Copper-phosphorus welding ring and preparation method and application thereof
阅读说明：本技术 铜磷焊环及其制备方法和应用 (Copper-phosphorus welding ring and preparation method and application thereof ) 是由 董显 张冠星 张雷 董宏伟 常云峰 薛行雁 于 2020-07-14 设计创作，主要内容包括：本发明涉及金属钎焊材料技术领域,尤其是涉及一种铜磷焊环及其制备方法。铜磷焊环,包括焊环本体和设置于所述焊环本体的一侧端面或两侧端面的反应层；所述焊环本体包括铜磷钎料和钎剂；所述反应层包括硫酸铜。本发明的预成形铜磷焊环,在焊环本体一侧或两侧的端面设置有硫酸铜反应层,基于接触反应,在加热过程中,硫酸铜先与钢基体发生反应,在其表面生成一层铜,有效阻止铜磷钎料中的P与Fe元素反应生产脆性化合物,从而提高钎缝连接强度。(The invention relates to the technical field of metal brazing materials, in particular to a copper-phosphorus welding ring and a preparation method thereof. The copper-phosphorus welding ring comprises a welding ring body and reaction layers arranged on one side end face or two side end faces of the welding ring body; the welding ring body comprises copper-phosphorus brazing filler metal and brazing flux; the reaction layer includes copper sulfate. According to the preformed copper-phosphorus welding ring, the copper sulfate reaction layer is arranged on the end face of one side or two sides of the welding ring body, copper sulfate firstly reacts with the steel matrix in the heating process based on contact reaction, a layer of copper is generated on the surface of the copper sulfate, P in the copper-phosphorus brazing filler metal is effectively prevented from reacting with Fe to produce a brittle compound, and therefore the brazing seam connection strength is improved.)
1. The copper-phosphorus welding ring is characterized by comprising a welding ring body and reaction layers arranged on one side end face or two side end faces of the welding ring body;
the welding ring body comprises copper-phosphorus brazing filler metal and brazing flux; the reaction layer includes copper sulfate.
2. The brazing ring of claim 1, wherein said reaction layer has a thickness of 1mm to 2 mm;
preferably, the mass ratio of the welding ring body to the reaction layer is (4-20): 1.
3. The brazing ring according to claim 1 or 2, wherein the brazing ring comprises 70-80% by mass of brazing filler metal, 10-15% by mass of flux and 5-20% by mass of copper sulfate.
4. The brazing ring according to claim 1, wherein the mass ratio of the brazing filler metal to the brazing flux in the brazing ring body is (4-8): 1;
preferably, in the welding ring body, the mass ratio of the copper-phosphorus brazing filler metal to the brazing flux is (4.5-8): 1.
5. The brazing ring according to claim 1 or 4, wherein said brazing filler metal comprises, in mass percent: 5-8% of phosphorus, 0-20% of silver and the balance of copper;
preferably, the brazing flux comprises the following components in percentage by mass: 30-70% of potassium fluoborate, 5-20% of boric anhydride, 5-60% of borax and 5-20% of potassium bifluoride.
6. The brazing ring of claim 1, wherein said brazing filler metal, said flux and said copper sulfate are all in powder form;
preferably, the particle sizes of the copper-phosphorus brazing filler metal, the brazing flux and the copper sulfate are 100 meshes or less;
preferably, the copper sulfate is anhydrous copper sulfate.
7. A method of forming a brazing ring according to any one of claims 1 to 6, comprising the steps of:
and respectively filling the mixture of the copper-phosphorus brazing filler metal and the brazing flux and the copper sulfate into a mold of the copper-phosphorus welding ring, and performing compression molding.
8. The method of claim 7, wherein the mold of the brazing ring is filled with a mixture of brazing filler metal and flux, then filled with copper sulfate, and press-formed; or, filling copper sulfate into the mold of the copper-phosphorus welding ring, then filling the mixture of copper-phosphorus brazing filler metal and brazing flux, and pressing and forming.
9. The method of claim 7, wherein the mold for the brazing ring is filled with 1/3-1/2 wt% of copper sulfate, a mixture of brazing filler metal and flux, and the balance of copper sulfate, and press-formed.
10. Use of a brazing ring according to any one of claims 1 to 6 for brazing steel-copper or steel-steel tubular metal.
Technical Field
The invention relates to the technical field of metal brazing materials, in particular to a copper-phosphorus welding ring and a preparation method and application thereof.
Background
At present, the brazing carbon steel pipe mainly adopts silver-based brazing filler metal, the silver content of the brazing filler metal is generally more than 25%, and the high-silver brazing filler metal not only consumes a large amount of silver resources, but also has higher cost due to higher recovery difficulty of the brazing filler metal. To reduce costs, there is a need to develop low silver or silver-free solders to replace high silver solders. The copper-phosphorus brazing filler metal is widely applied and has strength and heat resistance which are not inferior to those of common silver brazing filler metal, but in the brazing process, P elements in the copper-phosphorus brazing filler metal can react with Fe in a base metal to form a layer of brittle compound at an interface, so that steel and copper cannot be effectively connected, and the application range of the copper-phosphorus brazing filler metal is limited.
The invention patent application with the application number of 201710998882.9 provides a magnetic field induction welding method, which is characterized in that a composite solder containing magnetic metal powder is heated to be melted, the magnetic metal powder in the composite solder is distributed along the direction of a directional magnetic field under the action of the directional magnetic field to form a lap joint or occlusion microstructure with a steel matrix, and the reaction of P element in the solder and Fe in the steel matrix is weakened.
Disclosure of Invention
The invention aims to provide a copper-phosphorus welding ring to solve the technical problem that the strength and the cost of a steel brazing seam cannot be considered simultaneously in the prior art.
The second purpose of the invention is to provide a preparation method of the copper-phosphorus welding ring, which is simple to operate and has good repeatability.
The third purpose of the invention is to provide the application of the copper-phosphorus welding ring in the field of steel-copper and steel-steel tubular metal brazing.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the copper-phosphorus welding ring comprises a welding ring body and reaction layers arranged on one side end face or two side end faces of the welding ring body;
the welding ring body comprises copper-phosphorus brazing filler metal and brazing flux; the reaction layer includes copper sulfate.
According to the preformed copper-phosphorus welding ring, the copper sulfate reaction layer is arranged on the end face of one side or two sides of the welding ring body, copper sulfate firstly reacts with the steel matrix in the heating process based on contact reaction, a layer of copper is generated on the surface of the copper sulfate, P in the copper-phosphorus brazing filler metal is effectively prevented from reacting with Fe to produce a brittle compound, and therefore the brazing seam connection strength is improved.
In actual operation, the reaction layer is arranged on one side end face or two side end faces, and the reaction layer can be selected according to actual application scenes. If the copper-phosphorus welding ring only needs one end to be brazed with the steel tubular metal, the reaction layer can be arranged on one side end face only; if both ends of the brazing ring are brazed to the tubular metal, it is preferable to provide reaction layers on both end faces.
Specifically, the end section of the reaction layer is correspondingly attached to the end section of the welding ring body. Further, the end cross-sectional dimension of the reaction layer is greater than or equal to the end cross-sectional dimension of the weld ring body; preferably, the end cross-sectional dimension of the reaction layer is equal to the end cross-sectional dimension of the weld ring body.
In a specific embodiment of the present invention, the weld ring body has a circular ring structure. In a specific embodiment of the present invention, the reaction layer has a thickness of 1mm to 2 mm.
In an embodiment of the invention, the mass ratio of the welding ring body to the reaction layer is (4-20): 1, and preferably (5-15): 1.
The mass ratio can be adjusted according to actual requirements so as to adjust the thickness of the reaction layer on the end face of the welding ring body. In various embodiments, the ratio of mass of the stent body to mass of the reaction layer can be 4: 1, 5: 1, 6: 1, 7: 1, 8: 1, 9: 1, 10: 1, 11: 1, 12: 1, 13: 1, 14: 1, 15: 1, 16: 1, 17: 1, 18: 1, 19: 1, 20: 1, and so forth.
In an embodiment of the invention, the mass ratio of the copper-phosphorus brazing filler metal to the brazing flux in the welding ring body is (4-8): 1, and preferably (4.5-8): 1.
In various embodiments, the mass ratio of brazing filler metal to brazing flux in the ring body can be 4: 1, 4.5: 1, 5: 1, 5.5: 1, 6: 1, 6.5: 1, 7: 1, 7.5: 1, 8: 1, etc.
In a specific embodiment of the invention, the copper-phosphorus brazing filler metal comprises the following components in percentage by mass: 5-8% of phosphorus, 0-20% of silver and the balance of copper.
In a specific embodiment of the invention, the brazing flux comprises the following components in percentage by mass: 30-70% of potassium fluoborate, 5-20% of boric anhydride, 5-60% of borax and 5-20% of potassium bifluoride.
In a preferred embodiment of the invention, the copper-phosphorus welding ring comprises, by mass, 70% -80% of copper-phosphorus brazing filler metal, 10% -15% of brazing flux and 5% -20% of copper sulfate.
As in the various embodiments, the copper phosphorus braze may be used in amounts of 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, etc.; the amount of flux may be 10%, 11%, 12%, 13%, 14%, 15%, etc.; copper sulfate may be used in amounts of 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, etc.
In a specific embodiment of the invention, the copper-phosphorus solder, the flux and the copper sulfate are all in powder form. Further, the particle sizes of the copper-phosphorus brazing filler metal, the brazing flux and the copper sulfate are 100 meshes or smaller. Wherein, the 100-mesh fine means that the particle size is 100 mesh or less than 100 mesh.
In a specific embodiment of the invention, the copper sulfate is anhydrous copper sulfate.
The invention also provides a preparation method of any one of the copper-phosphorus welding rings, which comprises the following steps:
and respectively filling the mixture of the copper-phosphorus brazing filler metal and the brazing flux and the copper sulfate into a mold of the copper-phosphorus welding ring, and performing compression molding.
The invention can obtain the preformed copper-phosphorus welding ring by pressing at room temperature, and has mature preparation process, convenient operation, good stability and lower preparation process cost.
In the specific embodiment of the invention, when one side end face of the welding ring body is provided with the reaction layer, the preparation method comprises the following steps:
firstly, filling a mixture of copper-phosphorus brazing filler metal and brazing flux into a mould of the copper-phosphorus welding ring, then filling copper sulfate into the mould, and performing compression molding; or, filling copper sulfate into the mold of the copper-phosphorus welding ring, then filling the mixture of copper-phosphorus brazing filler metal and brazing flux, and pressing and forming.
In the specific embodiment of the invention, when the two side end faces of the welding ring body are both provided with the reaction layers, the preparation method comprises the following steps:
firstly, 1/3-1/2 parts of copper sulfate is filled into a mould of the copper-phosphorus welding ring, then a mixture of copper-phosphorus brazing filler metal and a soldering flux is filled, and the balance of copper sulfate is filled, and the copper-phosphorus welding ring is formed by pressing.
And selecting a cold pressing die meeting the size requirement according to the specification of the welding ring.
In a specific embodiment of the invention, the preparation method of the copper-phosphorus brazing filler metal comprises the following steps: preparing the copper-phosphorus brazing filler metal by an atomization method according to the component proportion, and then sieving the brazing filler metal by a 100-mesh sieve.
In a specific embodiment of the present invention, the method for preparing the flux comprises: the brazing flux is prepared according to the component proportion by adopting a mechanical mixing method, and then the brazing flux passes through a 100-mesh screen.
In a specific embodiment of the present invention, the copper sulfate is previously treated through a 100-mesh sieve.
In a specific embodiment of the present invention, the mixture is mixed in a manner comprising: and (3) proportionally placing the copper-phosphorus brazing filler metal and the brazing flux into a mixer to be mixed for 60-90 min, such as 90 min.
The invention also provides application of any one of the copper-phosphorus welding rings in steel-copper or steel-steel tubular metal brazing.
The copper phosphorus welding ring disclosed by the invention is used in the field of brazing, and the brazing seam connection strength can be greatly improved.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, the end faces of one side or two sides of the welding ring body are provided with the copper sulfate reaction layer, based on contact reaction, in the heating process, copper sulfate firstly reacts with the steel matrix to generate a layer of copper on the surface, so that the reaction of P and Fe in the copper-phosphorus brazing filler metal to produce a brittle compound is effectively prevented, and the brazing seam connection strength is improved;
(2) the preparation process of the copper-phosphorus welding ring is mature, convenient and fast to operate, good in stability and low in preparation process cost;
(3) the copper-phosphorus welding ring can be used for brazing steel-copper or steel-steel tubular metal, can greatly improve the connection strength of a brazing seam, and widens the application range of copper-phosphorus brazing filler metal.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic view of a brazing ring according to an embodiment of the present invention; wherein (a) is a cross-sectional view in the A-A direction of (b);
FIG. 2 is a schematic view of a brazing ring according to another embodiment of the present invention; wherein (a) is a sectional view in the B-B direction of (B);
FIG. 3 is a microstructure diagram of the brazing seam interface after the brazing ring is welded according to an embodiment of the present invention.
Reference numerals:
1-a first reaction layer; 2, 4-welding a ring body; 3-a second reaction layer;
5-reaction layer.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. 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. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
FIG. 1 is a schematic view of a brazing ring according to an embodiment of the present invention; in FIG. 1, (a) is a sectional view taken along the line A-A of (b). As shown in fig. 1, the brazing ring of the present embodiment includes a brazing ring body 2 and reaction layers disposed on two side end surfaces of the brazing ring body 2. The reaction layers are a first reaction layer 1 and a second reaction layer 3 respectively. The welding ring body 2 comprises copper-phosphorus brazing filler metal and brazing flux; the first reaction layer 1 and the second reaction layer 3 each include copper sulfate.
Specifically, the end sections of the first reaction layer 1 and the second reaction layer 3 are correspondingly attached to the end section of the weld ring body 2.
Further, the welding ring body 2 is of a circular ring structure. The first reaction layer 1 and the second reaction layer 3 are annular structural layers corresponding to the annular structures. The inner diameter, the outer diameter, the wall thickness, the height and the like of the welding ring body 2 can be adjusted according to the requirements of practical application scenes.
As in the specific embodiment, the inner diameter of the weld ring body 2 may be 6mm to 30mm, the outer diameter may be 12mm to 40mm, the wall thickness may be 2mm to 5mm, and the height may be 5mm to 10 mm.
The ratio of the mass of the weld ring body 2 to the mass of the first reaction layer 1 to the mass of the second reaction layer 3 is (4-20): 1, preferably (5-15): 1.
The mass ratio can be adjusted according to actual requirements to adjust the thickness of the reaction layer on the end face of the welding ring body 2. In various embodiments, the ratio of the mass of the welding ring body 2 to the sum of the mass of the first reaction layer 1 and the mass of the second reaction layer 3 can be 4: 1, 5: 1, 6: 1, 7: 1, 8: 1, 9: 1, 10: 1, 11: 1, 12: 1, 13: 1, 14: 1, 15: 1, 16: 1, 17: 1, 18: 1, 19: 1, 20: 1, and so on.
In the embodiment of the invention, the mass ratio of the copper-phosphorus brazing filler metal to the brazing flux in the welding ring body 2 is (4-8): 1, and preferably (4.5-8): 1. The copper-phosphorus brazing filler metal comprises the following components in percentage by mass: 5-8% of phosphorus, 0-20% of silver and the balance of copper. The brazing flux comprises the following components in percentage by mass: 30-70% of potassium fluoborate, 5-20% of boric anhydride, 5-60% of borax and 5-20% of potassium bifluoride.
In a preferred embodiment of the invention, the copper-phosphorus welding ring comprises, by mass, 70% -80% of copper-phosphorus brazing filler metal, 10% -15% of brazing flux and 5% -20% of copper sulfate.
FIG. 2 is a schematic view of a brazing ring according to another embodiment of the present invention; in FIG. 2, (a) is a sectional view taken along the line B-B of (B). As shown in fig. 2, the brazing ring of the present embodiment includes a brazing ring body 4 and a
Specifically, the end section of the
Further, the welding ring body 4 is of a circular ring structure. The
As in the specific embodiment, the inner diameter of the weld ring body 4 may be 6mm to 30mm, the outer diameter may be 12mm to 40mm, the wall thickness may be 2mm to 5mm, and the height may be 5mm to 10 mm.
The mass ratio of the weld ring body 4 to the
The mass ratio can be adjusted according to actual requirements to adjust the thickness of the
In the embodiment of the invention, the mass ratio of the copper-phosphorus brazing filler metal to the brazing flux in the welding ring body 4 is (4-8): 1, and preferably (4.5-8): 1. The copper-phosphorus brazing filler metal comprises the following components in percentage by mass: 5-8% of phosphorus, 0-20% of silver and the balance of copper. The brazing flux comprises the following components in percentage by mass: 30-70% of potassium fluoborate, 5-20% of boric anhydride, 5-60% of borax and 5-20% of potassium bifluoride.
In a preferred embodiment of the invention, the copper-phosphorus welding ring comprises, by mass, 70% -80% of copper-phosphorus brazing filler metal, 10% -15% of brazing flux and 5% -20% of copper sulfate.
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