CN111004941B - Corrosion-resistant copper alloy material for plate heat exchanger and preparation method thereof - Google Patents
Corrosion-resistant copper alloy material for plate heat exchanger and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a corrosion-resistant copper alloy material for a plate heat exchanger and a preparation method thereof, belonging to the technical field of material preparation and processing. The invention relates to a corrosion-resistant copper alloy material for a plate heat exchanger, which comprises the following components in percentage by weight: cu 70% -80%; al 1% -5%; 0.1 to 3 percent of Sns; 0.02 to 0.3 percent of Ce; b0.01% -0.05%; 0.05 to 0.2 percent of P; the balance of Zn and a small amount of unavoidable impurities. According to the invention, copper and zinc are used as main raw materials, trace elements such as aluminum, boron, cerium, tin and phosphorus are added into the copper and zinc, and the copper alloy material with high strength, good heat conductivity and outstanding corrosion resistance is obtained through reasonable regulation and control of alloy components.
Description
Technical Field
The invention belongs to the technical field of material preparation and processing, and particularly relates to a corrosion-resistant copper alloy material for a plate heat exchanger and a preparation method thereof.
Background
The heat exchanger is a universal device widely applied to the industries of chemical industry, medicine, metallurgy, refrigeration and the like. At present, a Plate Heat Exchanger (PHE) becomes high-efficiency and compact Heat exchange equipment, is particularly suitable for liquid-liquid Heat transfer under the condition of turbulence, and is an ideal choice for central heating, refrigeration and air conditioning and domestic water Heat exchange. The PHE also has better corrosion resistance when being used as an internal structural component to keep certain strength. Meanwhile, the alloy is required to have higher plasticity and good forming performances such as deep drawing, bending and the like. At present, stainless steel and titanium plates occupy the dominant position in plate material selection of a plate heat exchanger, but cold medium water sources contain Mg to a certain degree2+、Ca2+When the scale-prone substances are removed by cheap chloride, the balance of Cl-is inevitably existed in the water medium. The stainless steel is difficult to overcome the defects of crevice corrosion, relatively low bacterial growth on the plate surface, relatively low heat conduction efficiency and the like under the Cl-water quality, and the titanium material serving as the plate material of the plate heat exchanger is troubled by the problems of short supply of the global titanium material, dependence on imported products, high price and the like, so that the dilemma of corrosion of the plate and overhigh initial cost of the products is caused. The use of plate heat exchangers in the oil, coastal power generation, marine engineering and energy industries is therefore limited.
Copper alloy has good ductility and high thermal conductivity, and is a heat conducting material widely used in heat sinks. The prior technical means mainly comprise: CN100467638C, CN102470741A, CN101717969, CN107022695B, etc., the copper alloy materials involved in the above techniques are difficult to simultaneously consider various performances such as high thermal conductivity, high strength, corrosion resistance, etc., and the production process of the copper alloy involved in the above technical means is still the traditional smelting-casting-annealing-forging, and the process has low production efficiency, low yield, large energy consumption, and is difficult to realize continuous production.
Disclosure of Invention
The invention aims to provide a corrosion-resistant copper alloy material for a plate heat exchanger and a preparation method thereof, and aims to solve the problem that the copper alloy material for the plate heat exchanger in the prior art is difficult to simultaneously give consideration to high heat conductivity, high strength and corrosion resistance.
In order to achieve the above object, the present invention is realized by:
the corrosion-resistant copper alloy material for the plate heat exchanger comprises the following components in percentage by weight:
the balance of Zn and a small amount of unavoidable impurities.
Further, the paint comprises the following components in percentage by weight: cu 75-77%, Al 1.5-2.5%, Sn 0.3-0.7%, Ce 0.02-0.08%, B0.01-0.03%, P0.08-0.12%, and Zn and small amount of inevitable impurities in balance.
On the other hand, the invention provides a preparation method of the corrosion-resistant copper alloy material for the plate heat exchanger, which comprises the following steps:
a) weighing the raw materials according to the component proportion, wherein P, Ce and B are added in the form of intermediate alloy;
b) placing Cu in an induction smelting furnace, heating to 1200-1300 ℃ to melt the raw materials, cooling to 1080-1150 ℃ after the raw materials are melted, then sequentially adding Al, a copper-boron intermediate alloy, a copper-cerium intermediate alloy, a copper-phosphorus intermediate alloy and Sn, cooling to 900-950 ℃ after the Sn is completely dissolved, adding Zn, then heating to 1050-1120 ℃ to smelt, adding a slagging agent into the alloy melt during smelting, and covering the surface of the alloy melt with charcoal to prevent the alloy melt from being oxidized;
c) introducing the alloy melt into a water-cooled crystallizer for upward continuous casting by using a tungsten rod, and obtaining a copper alloy rod after the alloy solution is directionally solidified;
d) and extruding and cold rolling the obtained copper alloy rod, and then annealing the cold-rolled copper alloy strip to obtain the copper alloy material.
Further, the annealing treatment temperature in the step d) is 300-400 ℃, and the annealing time is 2-3 h.
Further, the cold rolling in the step d) is room temperature cold rolling.
Further, in the step c), a tungsten rod with the diameter of 5 mm-50 mm is inserted into a proper position below the liquid level of the copper alloy liquid, an upward-drawing mechanical device is started after 1min to draw out the tungsten rod, the upward-drawing speed is controlled to be 1-6 mm/s to draw out the copper alloy rod, and the temperature difference of inlet water and outlet water of the crystallizer is controlled not to exceed 10 ℃, the temperature of the inlet water is controlled to be 25-30 ℃, and the temperature of the outlet water is controlled to be 35-40 ℃.
Compared with the prior art, the invention has the following beneficial effects:
from the perspective of improving material performance, the copper alloy material with high strength, good heat conduction performance and outstanding corrosion resistance is obtained by taking copper and zinc as main raw materials and adding trace elements such as aluminum, boron, cerium, tin, phosphorus and the like into the copper alloy material through reasonable regulation and control of alloy components; and the high-efficiency, low-energy-consumption and high-yield production of the corrosion-resistant copper alloy material for the plate heat exchanger is realized by the process of sequentially combining the processes of extrusion, rolling, annealing and the like through upward continuous casting.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a plot of weight gain over time for the salt spray test of example 1 of the present invention.
FIG. 2 is a photograph of a sample after etching in example 1 of the present invention.
FIG. 3 is a graph of corrosion weight gain over time for example 2 of the present invention.
FIG. 4 is a graph of corrosion weight gain over time for example 3 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
According to an embodiment of the invention, the corrosion-resistant copper alloy material for the plate heat exchanger comprises the following components in percentage by weight:
the balance of Zn and a small amount of unavoidable impurities.
As a preferable scheme of the embodiment of the invention, the corrosion-resistant copper alloy material for the plate heat exchanger comprises the following components in percentage by weight: cu 75-77%, Al 1.5-2.5%, Sn 0.3-0.7%, Ce 0.02-0.08%, B0.01-0.03%, P0.08-0.12%, and Zn and small amount of inevitable impurities in balance.
The preparation method of the corrosion-resistant copper alloy material for the plate heat exchanger provided by the embodiment of the invention comprises the following steps of:
a) weighing the raw materials according to the component proportion, wherein P, Ce and B are added in the form of intermediate alloy;
b) placing Cu in an induction smelting furnace, heating to 1200-1300 ℃ to melt the raw materials, cooling to 1080-1150 ℃ after the raw materials are melted, then sequentially adding Al, a copper-boron intermediate alloy, a copper-cerium intermediate alloy, a copper-phosphorus intermediate alloy and Sn, cooling to 900-950 ℃ after the Sn is completely dissolved, adding Zn, then heating to 1050-1120 ℃ to smelt, adding a slagging agent into the alloy melt during smelting, and covering the surface of the alloy melt with charcoal to prevent the alloy melt from being oxidized;
c) introducing the alloy melt into a water-cooled crystallizer for upward continuous casting by using a tungsten rod, and obtaining a copper alloy rod after the alloy solution is directionally solidified;
d) and extruding and cold rolling the obtained copper alloy rod, and then annealing the cold-rolled copper alloy strip to obtain the copper alloy material.
e) And d), performing punch forming on the copper alloy material obtained in the step d) to obtain the corrosion-resistant copper alloy plate type heat exchanger plate material.
In the embodiment of the invention, the annealing treatment temperature in the step d) is 300-400 ℃, and the annealing time is 2-3 h. The cold rolling is room temperature cold rolling.
In the step c), a tungsten rod with the diameter of 5-50 mm is inserted into a proper position below the liquid level of the copper alloy liquid, an upward-drawing mechanical device is started to draw the tungsten rod out after 1min, the upward-drawing speed is controlled to be 1-6 mm/s to draw the copper alloy rod out, and the temperature difference between inlet water and outlet water of a crystallizer is controlled not to exceed 10 ℃, the temperature of inlet water is controlled to be 25-30 ℃, and the temperature of outlet water is controlled to be 35-40 ℃.
In the invention, the addition of the boron element can improve the strength of the copper alloy and enhance the dezincification corrosion resistance of the alloy; the appropriate tin content can also inhibit the dezincification corrosion of brass; the corrosion resistance of the copper alloy in the solution can be effectively improved by adding cerium; the addition of aluminum improves the strength and corrosion resistance of the copper alloy; the phosphorus element can effectively improve the mechanical property of the copper alloy.
The method effectively improves the yield of the product by reasonably controlling the process flow, and the yield of the copper alloy plate heat exchanger plate in the embodiment of the invention is more than 95%; by controlling the process, continuous production can be realized, and the production efficiency is greatly improved; in the process, the copper alloy rod is crystallized through the crystallizer, the copper alloy rod has uniform components and extremely high porosity, and a large amount of energy consumed by die baking and ingot casting heat treatment in the casting production process is saved; the copper alloy has high thermal conductivity which can reach 280 w/mk-340 w/mk, tensile strength which can reach 450 MPa-900 MPa and low corrosion rate, and the average corrosion rate of the copper alloy soaked in 3.5 percent sodium chloride solution for 10 days is only 0.030 g/(m) g2h)～0.075g/(m2h)。
The following is a detailed description of specific embodiments.
Example 1
The corrosion-resistant copper alloy material for the plate heat exchanger in the embodiment comprises the following components in percentage by weight:
75% of copper, 2.3% of aluminum, 0.7% of tin, 0.02% of cerium, 0.01% of boron, 0.015% of phosphorus, and the balance of zinc and a small amount of unavoidable impurities. The preparation method comprises the following steps:
(1) the alloy is prepared according to the percentage of each element, copper is 75 percent, aluminum is 2.3 percent, tin is 0.7 percent, cerium is 0.02 percent, boron is 0.01 percent, phosphorus is 0.015 percent, and zinc is the rest, wherein the three elements of phosphorus, cerium and boron are added in the form of intermediate alloy.
(2) Firstly, placing copper in an induction smelting furnace, heating to 1250 ℃, cooling to 1080 ℃ after the copper is melted, adding aluminum, and sequentially adding a copper-boron intermediate alloy, a copper-cerium intermediate alloy, a copper-phosphorus intermediate alloy and tin into molten metal after the aluminum is completely dissolved. And after the tin is completely dissolved, cooling to 930 ℃, adding zinc into the molten metal, heating to 1050 ℃, adding a refining agent and a slagging agent into the molten metal, and covering charcoal on the surface of the molten alloy to prevent the molten alloy from being oxidized.
(3) The copper alloy liquid was introduced into a water-cooled crystallizer for upward continuous casting using a tungsten rod having a diameter of 25mm, and the copper alloy rod was taken out of the crystallizer at a speed of 25 cm/min.
(4) The copper alloy rods are guided into the extrusion wheel by means of a guide device, and the copper alloy rods are formed into a copper alloy strip (hereinafter referred to simply as "copper strip") having a thickness of 10mm and a width of 50mm by the extrusion wheel.
(5) And (4) guiding the copper strip into a roller for cold rolling to obtain the copper strip with the thickness of 2 mm.
(6) And (3) putting the rolled copper strip into a heating furnace for annealing treatment, wherein the heating temperature is 300-400 ℃, and the heat preservation time is 2-3 h.
(7) And cleaning the surface of the copper strip, and then performing punch forming on the copper strip by using a punch press to obtain a final product.
In the salt spray test, the curve of the weight gain of the copper alloy material obtained in example 1 of the present invention with time is shown in fig. 1, fig. 2 is a photograph of a sample of the copper alloy material obtained in example 1 of the present invention after corrosion, and it can be seen from the corrosion result in fig. 2 that the surface corrosion degree of the copper alloy material obtained in the present invention after corrosion is not severe, indicating that the corrosion resistance is better. The thermal conductivity of the copper alloy obtained by the embodiment under the control of material composition and process conditions can reach about 295wThe average corrosion weight gain rate of the alloy after 5 days of salt spray test at 35 ℃ is 0.0162 g/(m) and the tensile strength of the alloy is 830MPa2h)。
Example 2
The corrosion-resistant copper alloy material for the plate heat exchanger in the embodiment comprises the following components in percentage by weight:
72% of copper, 2% of aluminum, 0.5% of tin, 0.05% of cerium, 0.03% of boron, 0.01% of phosphorus, and the balance of zinc and a small amount of unavoidable impurities. The preparation method comprises the following steps:
(1) the material is prepared according to the percentage of each element, copper is 72 percent, aluminum is 2 percent, tin is 0.5 percent, cerium is 0.05 percent, boron is 0.03 percent, phosphorus is 0.01 percent, and zinc is the rest, wherein the three elements of phosphorus, cerium and boron are added in the form of intermediate alloy.
(2) Firstly, placing copper in an induction melting furnace, heating to 1250 ℃, cooling to 1100 ℃ after the copper alloy is melted, adding aluminum, and sequentially adding a copper-boron intermediate alloy, a copper-cerium intermediate alloy, a copper-phosphorus intermediate alloy and tin into molten metal after the aluminum is completely dissolved. And after the tin is completely dissolved, cooling to 900 ℃, adding zinc and the molten metal, heating to 1100 ℃, then adding a refining agent and a slagging agent into the molten metal, and covering charcoal on the surface of the alloy liquid to prevent the alloy liquid from being oxidized.
(3) The copper alloy liquid was introduced into a water-cooled crystallizer for upward continuous casting using a tungsten rod having a diameter of 30mm, and the copper alloy rod was taken out of the crystallizer at a speed of 20 cm/min.
(4) The copper alloy rod is guided into the extrusion wheel through a guide device, and the copper alloy rod forms a copper strip with the thickness of 10mm and the width of 60mm under the action of the extrusion wheel.
(5) And (4) guiding the copper strip into a roller for cold rolling to obtain the copper strip with the thickness of 2 mm.
(6) And (3) putting the rolled copper strip into a heating furnace for annealing treatment, wherein the heating temperature is 300-400 ℃, and the heat preservation time is 2-3 h.
(7) And cleaning the surface of the copper strip, and then performing punch forming on the copper strip by using a punch press to obtain a final product.
The corrosion gain of the copper alloy prepared in example 2 of the present invention is shown in the curve with time as shown in fig. 3. This example is a materialThe heat conductivity of the obtained copper alloy can reach about 340w/mk under the control of components and process conditions, the tensile strength is 600MPa, and the average corrosion rate after the copper alloy is soaked in a sodium chloride solution with the mass fraction of 3.5% for 10 days at room temperature is only 0.045 g/(m)2h)。
Example 3
The corrosion-resistant copper alloy material for the plate heat exchanger in the embodiment comprises the following components in percentage by weight:
76% of copper, 3% of aluminum, 0.5% of tin, 0.05% of cerium, 0.05% of boron, 0.01% of phosphorus, and the balance of zinc and a small amount of unavoidable impurities. The preparation method comprises the following steps:
(1) the material is prepared according to the percentage of each element, copper is 76%, aluminum is 3%, tin is 0.5%, cerium is 0.05%, boron is 0.05%, phosphorus is 0.01%, and zinc is the rest, wherein the three elements of phosphorus, cerium and boron are added in the form of intermediate alloy.
(2) Firstly, placing copper in an induction melting furnace, heating to 1200 ℃, cooling to 1120 ℃ after the copper alloy is melted, adding aluminum, and sequentially adding a copper-boron intermediate alloy, a copper-cerium intermediate alloy, a copper-phosphorus intermediate alloy and tin into molten metal after the aluminum is completely dissolved. And after the tin is completely dissolved, cooling to 920 ℃, adding zinc and the molten metal, heating to 1080 ℃, then adding a refining agent and a slagging agent into the molten metal, and covering charcoal on the surface of the molten alloy to prevent the molten alloy from being oxidized.
(3) The copper alloy liquid was introduced into a water-cooled crystallizer for upward continuous casting using a tungsten rod having a diameter of 20mm, and the copper alloy rod was taken out of the crystallizer at a rate of 35 cm/min.
(4) The copper alloy rod is guided into the extrusion wheel by a guide device, and the copper alloy rod forms a copper strip with the thickness of 10mm and the width of 45mm under the action of the extrusion wheel.
(5) And (4) guiding the copper strip into a roller for cold rolling to obtain the copper strip with the thickness of 2 mm.
(6) And (3) putting the rolled copper strip into a heating furnace for annealing treatment, wherein the heating temperature is 300-400 ℃, and the heat preservation time is 2-3 h.
(7) And cleaning the surface of the copper strip, and then performing punch forming on the copper strip by using a punch press to obtain a final product.
The corrosion gain of the copper alloy prepared in example 3 of the present invention is shown in the curve with time as shown in fig. 4. The heat conductivity of the copper alloy obtained by the method under the control of material components and process conditions can reach about 280w/mk, the tensile strength is 800MPa, and the average corrosion rate after the copper alloy is soaked in a sodium chloride solution with the mass fraction of 3.5% for 15 days at 50 ℃ is only 0.087g/(m & lt 7 & gt)2h)。
Example 4
The corrosion-resistant copper alloy material for the plate heat exchanger in the embodiment comprises the following components in percentage by weight:
77% of copper, 1.5% of aluminum, 0.3% of tin, 0.02% of cerium, 0.02% of boron, 0.01% of phosphorus, and the balance of zinc and a small amount of unavoidable impurities. The preparation method comprises the following steps:
(1) the raw materials are mixed according to the percentage of each element, copper is 77 percent, aluminum is 1.5 percent, tin is 0.3 percent, cerium is 0.02 percent, boron is 0.02 percent, phosphorus is 0.01 percent, and zinc is the rest, wherein the three elements of phosphorus, cerium and boron are added in the form of intermediate alloy.
(2) Firstly, placing copper in an induction smelting furnace, heating to 1200 ℃, cooling to 1090 ℃ after the copper alloy is melted, adding aluminum, and sequentially adding a copper-boron intermediate alloy, a copper-cerium intermediate alloy, a copper-phosphorus intermediate alloy and tin into molten metal after the aluminum is completely dissolved. And after the tin is completely dissolved, cooling to 950 ℃, adding zinc and the molten metal, heating to 1120 ℃, adding a refining agent and a slagging agent into the molten metal, and covering charcoal on the surface of the molten alloy to prevent the molten alloy from being oxidized.
(3) The copper alloy liquid was introduced into a water-cooled crystallizer for upward continuous casting using a tungsten rod having a diameter of 40mm, and the copper alloy rod was taken out of the crystallizer at a speed of 10 cm/min.
(4) The copper alloy rods are guided into the extrusion wheel by a guide device, and the copper alloy rods form a copper strip with the thickness of 10mm and the width of 120mm under the action of the extrusion wheel.
(5) And (4) guiding the copper strip into a roller for cold rolling to obtain the copper strip with the thickness of 2 mm.
(6) And (3) putting the rolled copper strip into a heating furnace for annealing treatment, wherein the heating temperature is 300-400 ℃, and the heat preservation time is 2-3 h.
(7) And cleaning the surface of the copper strip, and then performing punch forming on the copper strip by using a punch press to obtain a final product.
The heat conductivity of the copper alloy obtained by the method under the control of material components and process conditions can reach about 300w/mk, the tensile strength is 750MPa, and the average corrosion rate after soaking the copper alloy in a sodium chloride solution with the mass fraction of 3.5% for 5 days at 75 ℃ is only 0.093g/(m & lt 3 & gt)2h)。
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that are not thought of through the inventive work should be included in the scope of the present invention.
Claims (2)
1. The corrosion-resistant copper alloy material for the plate heat exchanger is characterized by comprising the following components in percentage by weight:
the balance of Zn and a small amount of inevitable impurities;
the preparation method of the corrosion-resistant copper alloy material for the plate heat exchanger comprises the following steps:
a) weighing the raw materials according to the component proportion, wherein P, Ce and B are added in the form of intermediate alloy;
b) placing Cu in an induction smelting furnace, heating to 1200-1300 ℃ to melt the raw materials, cooling to 1080-1150 ℃ after the raw materials are melted, then sequentially adding Al, a copper-boron intermediate alloy, a copper-cerium intermediate alloy, a copper-phosphorus intermediate alloy and Sn, cooling to 900-950 ℃ after the Sn is completely dissolved, adding Zn, then heating to 1050-1120 ℃ to smelt, adding a slagging agent into the alloy melt during smelting, and covering the surface of the alloy melt with charcoal to prevent the alloy melt from being oxidized;
c) introducing the alloy melt into a water-cooled crystallizer for upward continuous casting by using a tungsten rod, and obtaining a copper alloy rod after the alloy solution is directionally solidified;
d) extruding and cold rolling the obtained copper alloy rod, and then annealing the cold-rolled copper alloy strip to obtain the copper alloy material;
the annealing treatment temperature of the step d) is 300-400 ℃, and the annealing time is 2-3 h;
the cold rolling in the step d) is room temperature cold rolling;
in the step c), a tungsten rod with the diameter of 5-50 mm is inserted into a proper position below the liquid level of the copper alloy liquid, an upward drawing mechanical device is started after 1min to draw out the tungsten rod, the upward drawing speed is controlled to be 1-6 mm/s to draw out the copper alloy rod, and the temperature difference of inlet water and outlet water of the crystallizer is controlled to be not more than 10 ℃, the temperature of inlet water is 25-30 ℃, and the temperature of outlet water is 35-40 ℃ in the process.
2. The corrosion-resistant copper alloy material for a plate heat exchanger according to claim 1, which consists of, in weight percent: 75 to 77 percent of Cu, 1.5 to 2.5 percent of Al, 0.3 to 0.7 percent of Sn, 0.02 to 0.08 percent of Ce, 0.01 to 0.03 percent of B, 0.08 to 0.12 percent of P, and the balance of Zn and a small amount of inevitable impurities.
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