CN112695216B - Preparation method of manganese brass alloy with three strengthening phases - Google Patents
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Abstract
The invention relates to the field of manganese brass alloy materials, in particular to a preparation method of a manganese brass alloy with three strengthening phases. The alloy is prepared by mixing and smelting materials according to a proportion, carrying out molten salt electrolysis treatment on the melt, casting the melt into a cast ingot with good uniformity and fine crystal grains, and finally carrying out extrusion, quenching, stretching, peeling, annealing and straightening post-treatment processes.
Description
Technical Field
The invention relates to the field of manganese brass alloy materials, in particular to a preparation method of a manganese brass alloy with three strengthening phases.
Technical Field
Brass is an important copper alloy, and has low cost and excellent comprehensive properties including excellent corrosion resistance, good plastic workability, high strength, and good thermal and electrical conductivity, so that brass has wide applications in various fields of national economy, and is often used for manufacturing valves, drain pipes, radiators, and the like.
The simple Cu-Zn binary alloy is called common brass, the alloy has low strength and hardness and poor wear resistance, is not suitable for being used as a structural material, and limits the application field of copper alloy materials to a great extent. The high-strength wear-resistant complex brass is a complex multi-element alloy system formed by adding a small amount of Al, Mn, Si, Fe, Ni, Ti, Cr, Pb, Sn and other alloy elements on the basis of Cu-Zn binary alloy, has excellent comprehensive mechanical property, thermal conductivity, corrosion resistance, outstanding wear resistance and excellent hot-working formability, and can adapt to relatively severe working environments such as high speed, high wear resistance, high impact, low lubrication and the like, so that the brass can be rapidly applied to the preparation of heavy-load, high-speed hydraulic rotors, sliding shoes, self-lubricating bearings, precision forgings and the like since the development of the seventies of the last century. The high-strength wear-resistant brass at home and abroad is various, and can be roughly divided into manganese brass (Cu-Zn-Mn series) and aluminum brass (Cu-Zn-Al series) according to different added main alloy elements and hard phases, and compared with the aluminum brass, the manganese brass in the high-strength wear-resistant brass has low cost, excellent comprehensive performance and wider application range, so that the high-strength wear-resistant manganese brass material has huge market potential and important research value. With the continuous breakthrough of China's major science and technology in recent years, high-strength wear-resistant brass has wide and urgent needs in aviation, navigation and automobile industries, and the most prominent is in the field of automobile synchronizer gear rings.
With the rapid development of the automobile industry, higher requirements are put forward on the performance of a synchronizer gear ring material, and particularly, the comprehensive mechanical property and the wear resistance of a high-strength wear-resistant manganese brass material need to be further improved, the stability of the synchronizer gear ring is improved, and the service life of the synchronizer gear ring is prolonged. The method is an effective method for improving the mechanical property and the wear resistance of the complex brass by changing the proportion of alloy elements and designing corresponding heat treatment conditions to control the content of alpha phase and beta phase in the alloy and the shape, the size and the distribution condition of hard phase.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a high-strength wear-resistant manganese brass alloy, which adopts ingot casting extrusion production technology and carries out quenching treatment after extrusion to form the manganese brass alloy with three strengthening phases, wherein Cu, Zn, Co, Mn, Si, Ni, Fe, Al, Pb and Ce are used as raw materials, the mechanical property and the wear resistance of the manganese brass alloy are obviously improved, the thermal stability is excellent, and the service life is prolonged.
In order to achieve the above object, the technical solutions adopted by the present invention are specifically as follows.
A preparation method of a manganese brass alloy with three strengthening phases comprises the following steps:
1) smelting a blank: melting electrolytic copper, then adding Co, Mn, Si, Ni, Fe, Al, Pb and Ce in sequence according to the melting point from high to low, smelting, and finally adding Zn to prevent the volatilization of zinc element;
2) molten salt electrolysis treatment: heating the melt to 900-950 ℃, preserving heat for 15-20 min, carrying out electrolytic treatment in molten fluoride salt for 2-2.5 h, then carrying out slag skimming, standing for 5-10 min, and transferring into an iron core induction furnace for heat preservation;
3) ingot casting: processing the melt into a circular ingot with the diameter of 90-100 mm through horizontal continuous casting;
5) and (3) post-treatment: and carrying out isothermal extrusion, quenching, stretching, peeling, annealing and straightening treatment on the cast ingot to obtain the cast ingot.
The method comprises the steps of mixing and smelting materials according to a ratio, carrying out molten salt electrolytic treatment on a melt, casting the melt into a cast ingot with good uniformity and fine crystal grains, and carrying out extrusion, quenching, stretching, peeling, annealing and straightening post-treatment processes to obtain the manganese brass alloy with the three strengthening phases.
Further, the weight percentages of the materials are as follows: cu: 55-57%; co: 0.5-1.5%; mn: 2.0-4.0%; si: 1.0-2.0%; al: 3.0-5.0%; ni: 2.0-5.0%; fe: 1.0-2.0%; pb: 0.1-0.2%; ce: 0.1-0.2%; the balance of Zn.
Further, the specific operation steps of the billet smelting process are as follows:
placing an electrolytic copper block in a graphite crucible, covering dry charcoal on the surface of the graphite crucible, raising the temperature to 1200-1250 ℃ after Cu is melted, adding Co, Mn, Si, Ni and Fe, preserving heat for 20-50 min, reducing the temperature to 1000-1050 ℃ after Cu is completely melted, adding Al, Pb and Ce, preserving heat for 3-5 min, further reducing the temperature to 830-850 ℃, and adding Zn for smelting.
Further, the stirring speed in the blank smelting process is 80-400 r/min.
Further, in the molten salt electrolysis treatment process:
the electrolyte is Na3AlF6-AlF3And 0.05-0.2% of B element, wherein Na3AlF6And AlF3The addition weight ratio of (A) is 10-15: 1;
the electrolysis temperature is 900-950 ℃;
the current density is 0.4-0.6A/cm2。
The fused mass is treated by molten salt electrolysis, so that the generation of oxides in the alloy is reduced, the component distribution of the alloy is more uniform, the segregation of the alloy is reduced, the brittleness of the alloy is reduced, the hot processing performance is improved, and the thermal stability and the mechanical strength are improved.
Furthermore, the molten salt electrolysis treatment process also comprises an electromagnetic stirring process, the electromagnetic stirring frequency is 25-30 Hz, the electromagnetic stirring and the molten salt electrolysis treatment have a synergistic effect, the precipitation of a second phase can be further improved, the effect of refining grains is achieved, the segregation of the alloy is reduced, the uniformity of the product is improved, and therefore the purposes of enhancing the mechanical strength, the wear resistance and the hot working performance of the alloy are achieved.
Further, in the ingot casting process, the ingot casting temperature of the horizontal continuous casting is 1000-1050 ℃, the cooling water pressure is 0.05-0.2 MPa, and the continuous casting speed is 3-5 mm/s.
Further, in the post-treatment process, the specific operation steps of isothermal extrusion include:
1) primary extrusion: the extrusion temperature is 400-450 ℃, and the extrusion speed is 2.5-4 mm/s;
2) secondary extrusion: the extrusion temperature is 530-550 ℃, and the extrusion speed is 1-2.5 mm/s.
Further, in the post-treatment process, the specific operation steps of the quenching process include:
1) putting the extruded cast ingot into a furnace, preserving heat for 30-60 min at 400-450 ℃, then heating to 650-700 ℃ at a heating rate of 200-220 ℃/min, preserving heat for 20-30 min, and then putting into water at 25-60 ℃ for quenching;
2) and heating the quenched cast ingot to 380-420 ℃, and preserving heat for 2-3 h.
Compared with the prior heat treatment process of a finished product, the quenching treatment after the hot pressing treatment can separate out a small amount of alpha phase from the matrix structure, so that the alloy obtains good wear resistance, and the defects of great reduction of wear resistance and mechanical property caused by the separation of a large amount of alpha phase are avoided by the two heat preservation treatments in the quenching process, so that the extruded material structure is uniformly distributed, and the yield strength, the tensile strength and the wear resistance of the final product manganese brass alloy can be effectively improved.
Furthermore, in the post-treatment process, the stretching multiple is 15-20 times, and the stretching speed is 5-20 mm/s.
Furthermore, in the post-treatment process, the annealing temperature is 450-480 ℃, the annealing time is 3-4.5 hours, the temperature is reduced to 200-220 ℃ at the speed of 0.5-2 ℃/min after the annealing treatment, and then the temperature is continuously reduced to the room temperature at the speed of (Ce% × 2000 ℃ (5 ℃)/min). The cooling rate in the annealing treatment process is controlled, so that the residual stress of the product can be eliminated, the size is stabilized, the effect of refining crystal grains is achieved, the structure is more uniform, the uniformity of the product is improved, the mechanical strength is enhanced, and the wear resistance and the hot processing performance of the product are improved.
Further, the manganese brass alloy prepared by the method comprises the following components:
matrix: an alpha + beta phase;
strengthening phase: Mn-Si phase, Mn5Si3A phase and a Mn-Si-Ni phase; and the number of the first and second groups,
pb distributed in the state of free elemental spheres.
By adopting the technical scheme, Cu, Zn, Co, Mn, Si, Al, Ni, Fe and Pb are used as raw materials, and the manganese brass alloy with three strengthening phases is obtained by smelting, molten salt electrolysis treatment (accompanied with electromagnetic stirring), slag skimming, standing, converter, ingot casting, extrusion, quenching, stretching, skimming, annealing and straightening, so that the preparation method has strong operability, the plasticity, toughness and strength of the manganese brass alloy are obviously improved, the brittleness is disappeared, the wear resistance is enhanced, and the service life is greatly prolonged; wherein, Al element changes the proportion of matrix phase, which refines crystal grains and improves mechanical property and wear resistance; the addition of Ni greatly changes the structure and the appearance of the alloy, and a Mn-Si-Ni phase connected with alpha appears, and the alloy has a Mn-Si phase and Mn5Si3Three strengthening phases of phase and Mn-Si-Ni phase, and the addition of Ni obviously improves the mechanical property and the wear resistance of the alloy.
The manganese brass alloy obtained based on the preparation method comprises the following elements in percentage by weight: cu: 55-57%; co: 0.5-1.5%; mn: 2.0-4.0%; si: 1.0-2.0%; al: 3.0-5.0%; ni: 2.0-5.0%; fe: 1.0-2.0%; pb: 0.1-0.2%; ce: 0.1-0.2%; the balance of Zn.
Applications of the foregoing manganese brass alloys include, but are not limited to:
1) application to watch parts; and/or
2) Applied to tap water pipes; and/or
3) Automotive parts; and/or
4) An aviation hydraulic component; and/or
5) The method is applied to the electric product assembly.
Due to the adoption of the technical scheme, the invention has the following technical effects:
1) the fused mass is treated by molten salt electrolysis, so that the generation of oxides in the alloy is reduced, the component distribution of the alloy is more uniform, the segregation of the alloy is reduced, the thermal stability and the mechanical strength of the alloy are improved, the electromagnetic stirring and the molten salt electrolysis have a synergistic effect, the precipitation of a second phase can be further improved, the effect of refining grains is achieved, and the segregation of the alloy is reduced, so that the aims of enhancing the mechanical strength and the wear resistance of the alloy are fulfilled;
2) compared with the prior heat treatment process of a finished product, the quenching treatment after the hot pressing treatment can separate out a small amount of alpha phase from the matrix structure, so that the alloy obtains good wear resistance, and the defects of great reduction of wear resistance and mechanical property caused by the separation of a large amount of alpha phase are avoided by carrying out heat preservation treatment twice in the quenching process, so that the extruded material structure is uniformly distributed, and the yield strength, the tensile strength and the wear resistance of the final product manganese brass alloy can be effectively improved;
4) the cooling rate in the annealing treatment process is controlled, so that the residual stress of the product can be eliminated, the size is stabilized, the effect of refining crystal grains is achieved, the structure is more uniform, the uniformity of the product is improved, the mechanical strength is enhanced, and the wear resistance and the hot processing performance of the product are improved;
3) the manganese brass alloy has three strengthening phases including Mn-Si phase and Mn5Si3The phase and the Mn-Si-Ni phase are subjected to quenching treatment after ingot casting extrusion by reasonably designing the components of the alloy and generating synergistic effect among the elements, so that the machining performance of the alloy is further improved, the high-temperature stability of the alloy is improved, the wear resistance and the mechanical property of the alloy are further optimized, the microstructure in the alloy is uniformly distributed, the service life is prolonged, and the requirement of the current generation is met.
Drawings
In order to make the aforementioned and other objects, features, and advantages of the invention, as well as others which will become apparent, reference is made to the following description taken in conjunction with the accompanying drawings in which:
FIG. 1 is a metallographic structure diagram of a manganese brass alloy prepared in example 1 of the present invention;
FIG. 2 is a metallographic structure diagram of a manganese brass alloy prepared in example 2 of the present invention;
FIG. 3 is an SEM image of a manganese brass alloy produced in example 1 of the present invention;
FIG. 4 is a graph showing the results of the thermal stability test of the manganese brass alloy of the present invention.
Detailed Description
To make the features and effects of the present invention comprehensible to those skilled in the art, general description and definitions are made below with reference to terms and expressions mentioned in the specification and claims. Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and in case of conflict, the definitions in this specification shall control.
In the present invention, when embodiments or examples are described, it is understood that it is not intended to limit the invention to these embodiments or examples, but on the contrary, the invention is intended to cover all alternatives, modifications and equivalents of the methods and materials described herein as may be included within the scope of the appended claims.
The invention provides a preparation method of a manganese brass alloy with three strengthening phases, which comprises the following steps:
1) smelting a blank: melting electrolytic copper, sequentially adding Co, Mn, Si, Ni, Fe, Al and Pb into the electrolytic copper according to the melting point, melting, keeping the stirring speed of 80-400 r/min in the melting process, and finally adding Zn to prevent the volatilization of zinc element;
2) molten salt electrolysis treatment: heating the melt to 900-950 ℃, preserving heat for 15-20 min, carrying out electrolytic treatment in molten fluoride salt for 2-2.5 h, then carrying out slag skimming, standing for 5-10 min, and transferring into an iron core induction furnace for heat preservation;
3) ingot casting: processing the melt into a circular ingot with the diameter of 90-100 mm through horizontal continuous casting;
5) and (3) post-treatment: and extruding, quenching, stretching, peeling, annealing and straightening the cast ingot to obtain the cast ingot.
Further, the blank smelting process specifically comprises the following steps: placing an electrolytic copper block in a graphite crucible, covering dry charcoal on the surface of the graphite crucible, raising the temperature to 1200-1250 ℃ after Cu is melted, adding Co, Mn, Si, Ni and Fe, preserving heat for 20-50 min, reducing the temperature to 1000-1050 ℃ after Cu is completely melted, adding Al, Pb and Ce, preserving heat for 3-5 min, further reducing the temperature to 830-850 ℃, and adding Zn for smelting;
during molten salt electrolysis treatment: the electrolyte is Na3AlF6-AlF3And 0.05-0.2% of B element, wherein Na3AlF6And AlF3The addition weight ratio of (A) is 10-15: 1; the electrolysis temperature is 900-950 ℃; the current density is 0.4-0.6A/cm2；
The ingot casting temperature of the horizontal continuous casting in the ingot casting process is 1000-1050 ℃, the cooling water pressure is 0.05-0.2 MPa, and the continuous casting speed is 3-5 m/s;
the concrete operation steps of the isothermal extrusion comprise: 1) primary extrusion: the extrusion temperature is 400-450 ℃, and the extrusion speed is 2.5-4 mm/s; 2) secondary extrusion: the extrusion temperature is 530-550 ℃, and the extrusion speed is 1-2.5 mm/s;
the quenching process of the post-treatment comprises the following specific operations: 1) putting the extruded cast ingot into a furnace, keeping the temperature for 30-60 min at 400-450 ℃, then heating to 650-700 ℃ at a heating rate of 200-220 ℃/min, keeping the temperature for 20-30 min, and then putting the cast ingot into water at 25-60 ℃ for quenching; 2) heating the quenched cast ingot to 380-420 ℃, and preserving heat for 2-3 h;
in the annealing process, the annealing temperature is 450-480 ℃, the annealing time is 3-4.5 h, the temperature is reduced to 200-220 ℃ at the speed of 0.5-2 ℃/min after annealing treatment, and then the temperature is continuously reduced to the room temperature at the speed of (Ce% × 2000 ℃/5 ℃)/min.
The invention provides a manganese brass alloy obtained based on the method, which comprises the following elements in percentage by weight: cu: 55-57%; co: 0.5-1.5%; mn: 2.0-4.0%; si: 1.0-2.0%; al: 3.0-5.0%; ni: 2.0-5.0%; fe: 1.0-2.0%; pb: 0.1-0.2%; ce: 0.1-0.2%; the balance of Zn.
The invention also provides the following applications of the manganese brass alloy:
1) application to watch parts; and/or
2) Applied to tap water pipes; and/or
3) Automotive parts; and/or
4) An aviation hydraulic component; and/or
5) The method is applied to the electric product assembly.
The following describes the technical solution of the present invention in further detail with reference to the detailed description and the accompanying drawings.
Table 1: the manganese brass alloy of examples 1-8 contains the following components in percentage by weight
Example 1: a manganese brass alloy having three strengthening phases:
the embodiment provides a manganese brass alloy with three strengthening phases, the component contents of which are shown in table 1, and the production process flow comprises the following steps: burdening → smelting → molten salt electrolysis treatment (electromagnetic stirring with stirring) → slag skimming, standing → converter → ingot casting → extrusion → quenching → stretching → skimming → annealing → straightening → finished product;
the specific operation steps are as follows:
1) placing an electrolytic copper block in a graphite crucible, covering dry charcoal on the surface of the electrolytic copper block, raising the temperature to 1250 ℃ after Cu is melted, adding Co, Mn, Si and Fe, preserving heat for 30min, reducing the temperature to 1050 ℃ after Cu is completely melted, adding Pb, preserving heat for 5min, further reducing the temperature to 850 ℃, adding Zn, and smelting into a melt;
2) heating the melt to 935 deg.C and maintaining the temperature for 20min, electrolyzing in molten fluoride salt for 2.5h under electromagnetic stirring with Na as electrolyte3AlF6-AlF3(weight ratio: 15:1) and 0.05-0.2% of B element, the electrolysis temperature is 930 ℃, and the current density is 0.5A/cm2The electromagnetic stirring frequency is 25 Hz;
3) removing slag from the melt, standing for 8min, and transferring into an iron core induction furnace for heat preservation;
3) horizontally continuously casting the melt at 1050 ℃ to form a circular ingot with the diameter of 90-100 mm, wherein the pressure of cooling water is 0.1MPa, and the continuous casting speed is 5 m/s;
4) extruding the cast ingot at the speed of 3.5mm/s at the temperature of 540 ℃, then extruding at the speed of 1.5, then preserving heat for 40min at the temperature of 450 ℃, then heating to 680 ℃ at the speed of 210 ℃/min and preserving heat for 20min, then putting the cast ingot into water at the temperature of 30 ℃ for quenching, heating the quenched cast ingot to 400 ℃, preserving heat for 2h, then stretching, peeling, annealing at the temperature of 460 ℃ for 4h, cooling to 215 ℃ at the speed of 1.5 ℃/min, then continuing cooling to room temperature at the speed of 8 ℃/min, and straightening to obtain the alloy steel.
Example 2: another manganese brass alloy with three strengthening phases:
this example provides another manganese brass alloy with three strengthening phases, the contents of which are shown in table 1, and the production process is substantially the same as that of example 1, except that in this example, the weight ratio of the materials added is: 56% of Cu, 1% of Co, 3% of Mn, 2% of Si, 4% of Al, 1.5% of Fe, 0.2% of Pb, 0.15% of Ce and the balance of Zn.
Example 3: another manganese brass alloy with three strengthening phases:
this example provides another manganese brass alloy with three strengthening phases, the contents of which are shown in table 1, and the production process is substantially the same as that of example 1, except that in this example, the weight ratio of the materials added is: 56% of Cu, 1% of Co, 3% of Mn, 2% of Si, 4% of Al, 1% of Ni, 1.5% of Fe, 0.2% of Pb, 0.15% of Ce and the balance of Zn.
Example 4: another manganese brass alloy with three strengthening phases:
this example provides another manganese brass alloy with three strengthening phases, the contents of which are shown in table 1, and the production process is substantially the same as that of example 1, except that in this example, the weight ratio of the materials added is: 56% of Cu, 1% of Co, 3% of Mn, 2% of Si, 4% of Al, 5% of Ni, 1.5% of Fe, 0.2% of Pb, 0.15% of Ce and the balance of Zn.
Example 5: another manganese brass alloy with three strengthening phases:
this example provides another manganese brass alloy with three strengthening phases, the contents of which are shown in table 1, and the production process is substantially the same as that of example 1, except that in this example, the weight ratio of the materials added is: 56% of Cu, 1% of Co, 3% of Mn, 2% of Si, 2% of Al, 3% of Ni, 1.5% of Fe, 0.2% of Pb, 0.15% of Ce and the balance of Zn.
Example 6: another manganese brass alloy with three strengthening phases:
this example provides another manganese brass alloy with three strengthening phases, the contents of which are shown in table 1, and the production process is substantially the same as that of example 1, except that in this example, the weight ratio of the materials added is: 56% of Cu, 1% of Co, 3% of Mn, 2% of Si, 5% of Al, 3% of Ni, 1.5% of Fe, 0.2% of Pb, 0.15% of Ce and the balance of Zn.
Example 7: another manganese brass alloy with three strengthening phases:
this example provides another manganese brass alloy with three strengthening phases, the contents of which are shown in table 1, and the production process is substantially the same as that of example 1, except that in this example, the weight ratio of the materials added is: 56% of Cu, 1% of Co, 5% of Mn, 2% of Si, 4% of Al, 3% of Ni, 1.5% of Fe, 0.2% of Pb, 0.15% of Ce and the balance of Zn.
Example 8: another manganese brass alloy with three strengthening phases:
this example provides another manganese brass alloy with three strengthening phases, the contents of which are shown in table 1, and the production process is substantially the same as that of example 1, except that in this example, the weight ratio of the materials added is: 56% of Cu, 1% of Co, 3% of Mn, 3% of Si, 4% of Al, 3% of Ni, 1.5% of Fe, 0.2% of Pb, 0.15% of Ce and the balance of Zn.
Example 9: another manganese brass alloy with three strengthening phases:
the embodiment provides another manganese brass alloy with three strengthening phases, and the addition amount of each material is the same as that of the embodiment, except that the production process flow comprises the following steps: batching → smelting → molten salt electrolysis → slagging off, standing → converter → ingot casting → extrusion → quenching → stretching → peeling → annealing → straightening → finished product.
Example 10: another manganese brass alloy with three strengthening phases:
the embodiment provides another manganese brass alloy with three strengthening phases, and the addition amount of each material is the same as that of the embodiment, except that the production process flow comprises the following steps: batching → smelting → electromagnetic stirring → slagging-off, standing → converter → ingot casting → extrusion → quenching → stretching → peeling → annealing → straightening → finished product.
Example 11: another manganese brass alloy with three strengthening phases:
the embodiment provides another manganese brass alloy with three strengthening phases, and the addition amount of each material is the same as that of the embodiment, except that the production process flow comprises the following steps: batching → smelting → molten salt electrolysis treatment (accompanied by electromagnetic stirring treatment) → slagging off, standing → converter → ingot casting → extrusion → stretching → peeling → annealing → straightening → finished product.
Example 12: another manganese brass alloy with three strengthening phases:
the embodiment provides another manganese brass alloy with three strengthening phases, and the addition amount of each material is the same as that of the embodiment, except that the production process flow comprises the following steps: burdening → smelting → molten salt electrolysis treatment (accompanied with electromagnetic stirring treatment) → slagging off, standing → converter → casting ingot → extrusion → quenching → stretching → peeling → annealing → straightening → finished product, the concrete operation steps of the quenching process are as follows: heating the melt to 680 ℃ at the heating rate of 210 ℃/min, preserving heat for 20min, and then putting the melt into water at 30 ℃ for quenching; and heating the quenched cast ingot to 400 ℃, and preserving heat for 2 hours.
Example 13: another manganese brass alloy with three strengthening phases:
the embodiment provides another manganese brass alloy with three strengthening phases, and the addition amount of each material is the same as that of the embodiment, except that the production process flow comprises the following steps: burdening → smelting → molten salt electrolysis treatment (accompanied with electromagnetic stirring treatment) → slagging off, standing → converter → ingot casting → extrusion → quenching → stretching → peeling → annealing → straightening → finished product, the specific operation steps of the annealing process are as follows: the ingot was annealed at 460 ℃ for 4h, cooled to room temperature at a rate of 1.5 ℃/min and fully annealed.
Example 14: another manganese brass alloy with three strengthening phases:
the embodiment provides another manganese brass alloy with three strengthening phases, and the addition amount of each material is the same as that of the embodiment, except that the production process flow comprises the following steps: burdening → smelting → molten salt electrolysis treatment (accompanied with electromagnetic stirring treatment) → slagging off, standing → converter → ingot casting → extrusion → quenching → stretching → peeling → annealing → straightening → finished product, the specific operation steps of the annealing process are as follows: the ingot is annealed at 460 ℃ for 4h, cooled to room temperature at a rate of 8 ℃/min and completely annealed.
Experimental example 1: mechanical properties:
the manganese brass alloys in examples 1 to 14 were subjected to tensile strength, yield strength, elongation, and brinell hardness tests, wherein the tensile strength, elongation, and yield strength were measured with reference to GB/T228.1-2010, and the brinell hardness was measured with reference to GB/T231.1-2009, respectively. The test results of the manganese brass alloy in the extruded state, the stretched state and the annealed state are respectively shown in table 2.
Table 2: mechanical properties of manganese brass alloy
| Examples | Tensile strength/MPa | Yield strength/MPa | Elongation/percent | Brinell hardness/ |
| 1 | 770.6 | 422.8 | 25.5 | 187.0 |
| 2 | 557.5 | 204.5 | 17.5 | 142.5 |
| 3 | 697.5 | 285.4 | 21.0 | 163.2 |
| 4 | 780.0 | 425.0 | 30.7 | 190.0 |
| 5 | 625.3 | 247.6 | 20.0 | 152.7 |
| 6 | 755.4 | 420.0 | 27.5 | 185.5 |
| 7 | 712.5 | 305.4 | 12.5 | 188.0 |
| 8 | 705.6 | 288.2 | 13.1 | 185.8 |
| 9 | 724.5 | 368.4 | 20.8 | 180.4 |
| 10 | 585.7 | 270.5 | 14.5 | 154.5 |
| 11 | 560.0 | 220.5 | 24.3 | 162.5 |
| 12 | 668.5 | 305.0 | 22.5 | 168.6 |
| 13 | 725.4 | 387.2 | 27.2 | 172.7 |
| 14 | 688.2 | 358.4 | 20.3 | 175.8 |
As can be observed from Table 2, the manganese brass alloy prepared by the method has high tensile strength, high yield strength, high elongation and high hardness, the tensile strength is higher than 557MPa, the yield strength is higher than 204MPa, and the hardness is higher than 142 HB; compared with the examples 1 to 4, the tensile strength, the yield strength, the hardness and the elongation of the alloy are greatly improved along with the addition of Ni, because Ni mainly plays a role in refining the structure in the alloy, the strength of the alloy is improved, the mechanical property of the material tends to be stable along with the increase of the Ni content, and when the Ni content is excessive, the alpha phase in the structure is excessively precipitated, and the mechanical property of the material is reduced on the contrary; comparing examples 1, 5 and 6, it can be seen that with the increase of Al content, the tensile strength, yield strength, hardness and elongation of the alloy increase and the trend becomes slow, Al element can be dissolved with Cu to refine grains, and the strength and plasticity of the material are improved; comparing examples 1, 7 and 8, it can be seen that when the addition amount of Mn and Si is too much, the brittleness of the alloy is increased, and the tensile strength, yield strength, elongation and hardness are reduced; as can be seen from comparison of examples 1, 9 and 10, the melt is subjected to electromagnetic stirring in the molten salt electrolysis treatment process, and the two have synergistic effect, so that the mechanical strength of the alloy can be enhanced; it can be seen from comparison examples 1, 11, and 12 that the mechanical properties of the alloy can be improved by quenching after the ingot is extruded, the strength of the alloy can be further improved by performing heat preservation twice, and it can be seen from comparison examples 1, 13, and 14 that the cooling rate in the annealing treatment process is controlled, and the strength of the alloy prepared by cooling at different rates is higher than that of the alloy prepared by cooling at the same rate, which indicates that the control of cooling at different rates is more favorable for eliminating stress, improving the uniformity of the product, and improving the strength.
Experimental example 2: wear resistance:
the manganese brass alloy prepared in the embodiment 1-14 is used as a detection object, the wear resistance of the alloy is determined by referring to GB/T12444-2006, and the wear resistance of the alloy is represented by a friction coefficient and a wear volume. The test results are shown in table 3.
Table 3: wear resistance of manganese brass alloy
| Examples | Average coefficient of friction | Wear volume (10)-15m3/m) | Examples | Average coefficient of friction | Wear volume (10)-15m3/m) |
| 1 | 0.098 | 3450 | 8 | 0.152 | 3085 |
| 2 | 0.102 | 8255 | 9 | 0.284 | 6428 |
| 3 | 0.100 | 3408 | 10 | 0.228 | 5455 |
| 4 | 0.105 | 3350 | 11 | 0.161 | 6844 |
| 5 | 0.145 | 3684 | 12 | 0.125 | 5538 |
| 6 | 0.158 | 3256 | 13 | 0.128 | 5822 |
| 7 | 0.173 | 3050 | 14 | 0.134 | 6754 |
The friction coefficient is known to be mainly related to the roughness of the alloy surface, and as shown in table 3, the friction coefficient of the alloy prepared by the invention is lower, the difference of the friction coefficients of all the alloys is smaller, and the friction coefficient of the alloy prepared by the invention has no obvious change along with the increase of the abrasion time, which indicates that the roughness of the surface of the alloy prepared by the invention is smaller.
As shown in table 3, the wear volume of the alloy of example 2 is the largest, and it can be seen from comparison examples 1 to 6 that, with the addition of Al and Ni, the wear volume of the alloy decreases because the second phase appears in the alloy and the size of the silicon-manganese phase particles decreases, which improves the wear resistance of the alloy, but the wear volume difference of the alloys of examples 1, 3, 5 and 6 is smaller, which indicates that when the content of Al increases and the addition amount of Ni is lower, the second phase is not changed and the influence on the wear volume of the alloy is smaller; compared with the examples 1, 7 and 8, the increase of the content of Mn and Si in the alloy has obvious refining effect on the matrix phase and the reinforcing phase, so that silicon-manganese phase particles with smaller sizes are uniformly distributed in the alloy, the plastic deformation resistance of the metal on the wear surface is enhanced, and the wear resistance of the alloy is improved; compared with the examples 1 and 9-12, the molten salt electrolysis treatment, the electromagnetic stirring and the quenching treatment after the hot pressing both can refine grains and improve the wear resistance of the material; it can be seen from comparison of examples 1, 13 and 14 that, in the annealing treatment process, compared with the same temperature reduction, the temperature reduction treatment by controlling different rates is more favorable for improving the uniformity of the product surface and improving the wear resistance.
Example 3: thermal stability performance:
the manganese brass alloy of the embodiment 1-14 of the invention is put in a 200 ℃ holding furnace according to the GB/T228 standard for long-time high-temperature treatment for 100 hours, and after cooling, the tensile strength test is carried out according to the GB/T228 standard, and the specific detection result is shown in FIG. 4.
As can be seen from the figure, the manganese brass alloy prepared by the method disclosed by the invention can still keep higher tensile strength after being treated at the high temperature of 200 ℃ for 10 hours, the tensile strength of the manganese brass alloy can keep 84.6% of the original strength at most, and the manganese brass alloy has higher thermal stability; it can be seen from comparison of examples 1 and 9 to 12 that the molten salt electrolysis treatment, the electromagnetic stirring treatment and the quenching treatment after the hot pressing have a large influence on the thermal stability of the alloy, mainly because the molten salt electrolysis treatment, the electromagnetic stirring treatment and the quenching treatment after the hot pressing can significantly improve the microstructure of the material, and the precipitation distribution of the second phase of the alloy is more uniform by controlling the treatment conditions, so that the tissue distribution of the extruded material is uniform, and during the subsequent high-temperature stability performance test, the material tissue distribution is uniform, so that the long-term thermal stability performance can be still maintained at 200 ℃.
Experimental example 4: hot workability:
the alloy prepared in the examples 1 to 14 is used as a material, cut into samples with the diameter of 15mm and the length of 25mm, respectively kept at 740 ℃ and 635 ℃ for 20min, then placed longitudinally, with a thermal compression capacity of 10 tons and equipped with an Amsler tester of an electric furnace, compressing at high temperature at a strain rate of 0.02/s and a working ratio of 80% to give a thickness of 5mm, observing the sample with a magnifying glass of 10 times magnification, when an opening of 0.2mm or more was observed, it was judged as cracked, and the case where no cracking occurred under both conditions of 740 ℃ and 635 ℃ was evaluated as "good", the case where rupture occurred at 740 ℃ but not at 635 ℃ was evaluated as "Δ" (fair), the case where rupture did not occur at 740 ℃ but at 635 ℃ was evaluated as "a" (fair), and the case where rupture occurred at both conditions of 740 ℃ and 635 ℃ was evaluated as "x" (por). The test results are shown in table 4.
TABLE 4 Hot workability
| Examples | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| Hot working property | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Examples | 8 | 9 | 10 | 11 | 12 | 13 | 14 |
| Hot working property | ○ | △ | △ | △ | ○ | △ | △ |
As shown in Table 4, the manganese brass prepared by the invention has excellent thermal stability, no cracking phenomenon is found after the treatment at 635 ℃, and the alloy of the examples 1-8 can still not crack at 740 ℃, which shows that the components of the alloy have no obvious influence on the thermal stability, and the comparative examples 9-12 show that the molten salt electrolysis treatment, the electromagnetic stirring and the quenching treatment can achieve the effects of grain refinement, product uniformity improvement and quality improvement, and are beneficial to improving the thermal processing performance of the alloy; it can be seen from comparison of examples 1, 13 and 14 that the control of the cooling process at different rates is more beneficial to improving the thermal stability of the product surface compared with the same temperature.
Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein.
While the above detailed description has shown, described, and pointed out novel features as applied to various embodiments, it will be understood that various omissions, substitutions, and changes in the form and details of the device or method illustrated may be made without departing from the spirit of the disclosure. In addition, the various features and methods described above may be used independently of one another, or may be combined in various ways. All possible combinations and sub-combinations are intended to fall within the scope of the present disclosure. Many of the embodiments described above include similar components, and thus, these similar components are interchangeable in different embodiments. While the invention has been disclosed in the context of certain embodiments and examples, it will be understood by those skilled in the art that the invention extends beyond the specifically disclosed embodiments to other alternative embodiments and/or uses and obvious modifications and equivalents thereof. Accordingly, the invention is not intended to be limited by the specific disclosure of preferred embodiments herein.
Claims (7)
1. A preparation method of a manganese brass alloy with three strengthening phases is characterized by comprising the following steps:
1) smelting a blank: melting electrolytic copper, then adding Co, Mn, Si, Ni, Fe, Al, Pb and Ce in sequence according to the melting point from high to low, smelting, and finally adding Zn to prevent the volatilization of zinc element;
2) molten salt electrolysis treatment: heating the melt to 900-950 ℃, preserving heat for 15-20 min, carrying out electrolytic treatment in molten fluoride salt for 2-2.5 h, then carrying out slag skimming, standing for 5-10 min, and transferring into an iron core induction furnace for heat preservation;
3) ingot casting: processing the melt into a circular ingot with the diameter of 90-100 mm through horizontal continuous casting;
5) and (3) post-treatment: carrying out isothermal extrusion, quenching, stretching, peeling, annealing and straightening treatment on the cast ingot to obtain the cast ingot;
the weight percentages of the materials are as follows: cu: 55-57%; co: 0.5-1.5%; mn: 2.0-4.0%; si: 1.0-2.0%; al: 3.0-5.0%; ni: 2.0-5.0%; fe: 1.0-2.0%; pb: 0.1-0.2%; ce: 0.1-0.2%; the balance of Zn;
in the molten salt electrolytic treatment process:
the electrolyte is Na3AlF6-AlF3And 0.05-0.2% of B element, wherein Na3AlF6And AlF3The addition weight ratio of (A) is 10-15: 1;
the electrolysis temperature is 900-950 ℃;
the current density is 0.4-0.6A/cm2；
The quenching process comprises the following specific operation steps:
1) putting the extruded cast ingot into a furnace, heating to 400-450 ℃ at a heating rate of 150-180 ℃/min, preserving heat for 30-60 min, heating to 650-700 ℃ at a heating rate of 200-220 ℃/min, preserving heat for 20-30 min, and then putting into water at 25-60 ℃ for quenching;
2) heating the quenched cast ingot to 380-420 ℃, and preserving heat for 2-3 h;
the three strengthening terms are Mn-Si phase and Mn5Si3A phase and a Mn-Si-Ni phase.
2. The method of claim 1, wherein the specific operational steps of the smelting process include:
placing an electrolytic copper block in a graphite crucible, covering dry charcoal on the surface of the graphite crucible, raising the temperature to 1200-1250 ℃ after Cu is melted, adding Co, Mn, Si, Ni and Fe, preserving heat for 20-50 min, reducing the temperature to 1000-1050 ℃ after Cu is completely melted, adding Al, Pb and Ce, preserving heat for 3-5 min, further reducing the temperature to 830-850 ℃, and adding Zn for smelting.
3. The method according to claim 1, wherein the electromagnetic stirring is accompanied during the molten salt electrolysis treatment, and the electromagnetic frequency is 25 to 30 Hz.
4. The method according to claim 1, wherein the specific steps of isothermal pressing comprise:
1) primary extrusion: the extrusion temperature is 400-450 ℃, and the extrusion speed is 2.5-4 mm/s;
2) secondary extrusion: the extrusion temperature is 530-550 ℃, and the extrusion speed is 1-2.5 mm/s.
5. The method of claim 1, wherein the annealing temperature is 450-480 ℃, the annealing time is 3-4.5 hours, the temperature is reduced to 200-220 ℃ at a rate of 0.5-2 ℃/min after the annealing treatment, and then the temperature is continuously reduced to room temperature at a rate of (Ce% × 2000 ℃ +5 ℃)/min.
6. A manganese brass alloy having three strengthening phases produced by the method of any one of claims 1 to 5, comprising:
matrix: an alpha + beta phase;
strengthening phase: Mn-Si phase, Mn5Si3A phase and a Mn-Si-Ni phase; and the number of the first and second groups,
pb distributed in the state of free elemental spheres.
7. Use of a manganese brass alloy having three strengthening phases in accordance with claim 6, comprising:
1) application to watch parts; and/or
2) Applied to tap water pipes; and/or
3) Automotive parts; and/or
4) An aviation hydraulic component; and/or
5) The method is applied to the electric product assembly.
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