CN111074089A - Wear-resistant corrosion-resistant multi-element manganese aluminum bronze brazing alloy and preparation method thereof - Google Patents
Wear-resistant corrosion-resistant multi-element manganese aluminum bronze brazing alloy and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of alloy manufacturing, and particularly relates to a wear-resistant corrosion-resistant multi-element manganese-aluminum bronze brazing alloy and a preparation method thereof. The wear-resistant corrosion-resistant multi-element manganese aluminum bronze brazing alloy comprises the following components in parts by weight: 7-10% of Al; 8-11% of Mn; 1.5 to 3.0 percent of Fe; 1.5 to 2.5 percent of Ni; 0.005-0.03% of B; 0.05 to 0.1 percent of Y; 0.08-0.20% of La, and the weight ratio of the three elements of Y and La is 1: 10: 15-1: 3: 6, and other impurities are less than or equal to 0.5 percent. The balance being Cu. The invention is composed of Al, Mn, Fe, Ni, B, Y, La and Cu, the casting temperature is equal to or lower than 1050 ℃, and the mechanical property is good. The alloy material is used for cladding the inner wall of the cylinder in the hydraulic support, has bright surface, less deformation, hardness of more than HB240, good wear resistance and corrosion resistance, has the service life of 2 times that of the raw materials in the prior operation, and is still normally used.
Description
Technical Field
The invention belongs to the field of alloy manufacturing, and particularly relates to a wear-resistant corrosion-resistant multi-element manganese-aluminum bronze brazing alloy and a preparation method thereof.
Background
At present, wear-resistant copper parts and brazing materials thereof used on cylinders, bearings, valves, rollers and the like are required to adapt to harsh environments of high temperature, much dust, large load, corrosion, abrasion and the like. The materials used are typically aluminum bronze (e.g., ZQAL9-4, composition of Al 8-10%, Fe 2-4%, balance Cu), tin bronze (e.g., ZQSn10-1, composition of Sn 9-11%, P0.6-1.2%, balance Cu), etc. The ZQAL9-4 alloy has high dry grinding coefficient and poor heat conductivity, and is easy to generate dealuminization corrosion in environmental media, so the service life of the alloy is low. While ZQSn10-1 has a lower strength and toughness and a greatly reduced wear resistance in the case of poor lubrication. The use of ZCuAl8Mn13Fe3Ni2 alloy (Mn: 11.5-14%, Al 7-8.5%, Fe: 2.5-4%, Ni: 1.8-2.5%, balance Cu) does not satisfy the above-mentioned harsh environmental conditions with respect to wear resistance, corrosion resistance, etc. In addition, the existing smelting process generates more oxidation inclusions, the structure is thick, and the excellent mechanical property is influenced.
Patent CN1239148A high manganese aluminum bronze and processing method, its characterized in that: the chemical components of the material are (wt%) Cu 65-85%, Mn 10-18%, Al 5.0-9.0%, Ni 1.0-3.0%, Fe 2.0-4.0%, Ti 0.01-1.0% and Re 0.2-0.5%, and through heat treatment, heating to 850 +/-10 deg.C, holding for 40 min and quenching. Then tempering at 200 +/-10 ℃. Mechanical properties,. sigma.b.. 765MPa,. delta5＞4,ak＝140j/cm2HB 180-; if the weld is cast after overlaying, its strength and hardness will be much lower. In addition, the alloy of the patent has no wear resistance, and the effect data of a corrosion resistance experiment show that the alloy has no advantages in the aspect.
Disclosure of Invention
The invention aims to provide a wear-resistant corrosion-resistant multi-element manganese aluminum bronze brazing alloy and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the wear-resistant corrosion-resistant multi-element manganese aluminum bronze brazing alloy comprises the following components in parts by weight: 7-10% of Al; 8-11% of Mn; 1.5 to 3.0 percent of Fe; 1.5 to 2.5 percent of Ni; 0.005-0.03% of B; 0.05 to 0.1 percent of Y; 0.08-0.20% of La, and the weight ratio of the three elements of B, Y and La is 1: 10: 15-1: 3: 6, and other impurities are less than or equal to 0.5 percent. The balance being Cu.
The application also comprises a preparation method of the wear-resistant corrosion-resistant multi-element manganese aluminum bronze brazing alloy, which comprises the following steps:
① charging, namely placing dry charcoal at the bottom of the crucible, and adding cathode copper and electrolytic manganese at the same time according to the proportion of Cu to Mn being less than or equal to 2, wherein the charging material needs to be compact;
② supplying power to increase temperature, increasing power to melt the furnace charge rapidly, heating to 1300-;
③ cutting off power, adding the rest copper, cooling to 1050-;
④ heating to 1100 deg.C and 1150 deg.C, keeping the temperature, introducing argon for 10 min, and analyzing the components in front of the furnace;
⑤, detecting the quality of the molten metal, pouring the molten metal into a graphite crucible preheated to the temperature of 200-;
⑥ horizontal continuous casting into wire blank wire rod;
⑦ stretching and annealing, adopting multi-mode continuous stretching, bright protection annealing, annealing temperature of 700 ℃, keeping temperature for 3 hours, and air cooling.
⑧ peeling and stretching, removing surface defects, stretching to obtain final product, inspecting, packaging, and storing.
The wear-resistant corrosion-resistant multi-element manganese aluminum bronze brazing alloy obtained by the method has the advantages that the alloy structure α is refined, and the K phase is in a small granular shape and is uniformly distributed.
The wear-resistant and corrosion-resistant multi-element manganese aluminum bronze brazing alloy obtained by the method has the advantages of less oxidation inclusions, compact structure and low matrix hardness.
The wear-resistant corrosion-resistant multi-element manganese aluminum bronze brazing alloy obtained by the method has the Brinell hardness of HB250-280, the tensile strength of 620-670Mpa, the elongation of 15-20%, the solid phase point of 965 ℃ and the liquid phase point of 985 ℃.
The dry friction coefficient of the wear-resistant corrosion-resistant multi-element manganese aluminum bronze brazing alloy obtained by the method at room temperature is less than 0.28, and the abrasion loss is less than 9.1 mg.
The friction coefficient of the wear-resistant corrosion-resistant multi-element manganese aluminum bronze brazing alloy obtained by the method under oil lubrication at room temperature is less than 0.11, and the abrasion loss is less than 3.5 mg.
The corrosion amount of the wear-resistant corrosion-resistant multi-element manganese aluminum bronze brazing alloy obtained by the method in a dynamic seawater corrosion experiment is less than 15.1(g/m 2).
The potential of the wear-resistant and corrosion-resistant multi-element manganese-aluminum bronze brazing alloy electrode obtained by the method is higher than-0.2430 mv.
Compared with the prior art, the invention has the beneficial effects that:
according to the principle of multicomponent strengthening of alloy materials, aluminum and manganese in multicomponent manganese aluminum bronze are main elements determining the alloy structure and performance, the main microstructure comprises a matrix α phase, a second phase β and a second phase k are equal, Mn reduces the solid solubility of A1 in α -Cu phase, can stabilize β phase, and postpones or even prevents eutectoid transformation (β - α + gamma-gamma2) When iron in the alloy reaches a certain value, a K-phase compound is formed, and nickel has the function of preventing 'slow cooling brittleness'.
The melting point of iron is as high as 1538 ℃, which is far higher than that of copper as a base material, the solid solubility of iron in copper is extremely low, the solubility of iron in copper liquid is 3.5% at 1050 ℃, the solubility of iron at 635 ℃ is reduced to 0.15%, the free dissolving energy of iron is high, and iron is not easy to combine with copper, iron exceeding the solid solubility exists in iron-rich phase particles, the average microhardness of the iron-rich phase particles is Hv659, which is about 5 times of that of the base body, and the iron-rich phase particles are embedded on the base body to form hard particles, so that the alloy becomes brittle. The solubility of manganese in copper is high, manganese is easy to dissolve in copper at high temperature, the solubility of iron in copper is extremely low, but the solid solubility of iron in copper-manganese alloy is high, and the manganese is added at high temperature and then the temperature is increased to add iron, so that the dissolution and solid solution of iron are facilitated, and iron-rich hard particles are reduced or eliminated.
The reason why the alloy strength is reduced and the plasticity is reduced remarkably as the casting temperature is increased is that the more uniform the alloy composition is, the slower the cooling rate from the beginning to the precipitation of α phases is, the lower the nucleation rate of α phases is, the lower the α phase which is continuously precipitated during the subsequent cooling process can be aggregated on a small amount of α nuclei, so that α phases become a small amount of large spherical particles and coarse grains, and further, Fe — Mn compounds become a net or large aggregate, which deteriorates the alloy properties.
The invention relates to a wear-resistant corrosion-resistant multi-element manganese-aluminum bronze brazing alloy, which overcomes the defects of high dry grinding coefficient and poor heat conductivity of ZQAL9-4 alloy, and is easy to generate dealuminization corrosion in an environmental medium, so that the service life of the brazing alloy is short. While ZQSn10-1 has a lower strength and toughness and a greatly reduced wear resistance in the case of poor lubrication. The wear resistance, corrosion resistance and the like of the alloy using ZCuAl8Mn13Fe3Ni2 cannot meet the conditions of harsh environments. In addition, the existing smelting process has the problems of more oxidation inclusions, coarse structure, influence on obtaining excellent mechanical properties and the like. Hardness values (average) were 2.53 times ZQAl9-4, 3.13 times ZQSn10-1, and 1.44 times ZCuAl8Mn13Fe3Ni2, respectively. The tensile strength (average) was 1.51 times ZQAl9-4 and 2.86 times ZQSn10-1, comparable to ZCuAl8Mn13Fe3Ni 2. The dry-milled coefficients of friction (averages) were 60% of ZQAl9-4, 74% of ZQSn10-1, and 51% of ZCuAl8Mn13Fe3Ni 2. The wear loss (average) was only 69% of ZQAl9-4, 73% of ZQSn10-1 and 33.2% of ZCuAl8Mn13Fe3Ni 2. The coefficient of friction (average) of the oil-lubricated mill was only 69% of ZQAl9-4, 73% of ZQSn10-1, and 33.2% of ZCuAl8Mn13Fe3Ni 2. The wear loss (average) was only 33.3% of ZQAl9-4, 30.9% of ZQSn10-1 and 21.6% of ZCuAl8Mn13Fe3Ni 2. The electrode potential is 0.0403mv higher than ZCuAl8Mn13Fe3Ni2 and is improved by 14.3 percent. The corrosion amount (average value) in the corrosion resistance test was only 51.8% of ZCuAl8Mn13Fe3Ni 2.
Compared with the original process (A in the table 4), the smelting and feeding sequence and the process (B in the table 4) in the manufacturing method of the invention have the advantages of less alloy oxide inclusions, compact structure and low matrix hardness.
The invention is composed of Al, Mn, Fe, Ni, B, Y, La and Cu, the casting temperature is equal to or lower than 1050 ℃, and the mechanical property is good. The alloy material is used for cladding the inner wall of the cylinder in the hydraulic support, has bright surface, less deformation, hardness of more than HB240, good wear resistance and corrosion resistance, has the service life of 2 times that of the raw materials in the prior operation, and is still normally used.
Description of the drawings:
FIG. 1(a) is a metallographic structure diagram of ZCuAl8Mn13Fe3Ni2 of a comparative example; (b) x-ray energy spectrum analysis chart of K phase;
FIG. 2(a) is a metallographic structure chart of example 4 of the present invention; (b) scanning electron microscope phase diagram.
The specific implementation mode is as follows:
in order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention will be further described in detail with reference to the accompanying drawings and preferred embodiments.
Examples 1 to 4: a wear-resistant corrosion-resistant multi-element manganese aluminum bronze brazing alloy is prepared by preparing materials according to the component proportions shown in Table 1; electrolytic cathode copper, electrolytic aluminum, electrolytic manganese, electrolytic nickel, iron wires or iron nails which are degreased and have smooth surfaces, aluminum-5% boron intermediate alloy, pure rare earth yttrium and lanthanum are selected. Heating and smelting by using a medium-frequency induction furnace and a graphite crucible.
A preparation method of a wear-resistant corrosion-resistant multi-element manganese aluminum bronze brazing alloy comprises the following steps:
① charging, namely placing dry charcoal at the bottom of the crucible, and adding cathode copper and electrolytic manganese at the same time according to the proportion of Cu to Mn being less than or equal to 2, wherein the charging material needs to be compact;
② supplying power to increase temperature, increasing power to melt the furnace charge rapidly, heating to 1300-;
③ cutting off power, adding the rest copper, cooling to 1050-;
④ heating to 1100 deg.C and 1150 deg.C, keeping the temperature, introducing argon for 10 min, and analyzing the components in front of the furnace;
⑤, detecting the quality of the molten metal, pouring the molten metal into a graphite crucible preheated to 200-;
⑥ horizontal continuous casting into wire blank wire rod;
⑦ stretching and annealing, adopting multi-mode continuous stretching, bright protection annealing, annealing temperature of 700 ℃, keeping temperature for 3 hours, and air cooling.
⑧ peeling and stretching, removing surface defects, stretching to obtain final product, inspecting, packaging, and storing.
Table 1 below is the chemical composition of the alloy of the invention and the comparative alloy.
TABLE 1
Table 2 below is the mechanical properties of each alloy of table 1. Preparing samples according to the technical conditions of GB/T1176 cast copper alloy and according to GB/T228.1 'Room temperature tensile test of metal materials'. GB/T231.1 "first part of Metal Brinell hardness test: experimental methods the procedures were carried out.
TABLE 2
FIG. 1(a) is a metallographic structure of comparative example ZCuAl8Mn13Fe3Ni2, which is coarse in structure, irregular in K-phase and uneven in distribution, (b) x-ray energy spectrum analysis of the K-phase, rich in Fe, Mn, Ni and Si, etc., FIG. 2(a) is a metallographic structure of example 4 of the present invention, the microstructure α and the K-phase are refined, and (b) phase diagram of a scanning electron microscope is used for observing that the K-phase is mostly in the form of small particles and is even in distribution.
Table 3 below is a friction wear test and a corrosion test for each alloy of table 1. The experimental conditions used for each data in the table illustrate: the friction and wear are tested according to GB/T3960-2016 Plastic sliding friction and wear test method, an M-2000 friction and wear tester is adopted, and the wear pair material is hardened GCr15, the hardness is 62HRC, the load is 196N, the rotating speed is 200r/min, and the test time is 2 hours. Lubricated with 32# motor oil.
Dynamic seawater corrosion experiment for corrosion test, corrosion medium: 5% NaCl + 1% H2O2+H2O. to keep sufficient oxygen in the medium, H is added at regular intervals2O2Due to H2O2Easily decomposed to generate oxygen. The experiment was carried out for 18 days, and the amount of corrosion was measured by stirring for 2 hours per day on average.
Measuring the potential of the electrode; processing a sample into 10x10x10mm, polishing, and then carrying out electrode potential measurement by using a calomel electrode position reference electrode and Bohai sea water as a medium, wherein the pH value of the sea water is 7.3, and the salinity is 3%.
TABLE 3
The ingredients of Table 4 below are Cu77.67, Mn10, Al6.5, Fe3, Ni2.5, B0.03, Y0.1 and La0.2. A is an original smelting process, and the adopted smelting process comprises the following steps: 1) 2/3Cu + Fe + Mn + Ni + charcoal is melted; 2) adding Al, Al-B, La and Y for melting; 3) the remaining 1/3Cu melted; 4) stirring cryolite and fishing slag; 5) and (4) continuously casting. B is the smelting process of the present invention. The smelting process of the present invention has less oxide inclusion, compact structure and low hardness of the base body.
TABLE 4
Table 5 below shows the casting temperature and mechanical properties of the alloys of the invention. The casting temperature higher than 1100 ℃ causes the structure to become coarse and form Fe-Mn brittle compounds, deteriorating the alloy properties. The alloy of the invention has a solid phase temperature of 965 ℃ and a liquid phase temperature of 985 ℃.
TABLE 5
The above description is only a preferred embodiment of the present invention, and for those skilled in the art, the present invention should not be limited by the description of the present invention, which should be interpreted as a limitation.
Claims (8)
1. The wear-resistant corrosion-resistant multi-element manganese aluminum bronze brazing alloy is characterized by comprising the following components in parts by weight: 7-10% of Al; 8-11% of Mn; 1.5 to 3.0 percent of Fe; 1.5 to 2.5 percent of Ni; 0.005-0.03% of B; 0.05 to 0.1 percent of Y; 0.08-0.20% of La, and the weight ratio of the three elements of Y and La is 1: 10: 15-1: 3: 6, and other impurities are less than or equal to 0.5 percent. The balance being Cu.
2. The preparation method of the wear-resistant corrosion-resistant multi-element manganese aluminum bronze brazing alloy according to claim 1, characterized by comprising the following steps of:
① charging, namely placing dry charcoal at the bottom of the crucible, and adding cathode copper and electrolytic manganese at the same time according to the proportion of Cu to Mn being less than or equal to 2, wherein the charging material needs to be compact;
② supplying power to increase temperature, increasing power to melt the furnace charge rapidly, heating to 1300-;
③ cutting off power, adding the rest copper, cooling to 1050-;
④ heating to 1100 deg.C and 1150 deg.C, keeping the temperature, introducing argon for 10 min, and analyzing the components in front of the furnace;
⑤, detecting the quality of the molten metal, pouring the molten metal into a graphite crucible preheated to 200-;
⑥ horizontal continuous casting into wire blank wire rod;
⑦ stretching and annealing, adopting multi-mode continuous stretching, bright protection annealing, annealing temperature of 700 ℃, keeping temperature for 3 hours, and air cooling.
⑧ peeling and stretching, removing surface defects, stretching to obtain final product, inspecting, packaging, and storing.
3. The preparation method according to claim 2, wherein the obtained wear-resistant corrosion-resistant multi-element manganese aluminum bronze brazing alloy is α refined, and the K phase is in a small granular shape and is uniformly distributed.
4. The preparation method of claim 2, wherein the obtained wear-resistant and corrosion-resistant multi-element manganese aluminum bronze brazing alloy is less in oxidation inclusion, compact in structure and low in matrix hardness.
5. The preparation method according to claim 2, wherein the obtained wear-resistant and corrosion-resistant multi-element manganese aluminum bronze brazing alloy has Brinell hardness HB250-280, tensile strength 620-670Mpa, elongation 15-20%, solid phase point 965 ℃ and liquid phase point 985 ℃.
6. The preparation method according to claim 2, wherein the dry friction coefficient at room temperature of the obtained wear-resistant corrosion-resistant multi-element manganese aluminum bronze brazing alloy is less than 0.28, and the abrasion loss is less than 9.1 mg.
7. The preparation method according to claim 2, wherein the friction coefficient under oil lubrication of the obtained wear-resistant and corrosion-resistant multi-element manganese aluminum bronze brazing alloy at room temperature is less than 0.11, and the abrasion loss is less than 3.5 mg.
8. The preparation method according to claim 2, wherein the corrosion amount of the obtained wear-resistant corrosion-resistant multi-element manganese aluminum bronze brazing alloy in a dynamic seawater corrosion test is less than 15.1 (g/m)2)。
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| CN112030034A (en) * | 2020-09-04 | 2020-12-04 | 孙勇 | Production process of high-quality QAL10-5-4 aluminum bronze alloy |
| CN113584343A (en) * | 2021-07-28 | 2021-11-02 | 宁波博威合金材料股份有限公司 | Corrosion-resistant high-manganese aluminum bronze alloy and preparation method thereof |
| CN115213586A (en) * | 2022-08-22 | 2022-10-21 | 江苏亨通电力智网科技有限公司 | Wear-resistant and corrosion-resistant manganese-aluminum bronze welding wire and preparation method thereof |
| CN115537596A (en) * | 2022-10-13 | 2022-12-30 | 郑州航空港区速达工业机械服务有限公司 | High-hardness corrosion-resistant nickel-aluminum bronze welding wire, preparation method thereof and application thereof in alloy cladding |
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| CN113584343A (en) * | 2021-07-28 | 2021-11-02 | 宁波博威合金材料股份有限公司 | Corrosion-resistant high-manganese aluminum bronze alloy and preparation method thereof |
| CN115213586A (en) * | 2022-08-22 | 2022-10-21 | 江苏亨通电力智网科技有限公司 | Wear-resistant and corrosion-resistant manganese-aluminum bronze welding wire and preparation method thereof |
| CN115537596A (en) * | 2022-10-13 | 2022-12-30 | 郑州航空港区速达工业机械服务有限公司 | High-hardness corrosion-resistant nickel-aluminum bronze welding wire, preparation method thereof and application thereof in alloy cladding |
| CN115537596B (en) * | 2022-10-13 | 2023-03-14 | 郑州航空港区速达工业机械服务有限公司 | High-hardness corrosion-resistant nickel-aluminum bronze welding wire, preparation method thereof and application thereof in alloy cladding |
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