn-Al solder powder, solder paste and a preparation method thereof.
The technical scheme adopted by the invention for realizing the technical purpose is as follows: the Zn-Al solder powder with high corrosion resistance comprises, by mass, 0.01-0.5% of Mo, 0.01-0.3% of Mn, 25-30% of Al and the balance of Zn.
As an optimized proposal of the Zn-Al solder powder with high corrosion resistance, the Zn-Al solder powder also contains 0.5 to 3 percent of Cu.
As another optimization scheme of the Zn-Al solder powder with high corrosion resistance, the Zn-Al solder powder also contains 0.01-0.5% of P.
The aluminum honeycomb plate brazing filler metal paste containing the Zn-Al brazing filler metal powder is prepared from the Zn-Al brazing filler metal powder, cesium fluoroaluminate brazing filler metal powder and triethanolamine, wherein the mass percent of the components is 5-12% of cesium fluoroaluminate brazing filler metal, 8-15% of triethanolamine and the balance of the Zn-Al brazing filler metal powder.
The preparation method of the aluminum honeycomb panel solder paste comprises the following steps:
1) weighing the components according to the proportion, and then uniformly mixing the components for forming the Zn-Al brazing filler metal powder and cesium fluoroaluminate brazing flux powder to form powder for later use;
2) injecting the weighed triethanolamine liquid into a container, and then placing the container in a water bath tank at 80-100 ℃ for water bath heating;
3) slowly adding the uniformly mixed powder in the step 1) into the triethanolamine liquid in the container in the step 2), and continuously stirring until paste is formed;
4) cooling the paste obtained in the step 3) to room temperature to obtain the product.
The design idea of the invention is as follows: the common zinc-aluminum solder in the market is Zn-2Al solder, the melting point of the solder is 382-415 ℃, and the solder is a common solder for aluminum alloy brazing. However, the melting point of the aluminum brazing flux cesium fluoroaluminate matched with the brazing filler metal is 480 ℃, and the active temperature is 480-500 ℃. Therefore, the brazing filler metal is melted, the brazing flux is not melted, so that the activity of the brazing flux cannot be normally exerted, and the matching degree of the brazing filler metal and the brazing flux is low.
The conventional operation in the field is to reduce the melting point temperature of the brazing filler metal, so that the brazing filler metal can be conveniently welded even without adding an active agent, but the conventional operation has the problem that the strength of a welding point of the brazing filler metal is reduced.
The invention develops a new method, and on the basis of the Zn-2Al solder, the melting temperature of the Zn-Al solder is increased to 445-500 ℃ by increasing the content of the Al element and adding the element Mo, so that the Zn-Al solder is matched with the soldering flux. Tests prove that the melting point of the brazing filler metal can be increased to the temperature matched with the brazing flux only by increasing the content of the aluminum element in the brazing filler metal to be more than 25%.
In addition, the Zn-Al solder has poor corrosion resistance, and the addition of Mo can enhance the grain boundary strength and corrosion potential of the solder, thereby improving the corrosion resistance of the solder. Meanwhile, the solder paste is easy to oxidize, and the strength of the solder can be improved by adding deoxidizing elements Mn and P. Triethanolamine is a low-temperature aluminum soldering flux, is used for preparing paste, and on one hand, the viscosity of the paste meets the use requirement, and on the other hand, the paste can be volatilized in a large amount in the brazing process without generating residues.
In the invention, the functions of the components are as follows:
zn: based on the traditional Zn-Al solder, the main elements of the solder;
al: the Al element content is increased, so that the melting temperature of the Zn-Al brazing filler metal can be increased to be matched with the activity temperature of the brazing flux, and the corrosion resistance of the brazing filler metal can also be improved;
cu: cu can improve the corrosion resistance of the Zn-Al solder to a certain extent;
mo: the Zn-Al brazing filler metal has good high-temperature performance and corrosion resistance, and is a key element for enhancing the corrosion resistance of the Zn-Al brazing filler metal; mo has high melting point and hard property and can be pinned at the grain boundary of the brazing filler metal; the electrode potential of Mo is higher, which is beneficial to improving the mixed potential of the brazing filler metal and enhancing the corrosion resistance of the brazing filler metal;
mn: deoxidizing, improving the brazing performance of the brazing filler metal paste and playing a role in dispersion strengthening;
p: deoxidizing, improving the brazing performance of the brazing filler metal paste, and refining the grain size of brazing seams;
cesium fluoroaluminate: the aluminum brazing flux matched with the Zn-Al brazing filler metal plays a role in removing films and assisting in flowing;
triethanolamine: the high temperature can be completely volatilized, and the adhesive has the function of a binder.
During the long-term placement of the Zn-2Al solder welding spot, water vapor in the air can form a water film on the surface of the welding spot. Because the electrode potential (-0.763 v) of Zn is higher than the electrode potential (-1.680 v) of Al, a potential difference is formed between the two, and the welding spot is subjected to electrochemical corrosion by taking an alpha phase (Al-rich phase) as an anode and taking a beta phase (Zn-rich phase) as a cathode under the action of a water film, wherein the corrosion process is as follows:
Zn→Zn2++2e﹣；
Al→Al3++3e﹣；
2H2O +O2+4e﹣→4OH﹣；
studies have shown that 1mol of metal, when converted to corrosion products by the action of a corrosion cell, changes in Gibbs free energy Δ G as:
ΔG=-nF（Ee-Ea）
wherein n represents the number of electron transfers in the etching reaction;
F-Faraday constant;
ea — equilibrium potential for anodic (aluminum rich phase) reactions;
ee-equilibrium potential for the cathodic (zinc-rich) reaction.
In the above formula, nF is always positive, so that only when Ee-Ea > 0, Δ G of the reaction is negative (free energy decreases), and corrosion of the anode metal proceeds spontaneously. It follows that the higher the potential of the anodic metal (Al-rich phase), the more difficult it corrodes, indicating the better thermodynamic stability of the anodic metal (Al-rich phase).
Therefore, the element Mo with higher potential (electrode potential-0.2) is added in the invention, thereby improving the mixed potential of the solder paste welding spot alloy and enhancing the corrosion resistance of the welding spot. In addition, Mo contributes to the formation of dense Mo2O3And the thin film prevents the corrosion from further expanding towards the interior of the welding spot.
Compared with the prior art, the invention has the following beneficial effects:
1) according to the invention, the Al element content in the Zn-Al solder is increased, and the Mo element is added, so that the melting point of the Zn-Al solder is increased to 445-500 ℃, the matching degree with the active temperature (480-500 ℃) of the cesium fluoroaluminate soldering flux is high, and the mechanical property of a soldered joint is good;
2) according to the invention, by adding Mo element, the mixing potential of the solder paste welding spot alloy can be improved, and the corrosion resistance of the welding spot is enhanced; in addition, Mo contributes to the formation of dense Mo2O3A thin film to prevent further expansion of corrosion into the interior of the solder joint;
3) the solder paste contains strengthening elements such as Mn, P, Cu and the like, has obvious corrosion resistance and oxidation resistance, and has long service life of soldered joints.
Drawings
FIG. 1 is a morphology chart observed under a scanning electron microscope after solder joints made by a sample of example 1 of the present invention and a sample of comparative example 2 are soaked in 3% saline for 100 hours.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. In the preparation method of the following embodiments of the present invention, "3) the uniformly mixed powder in step 1) is slowly added into the triethanolamine liquid in the container in step 2) and continuously stirred until a paste is formed," wherein the slow addition is actually a routine operation of the skilled in the art during preparation, and does not involve the addition speed and the like, and the skilled in the art can completely add the powder according to the existing preparation knowledge mastered by the skilled in the art, and the stirring operation does not involve the stirring parameters, and only needs to uniformly mix the powder and the triethanolamine liquid.
Example 1
The Zn-Al solder powder with high corrosion resistance comprises 0.01 mass percent of Mo, 0.01 mass percent of Mn, 25 mass percent of Al and the balance of Zn.
The brazing paste for the aluminum honeycomb plate containing the Zn-Al brazing filler metal powder is prepared from the Zn-Al brazing filler metal powder, cesium fluoroaluminate brazing filler metal powder and triethanolamine, wherein the mass percentages of the components are 5% of cesium fluoroaluminate brazing filler metal, 8% of triethanolamine and the balance of the Zn-Al brazing filler metal powder.
The preparation method of the aluminum honeycomb panel solder paste comprises the following steps:
1) weighing the components according to the proportion, and then uniformly mixing the components for forming the Zn-Al brazing filler metal powder and cesium fluoroaluminate brazing flux powder to form powder for later use;
2) injecting the weighed triethanolamine liquid into a container, and then placing the container in a water bath tank at 80 ℃ for water bath heating;
3) slowly adding the uniformly mixed powder in the step 1) into the triethanolamine liquid in the container in the step 2), and continuously stirring until paste is formed;
4) cooling the paste obtained in the step 3) to room temperature to obtain the product.
Example 2
The Zn-Al solder powder with high corrosion resistance comprises 0.5% of Mo, 0.3% of Mn, 30% of Al and the balance of Zn in percentage by mass.
The brazing paste for the aluminum honeycomb plate containing the Zn-Al brazing filler metal powder is prepared from the Zn-Al brazing filler metal powder, cesium fluoroaluminate brazing filler metal powder and triethanolamine, wherein the mass percentages of the components are 12% of cesium fluoroaluminate brazing filler metal, 15% of triethanolamine and the balance of the Zn-Al brazing filler metal powder.
The preparation method of the aluminum honeycomb panel solder paste comprises the following steps:
1) weighing the components according to the proportion, and then uniformly mixing the components for forming the Zn-Al brazing filler metal powder and cesium fluoroaluminate brazing flux powder to form powder for later use;
2) injecting the weighed triethanolamine liquid into a container, and then placing the container in a water bath tank at 100 ℃ for water bath heating;
3) slowly adding the uniformly mixed powder in the step 1) into the triethanolamine liquid in the container in the step 2), and continuously stirring until paste is formed;
4) cooling the paste obtained in the step 3) to room temperature to obtain the product.
Example 3
The Zn-Al solder powder with high corrosion resistance comprises the following components, by mass, 0.25% of Mo, 0.16% of Mn, 27.5% of Al and the balance of Zn.
The aluminum honeycomb plate brazing filler metal paste containing the Zn-Al brazing filler metal powder is prepared from the Zn-Al brazing filler metal powder, cesium fluoroaluminate brazing filler metal powder and triethanolamine, wherein the mass percent of each component is 8.5% of cesium fluoroaluminate brazing filler metal, 11.5% of triethanolamine and the balance of the Zn-Al brazing filler metal powder.
The preparation method of the aluminum honeycomb panel solder paste comprises the following steps:
1) weighing the components according to the proportion, and then uniformly mixing the components for forming the Zn-Al brazing filler metal powder and cesium fluoroaluminate brazing flux powder to form powder for later use;
2) injecting the weighed triethanolamine liquid into a container, and then placing the container in a water bath tank at 90 ℃ for water bath heating;
3) slowly adding the uniformly mixed powder in the step 1) into the triethanolamine liquid in the container in the step 2), and continuously stirring until paste is formed;
4) cooling the paste obtained in the step 3) to room temperature to obtain the product.
Example 4
The Zn-Al solder powder with high corrosion resistance comprises the following components, by mass, 0.1% of Mo, 0.25% of Mn, 26% of Al, 0.5% of Cu and the balance of Zn.
The brazing paste for the aluminum honeycomb plate containing the Zn-Al brazing filler metal powder is prepared from the Zn-Al brazing filler metal powder, cesium fluoroaluminate brazing filler metal powder and triethanolamine, wherein the mass percentages of the components are 6% of cesium fluoroaluminate brazing filler metal, 9% of triethanolamine and the balance of the Zn-Al brazing filler metal powder.
The preparation method of the aluminum honeycomb panel solder paste comprises the following steps:
1) weighing the components according to the proportion, and then uniformly mixing the components for forming the Zn-Al brazing filler metal powder and cesium fluoroaluminate brazing flux powder to form powder for later use;
2) injecting the weighed triethanolamine liquid into a container, and then placing the container in a water bath tank at 85 ℃ for water bath heating;
3) slowly adding the uniformly mixed powder in the step 1) into the triethanolamine liquid in the container in the step 2), and continuously stirring until paste is formed;
4) cooling the paste obtained in the step 3) to room temperature to obtain the product.
Example 5
The Zn-Al solder powder with high corrosion resistance comprises the following components, by mass, 0.2% of Mo, 0.1% of Mn, 27% of Al, 3% of Cu and the balance of Zn.
The brazing paste for the aluminum honeycomb plate containing the Zn-Al brazing filler metal powder is prepared from the Zn-Al brazing filler metal powder, cesium fluoroaluminate brazing filler metal powder and triethanolamine, wherein the mass percentages of the components are 7% of cesium fluoroaluminate brazing filler metal, 10% of triethanolamine and the balance of Zn-Al brazing filler metal powder.
The preparation method of the aluminum honeycomb panel solder paste comprises the following steps:
1) weighing the components according to the proportion, and then uniformly mixing the components for forming the Zn-Al brazing filler metal powder and cesium fluoroaluminate brazing flux powder to form powder for later use;
2) injecting the weighed triethanolamine liquid into a container, and then placing the container in a water bath tank at 90 ℃ for water bath heating;
3) slowly adding the uniformly mixed powder in the step 1) into the triethanolamine liquid in the container in the step 2), and continuously stirring until paste is formed;
4) cooling the paste obtained in the step 3) to room temperature to obtain the product.
Example 6
The Zn-Al solder powder with high corrosion resistance comprises the following components, by mass, 0.4% of Mo, 0.25% of Mn, 28% of Al, 1.75% of Cu and the balance of Zn.
The brazing paste for the aluminum honeycomb plate containing the Zn-Al brazing filler metal powder is prepared from the Zn-Al brazing filler metal powder, cesium fluoroaluminate brazing filler metal powder and triethanolamine, wherein the mass percentages of the components are 9% of cesium fluoroaluminate brazing filler metal, 11% of triethanolamine and the balance of the Zn-Al brazing filler metal powder.
The preparation method of the aluminum honeycomb panel solder paste comprises the following steps:
1) weighing the components according to the proportion, and then uniformly mixing the components for forming the Zn-Al brazing filler metal powder and cesium fluoroaluminate brazing flux powder to form powder for later use;
2) injecting the weighed triethanolamine liquid into a container, and then placing the container in a water bath tank at 100 ℃ for water bath heating;
3) slowly adding the uniformly mixed powder in the step 1) into the triethanolamine liquid in the container in the step 2), and continuously stirring until paste is formed;
4) cooling the paste obtained in the step 3) to room temperature to obtain the product.
Example 7
The Zn-Al solder powder with high corrosion resistance comprises the following components, by mass, 0.45% of Mo, 0.18% of Mn, 29% of Al, 0.01% of P and the balance of Zn.
The brazing paste for the aluminum honeycomb plate containing the Zn-Al brazing filler metal powder is prepared from the Zn-Al brazing filler metal powder, cesium fluoroaluminate brazing filler metal powder and triethanolamine, wherein the mass percentages of the components are 11% of cesium fluoroaluminate brazing filler metal, 12% of triethanolamine and the balance of the Zn-Al brazing filler metal powder.
The preparation method of the aluminum honeycomb panel solder paste comprises the following steps:
1) weighing the components according to the proportion, and then uniformly mixing the components for forming the Zn-Al brazing filler metal powder and cesium fluoroaluminate brazing flux powder to form powder for later use;
2) injecting the weighed triethanolamine liquid into a container, and then placing the container in a water bath tank at 90 ℃ for water bath heating;
3) slowly adding the uniformly mixed powder in the step 1) into the triethanolamine liquid in the container in the step 2), and continuously stirring until paste is formed;
4) cooling the paste obtained in the step 3) to room temperature to obtain the product.
Example 8
The Zn-Al solder powder with high corrosion resistance comprises the following components, by mass, 0.05% of Mo, 0.25% of Mn, 28.5% of Al, 0.5% of P and the balance of Zn.
The aluminum honeycomb plate brazing filler metal paste containing the Zn-Al brazing filler metal powder is prepared from the Zn-Al brazing filler metal powder, cesium fluoroaluminate brazing filler metal powder and triethanolamine, wherein the mass percent of the components is 11.5% of cesium fluoroaluminate brazing filler metal, 13.5% of triethanolamine and the balance of the Zn-Al brazing filler metal powder.
The preparation method of the aluminum honeycomb panel solder paste comprises the following steps:
1) weighing the components according to the proportion, and then uniformly mixing the components for forming the Zn-Al brazing filler metal powder and cesium fluoroaluminate brazing flux powder to form powder for later use;
2) injecting the weighed triethanolamine liquid into a container, and then placing the container in a water bath tank at 95 ℃ for water bath heating;
3) slowly adding the uniformly mixed powder in the step 1) into the triethanolamine liquid in the container in the step 2), and continuously stirring until paste is formed;
4) cooling the paste obtained in the step 3) to room temperature to obtain the product.
Example 9
The Zn-Al solder powder with high corrosion resistance comprises the following components, by mass, 0.33% of Mo, 0.22% of Mn, 26.5% of Al, 0.25% of P and the balance of Zn.
The aluminum honeycomb plate brazing filler metal paste containing the Zn-Al brazing filler metal powder is prepared from the Zn-Al brazing filler metal powder, cesium fluoroaluminate brazing filler metal powder and triethanolamine, wherein the mass percent of each component is 8.5% of cesium fluoroaluminate brazing filler metal, 10.5% of triethanolamine and the balance of the Zn-Al brazing filler metal powder.
The preparation method of the aluminum honeycomb panel solder paste comprises the following steps:
1) weighing the components according to the proportion, and then uniformly mixing the components for forming the Zn-Al brazing filler metal powder and cesium fluoroaluminate brazing flux powder to form powder for later use;
2) injecting the weighed triethanolamine liquid into a container, and then placing the container in a water bath tank at 90 ℃ for water bath heating;
3) slowly adding the uniformly mixed powder in the step 1) into the triethanolamine liquid in the container in the step 2), and continuously stirring until paste is formed;
4) cooling the paste obtained in the step 3) to room temperature to obtain the product.
Example 10
The Zn-Al solder powder with high corrosion resistance comprises the following components, by mass, 0.01% of Mo, 0.01% of Mn, 25% of Al, 0.5% of Cu, 0.01% of P and the balance of Zn.
The brazing paste for the aluminum honeycomb plate containing the Zn-Al brazing filler metal powder is prepared from the Zn-Al brazing filler metal powder, cesium fluoroaluminate brazing filler metal powder and triethanolamine, wherein the mass percentages of the components are 5% of cesium fluoroaluminate brazing filler metal, 8% of triethanolamine and the balance of the Zn-Al brazing filler metal powder.
The preparation method of the aluminum honeycomb panel solder paste comprises the following steps:
1) weighing the components according to the proportion, and then uniformly mixing the components for forming the Zn-Al brazing filler metal powder and cesium fluoroaluminate brazing flux powder to form powder for later use;
2) injecting the weighed triethanolamine liquid into a container, and then placing the container in a water bath tank at 80 ℃ for water bath heating;
3) slowly adding the uniformly mixed powder in the step 1) into the triethanolamine liquid in the container in the step 2), and continuously stirring until paste is formed;
4) cooling the paste obtained in the step 3) to room temperature to obtain the product.
Example 11
The Zn-Al solder powder with high corrosion resistance comprises the following components, by mass, 0.5% of Mo, 0.3% of Mn, 30% of Al, 3% of Cu, 0.5% of P and the balance of Zn.
The brazing paste for the aluminum honeycomb plate containing the Zn-Al brazing filler metal powder is prepared from the Zn-Al brazing filler metal powder, cesium fluoroaluminate brazing filler metal powder and triethanolamine, wherein the mass percentages of the components are 12% of cesium fluoroaluminate brazing filler metal, 15% of triethanolamine and the balance of the Zn-Al brazing filler metal powder.
The preparation method of the aluminum honeycomb panel solder paste comprises the following steps:
1) weighing the components according to the proportion, and then uniformly mixing the components for forming the Zn-Al brazing filler metal powder and cesium fluoroaluminate brazing flux powder to form powder for later use;
2) injecting the weighed triethanolamine liquid into a container, and then placing the container in a water bath tank at 100 ℃ for water bath heating;
3) slowly adding the uniformly mixed powder in the step 1) into the triethanolamine liquid in the container in the step 2), and continuously stirring until paste is formed;
4) cooling the paste obtained in the step 3) to room temperature to obtain the product.
Example 12
The Zn-Al solder powder with high corrosion resistance comprises the following components, by mass, 0.26% of Mo, 0.16% of Mn, 27.5% of Al, 1.75% of Cu, 0.25% of P and the balance of Zn.
The aluminum honeycomb plate brazing filler metal paste containing the Zn-Al brazing filler metal powder is prepared from the Zn-Al brazing filler metal powder, cesium fluoroaluminate brazing filler metal powder and triethanolamine, wherein the mass percent of each component is 8.5% of cesium fluoroaluminate brazing filler metal, 11.5% of triethanolamine and the balance of the Zn-Al brazing filler metal powder.
The preparation method of the aluminum honeycomb panel solder paste comprises the following steps:
1) weighing the components according to the proportion, and then uniformly mixing the components for forming the Zn-Al brazing filler metal powder and cesium fluoroaluminate brazing flux powder to form powder for later use;
2) injecting the weighed triethanolamine liquid into a container, and then placing the container in a water bath tank at 90 ℃ for water bath heating;
3) slowly adding the uniformly mixed powder in the step 1) into the triethanolamine liquid in the container in the step 2), and continuously stirring until paste is formed;
4) cooling the paste obtained in the step 3) to room temperature to obtain the product.
Comparative example 1: the composition and preparation were the same as in example 3 except that Mo was not contained.
Comparative example 2: the composition and preparation method thereof were the same as in example 3 except that the Zn-Al solder powder was replaced with the existing Zn-2 Al.
The following experiments were carried out on samples of examples 1 to 12 and comparative examples 1 to 2, respectively:
1) detecting the melting point of the product;
2) and (3) testing the tensile strength of the joints manufactured respectively according to the regulations of GB/T11363 and 2008 'soldered joint strength test method'. Brazing the brazing pastes prepared in the embodiments by adopting a furnace brazing mode, wherein a base material is 6063 aluminum alloy, a brazed joint is a butt joint, and after brazing, tensile strength tests are carried out on the joints;
3) using each sample, a weld of the same weight (about 5 grams) was brazed to a 6063 aluminum alloy panel and immersed in 3% saline for 100 hours to see the weight loss before and after corrosion.
The detection results are as follows:
example 1: the melting point is 452 ℃, the strength of a soldered joint is 130.6MPa, and the weight loss is 0.0.517 g;
example 2: the melting point is 448 ℃, the strength of the soldered joint is 135.5MPa, and the weight loss is 0.338 g;
example 3: the melting point is 445 ℃, the strength of a soldered joint is 138.1MPa, and the weight loss is 0.356 g;
example 4: the melting point is 478 ℃, the strength of a soldered joint is 140.3MPa, and the weight loss is 0.253 g;
example 5: the melting point is 472 ℃, the strength of the soldered joint is 145.8MPa, and the weight loss is 0.246 g;
example 6: the melting point is 485 ℃, the strength of a soldered joint is 142.2MPa, and the weight loss is 0.237 g;
example 7: the melting point is 480 ℃, the strength of a soldered joint is 137.2MPa, and the weight loss is 0.509 g;
example 8: the melting point is 492 ℃, the strength of a soldered joint is 135.1MPa, and the weight loss is 0.542 g;
example 9: the melting point is 482 ℃, the strength of the brazing joint is 131.8MPa, and the weight loss is 0.517 g;
example 10: the melting point is 457 ℃, the strength of a soldered joint is 147.3MPa, and the weight loss is 0.411 g;
example 11: the melting point is 500 ℃, the strength of a soldered joint is 151.1MPa, and the weight loss is 0.212 g;
example 12: the melting point is 497 ℃, the strength of a soldered joint is 148.7MPa, and the weight loss is 0.323 g;
comparative example 1: the melting point is 423 ℃, the strength of the soldered joint is 108.6MPa, and the weight loss is 0.774 g;
comparative example 2: the melting point is 410 ℃, the strength of a soldered joint is 83.8MPa, and the weight loss is 1.588 g.
The shapes of welding spots manufactured by the sample of the embodiment 1 and the sample of the comparative example 2 are observed under a scanning electron microscope after being soaked in 3% saline water for 100 hours, as shown in the attached drawing 1, the grain boundary of the brazing paste welding spot of the embodiment 1 is clear and intact, and the grain boundary in the comparative example 2 is fuzzy and has corrosion signs, namely, compared with the existing Zn-2Al solder powder, the corrosion resistance of the Zn-Al solder powder is greatly improved.
Claims (4)
1. An aluminum honeycomb plate brazing filler metal paste containing high-corrosion-resistance Zn-Al brazing filler metal powder is characterized in that: the brazing filler metal paste is prepared from Zn-Al brazing filler metal powder, cesium fluoroaluminate brazing filler metal powder and triethanolamine, wherein the mass percentages of the components are 5-12% of cesium fluoroaluminate brazing filler metal, 8-15% of triethanolamine and the balance of Zn-Al brazing filler metal powder; the Zn-Al solder powder comprises, by mass, 0.01-0.5% of Mo, 0.01-0.3% of Mn, 25-30% of Al and the balance of Zn.
2. The aluminum honeycomb panel brazing filler metal paste containing Zn — Al brazing filler metal powder with high corrosion resistance according to claim 1, wherein: the Zn-Al solder powder also contains 0.5-3% of Cu.
3. An aluminum honeycomb panel brazing filler metal paste containing a high corrosion resistance Zn-Al brazing filler metal powder according to claim 1 or 2, wherein: the Zn-Al solder powder also contains 0.01-0.5% of P.
4. A method of making an aluminum honeycomb panel braze paste as recited in claim 1 comprising the steps of:
1) weighing the components according to the proportion of claim 1, and then uniformly mixing the components for forming Zn-Al solder powder and cesium fluoroaluminate solder powder to form powder for later use;
2) injecting the weighed triethanolamine liquid into a container, and then placing the container in a water bath tank at 80-100 ℃ for water bath heating;
3) slowly adding the uniformly mixed powder in the step 1) into the triethanolamine liquid in the container in the step 2), and continuously stirring until paste is formed;
4) cooling the paste obtained in the step 3) to room temperature to obtain the product.
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| US3014798A (en) * | 1960-05-26 | 1961-12-26 | Clyde E D Campbell | Aluminum solder and filler alloy |
| DE1962760C3 (en) * | 1969-12-15 | 1980-04-03 | Vereinigte Aluminium-Werke Ag, 5300 Bonn | Use of an aluminum-based solder for flux-free brazing of aluminum materials in protective gas, inert gas or vacuum |
| JP4641267B2 (en) * | 2006-02-17 | 2011-03-02 | 株式会社デンソー | Low melting point brazing material for aluminum heat exchanger and method for producing aluminum heat exchanger |
| CN102581508A (en) * | 2012-03-01 | 2012-07-18 | 江苏科技大学 | Intermediate-temperature zinc-aluminum soldering wire |
| CN103934590B (en) * | 2014-04-13 | 2016-08-17 | 北京工业大学 | A kind of ZnAlMgIn high-temp leadless solder |
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Address after: 315700 no.929 Binhai Avenue, Danxi street, Xiangshan County, Ningbo City, Zhejiang Province (main building) 2002 Patentee after: Ningbo Intelligent Machine Tool Research Institute Co., Ltd. of China National Machinery Institute Group Patentee after: ZHENGZHOU RESEARCH INSTITUTE OF MECHANICAL ENGINEERING Co.,Ltd. Address before: 8 / F, 1111 Tian'an Road, damuwan new town, Xiangshan County, Ningbo City, Zhejiang Province 315700 Patentee before: China Machinery Intelligent Equipment Innovation Research Institute (Ningbo) Co.,Ltd. Patentee before: ZHENGZHOU RESEARCH INSTITUTE OF MECHANICAL ENGINEERING Co.,Ltd. |