CN113462926B - High-strength wear-resistant high-lead tin bronze material and preparation method thereof - Google Patents
High-strength wear-resistant high-lead tin bronze material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-strength wear-resistant high-lead tin bronze material which comprises the following components in percentage by weight: 19-21 wt.% of Pb, 4.5-5.5 wt.% of Sn, 1.5-2.5 wt.% of Zn, 0.05-0.1 wt.% of P, 2-3 wt.% of Ni, 0.05-0.2 wt.% of AlTiC alloy, 0.05-0.2 wt.% of B and 0.04-0.07 wt.% of Y, and the balance copper, wherein electrolytic copper, copper-boron alloy and pure nickel are smelted until melting, 2/3 of phosphorus-copper alloy is added for deoxidizing and degassing treatment, alTiC alloy, copper-yttrium alloy, zinc, lead and tin are added, and finally the rest 1/3 of phosphorus-copper alloy is added for deoxidizing and degassing treatment again, and the alloy is heated to 1200 ℃ for tapping and casting. The high-lead tin bronze alloy prepared by the invention can meet the severe performance requirements of high PV (more than or equal to 100MPa ∙ m/s), high pressure resistance, strain resistance, wear resistance, high strength casting and the like.
Description
Technical Field
The invention belongs to the technical field of alloy material preparation, and particularly relates to a lead-tin bronze material and a preparation method thereof. The lead-tin bronze material has the mechanical properties of high strength, high PV, wear resistance, high pressure resistance and the like.
Background
The high-lead tin bronze is a lead tin bronze alloy with lead content of more than 10wt.%, and is used as a self-lubricating material and is a common antifriction material for the traditional casting process. Because the high-lead tin bronze has excellent performances such as high fatigue strength, heat conductivity, wear resistance, impact resistance and the like, the high-lead tin bronze is widely applied to the selection of wear-resistant parts such as bearings, bearing bushes, space pump rotors, turbines, guide plates and the like.
However, when the existing high-lead tin bronze is used as a material of a bimetal cylinder body, the high-strength wear-resistant requirement in the actual working condition can not be met under the conditions of high temperature, high speed and heavy load, and the problems of cylinder detachment, cylinder holding, copper adhesion and the like are easy to occur. The failure of the cylinder part is caused by insufficient strength of the copper alloy material, and serious specific gravity segregation of lead in a structure, so that the wear resistance of the material is reduced. According to statistics, the friction wear causes great economic loss to the country, and the annual loss accounts for about 2-8% of the total national production value, while the loss caused by abrasive wear accounts for l-4% of the total national production value.
For example, a plunger pump cylinder (also known as a "rotor") is one of the important components of a hydraulic machine, whose performance and quality determine transmission efficiency and even service life. The cylinder body, the plunger and the valve plate are two pairs of key friction pairs of the hydraulic pump, and are required to be manufactured from alloy with antifriction and wear-resistant properties. The antifriction and wear-resistant properties of high lead bronze and the relatively extremely low coefficient of friction are important advantages and basis for the use thereof as wear-resistant material for the manufacture of cylinders, but in the actual production process, a number of defects and problems are found.
Firstly, the dead weight problem is that the density of copper is 8.9g/cm 3 Density of lead 11.34g/cm 3 The two are not in solid solution. The lead content added into the copper matrix has sensitive influence on the structure and the structure of the alloy, the density difference of the lead content and the copper matrix is large, the solid solubility of the lead content and the copper matrix is extremely low, the lead content and the copper matrix are mixed in a simple substance form in smelting, the molten liquid is layered due to specific gravity without intervention of external measures, the molten liquid with uniform structure components cannot be formed, and the dead weight of the whole part is greatly increased.
Secondly, the primary failure modes of plunger pumps include wear, fatigue and aging.
Thirdly, the copper matrix of the high-lead tin bronze is strong and low in hardness, and the matrix is split by the aid of lead particles distributed in the copper matrix, so that mechanical properties are greatly reduced, and the bearing capacity and the impact resistance of the cylinder body can be greatly affected by independent molding.
With the advancement of technology, adding alloy elements such as rare earth and Ni, pb, fe, mn, al, P into high-lead tin bronze is one of the main methods for improving the performance of high-lead tin bronze alloy.
M. Aksoy(A note on the effect of Pb on the microstructure and mechanical properties of leaded-tin bronze[J]J. Mater Process Tech, 2002, 124 (1), 113-119) and H.Turhan (The effect of manganese on the microstructure and mechanical properties of leaded-tin bronze [ J ]]J. Mater Process Tech., 2001, 32 (14), 207-211)) by matrix alloying, mn is obtained by adding Fe, mn, si, P, S and other elements to a bearing material having a high lead content 5 Si 3 、Fe 3 The S and other hard disperse phases are separated out from the matrix, so that the sintering resistance and the wear resistance of the material are improved.
However, the coefficient of friction of the high lead tin bronze Cu-5Sn-20Pb cast by centrifugal casting is 0.38% in the 27 to 118N load range, and the coefficient of friction of the CuSn10Pb10 tin bronze prepared by S.Eque et al (Wear Wear, 2011, 273 (1): 9-16) is 0.4 to 0.7, both of which are high, as described in M.Kestursaita et al (Wear performance of copper-graphite composite and a leaded copper alloy [ J ]. Engineering, and Materials Science and frictional mechanisms of copper-based bearing alloys [ J ]. 2003, 134 (339): 150-158).
Ji Zhanjun (Study on lead segregation in centrifugally cast high lead bronze [ D ]. Shenyang: shenyang University, 2014.) the microscopic morphology of high-lead bronze alloys with different lead contents, S content and rare earth content is studied, and when S is not added, the lead segregation of the centrifugally cast high-lead bronze alloy is serious and is intensively distributed in a block shape and a strip shape; after S is added, lead segregation is effectively controlled. However, although the lead particles are thinned, the S element is added to improve segregation, meanwhile, the brittleness of the casting is improved, the control difficulty of the S addition amount is high, and the quality of the casting is influenced by excessive S.
Wang Mingjie (influence of trace elements on lead-tin bronze structure and performance [ J ]. Hot working process, 2016, 45 (5): 95-97.) increases tensile strength and wear resistance by adding trace rare earth elements and phosphorus to high lead-tin bronze, and refines the structure and improves performance. The tensile strength of the high-lead tin bronze reaches 192MPa when the casting temperature is 1250 ℃, the lanthanum-cerium-rare earth content is 0.2wt.% and the P content is 0.5 wt.%. Although the high lead tin bronze structure in this study was controlled, the mechanical properties were low.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a high-strength wear-resistant high-lead tin bronze material and a preparation method thereof. The high-lead tin bronze alloy prepared by the invention can meet the harsh requirements of high PV (more than or equal to 100MPa ∙ m/s), high pressure resistance, strain resistance, wear resistance and the like.
The high-strength wear-resistant high-lead tin bronze material disclosed by the invention comprises the following components in percentage by weight: 19 to 21wt.% of Pb, 4.5 to 5.5wt.% of Sn, 1.5 to 2.5wt.% of Zn, 0.05 to 0.1wt.% of P, 2 to 3wt.% of Ni, 0.05 to 0.2wt.% of AlTiC alloy, 0.05 to 0.2wt.% of B, 0.04 to 0.07wt.% of Y and the balance of copper.
Wherein, the AlTiC alloy is a grain refiner widely used in the aluminum alloy manufacturing industry. AlTiC alloy is prepared by mixing 40-50 wt.% Al powder, 45-55 wt.% Ti powder and 5-15 wt.% C powder, compacting, self-propagating at high temperature under vacuum to obtain self-propagating product, adding the self-propagating product into molten aluminum liquid, diluting to Ti element content of 5-5.3 wt.%, and pouring to obtain intermediate alloy.
The novel grain refiner AlTiC-B-Y formed by combining AlTiC alloy, elemental boron and rare earth yttrium exists in the high-strength wear-resistant high-lead tin bronze material, and the high-lead tin bronze material is combined with high-content metallic nickel to improve the tissue structure of the high-lead tin bronze material, so that the strength of the alloy is improved by refining grains and strengthening grain boundaries.
The AlTiC alloy added in the high-strength wear-resistant high-lead tin bronze material has the effects of shortening the solidification range of the copper alloy, reducing the sinking and aggregation time of lead particles, enabling the lead particles to be small and uniformly distributed, and further refining grains.
The addition of rare earth yttrium in the novel grain refiner AlTiC-B-Y can react with harmful impurities (oxygen and sulfur) in the copper alloy to generate high-melting-point rare earth compound particles which are uniformly distributed in a copper matrix to form a crystal core, so that the structure of the copper alloy is refined; on the other hand, rare earth is gathered on the grain boundary, so that the surface defect of the new-phase grains generated can be filled, a layer of film is generated, and the grains are prevented from growing continuously, so that the grains are refined; meanwhile, as dendrite arms become more thin, lead particles are thinned. Proper amount of rare earth elements can refine dendrite arms, but excessive rare earth elements can cause loose defects of copper alloy tissues.
Boron is added into the novel grain refiner AlTiC-B-Y, and firstly, high-melting-point Ni can be generated 4 B 3 Particles, producing dispersion strengthening; secondly, boron plays a role of modifier in the copper alloy, and as needle-shaped phases and block-shaped phases are formed in the solidification process or before solidification, the boron plays a role of homogenizing nucleation partially; meanwhile, the solid solubility of boron in copper is very small, so that boron is easy to gather at a grain boundary, thereby preventing the grain from growing greatly and reducing the interface energy, and the effect of refining the grain is also achieved; in addition, boron is biased to the grain boundary, and the interface energy can be changed, so that the morphology of the second phase on the grain boundary is changed, the second phase is more easily spheroidized, and the grain boundary strength is improved.
On the other hand, the high nickel in the high-strength wear-resistant high-lead tin bronze material of the invention can react with the boron in the novel grain refiner to form Ni before copper solidification 4 B 3 The phase is separated out along with solidification of the copper alloy, is repelled by copper grains and is enriched at a grain boundary, and solute atom diffusion at the solidification interface, growth curvature of the interface, occurrence of nucleation again and the like are directly influenced, so that growth of the grains is inhibited, and the purpose of refining the grains is achieved.
The invention further provides a preparation method of the high-strength wear-resistant high-lead tin bronze material, which comprises the steps of smelting electrolytic copper, copper-boron alloy and pure nickel which are required to be subtracted from the copper amount carried in each added intermediate alloy according to the proportioning content, adding 2/3 of the proportioning content of phosphorus-copper alloy, carrying out primary deoxidization and degassing treatment on alloy liquid, adding the proportioning content of AlTiC alloy, copper-yttrium alloy, zinc, lead and tin, finally adding the rest 1/3 of the proportioning content of phosphorus-copper alloy, carrying out secondary deoxidization and degassing treatment, heating the alloy liquid to 1200 ℃ and discharging and casting to obtain the high-lead tin bronze material.
The above method is not the only method for preparing the high lead tin bronze material, and any of various other conventional alloy preparation methods capable of uniformly obtaining an alloy from the components may be used as the preparation method of the high lead tin bronze material of the present invention.
Among them, the copper-boron alloy and the copper-yttrium alloy are preferably adopted as raw materials and added in the form of intermediate alloy due to the higher melting points of boron and yttrium.
In the preparation method of the high-strength wear-resistant high-lead tin bronze material, the alloy liquid is stirred for a plurality of times all the time in the smelting process of the alloy liquid.
In the above preparation method of the present invention, it is preferable that pure nickel and copper-boron alloy are preheated to 220 ℃ or higher and then smelted together with electrolytic copper preheated to the same temperature.
In the preparation method of the invention, after the first deoxidation and degassing treatment of the alloy liquid, the AlTiC alloy and the copper yttrium alloy with the proportioning contents are added, and then the zinc, the lead and the tin with the proportioning contents are added in sequence according to the melting point sequence of the alloy elements.
In the above preparation method of the present invention, after adding one alloy or metal to the alloy liquid, another alloy or metal is added at intervals of 5 to 7 minutes.
Further, after each addition of one alloy or metal, the alloy liquid should be sufficiently stirred.
Still further, the present invention requires stirring of the alloy liquid for not less than 30 seconds before adding the remaining phosphor copper alloy.
Specifically, the tapping and casting temperature of the alloy liquid is controlled to 1200 ℃, and the deviation is not more than 20 ℃.
The microstructure analysis result aiming at the high-strength wear-resistant high-lead tin bronze material shows that the microstructure of the high-lead tin bronze alloy is improved by adding a novel grain refiner AlTiC-B-Y, and the strength and wear resistance of the alloy are improved by refining grains, reducing lead segregation, strengthening grain boundaries. Meanwhile, the addition of high nickel ensures the fluidity of alloy liquid, so that the alloy is solid-solution strengthened and the corrosion resistance is improved. Therefore, the high-lead tin bronze alloy prepared by the invention has excellent structural performance, improved mechanical property, reduced friction coefficient and improved wear resistance, and can meet the severe performance requirements of high PV (more than or equal to 100MPa ∙ m/s), high pressure resistance, strain resistance, wear resistance, high strength casting and the like.
The mechanical properties of the high-strength wear-resistant high-lead tin bronze material prepared by the invention, including tensile property, elongation, hardness and the like, are tested, and the test results are far higher than the mechanical property standard range of the common bearing alloy with the brand ZCUPb20Sn5 in GB/T1174-1992 cast bearing alloy shown in Table 1.
Wherein, the hardness can reach more than 70HB, the tensile strength can reach more than 240MPa, and the elongation exceeds 16%.
In addition, the friction and wear properties of the high-strength wear-resistant high-lead tin bronze material are measured under the conditions of a load of 250N, a linear speed of 3.610m/s and a PV value of 126MPa ∙ m/s, and the result shows that the dry friction coefficient of the high-lead tin bronze material prepared by the method is kept within the range of 0.07-0.11 and is lower than the friction coefficient of an AlTiC-B-Y alloy material without adding a novel grain refiner by 0.23-0.32.
Drawings
FIG. 1 is a graph showing the distribution morphology of lead particles in the alloys prepared in examples 1 to 3.
FIG. 2 is an SEM topography of the alloys prepared in examples 1-3.
FIG. 3 is a gold phase diagram of the structure of the alloy prepared in examples 1-2.
FIG. 4 is a structural gold phase diagram of the alloy of comparative example 1 prepared without the addition of the novel grain refiner and nickel.
FIG. 5 is a structural gold phase diagram of the alloy without the addition of the novel grain refiner, with the addition of 2wt.% nickel, for comparative example 2 preparation.
FIG. 6 is a structural gold phase diagram of the alloy without the addition of the novel grain refiner, with the addition of 3wt.% nickel, for comparative example 3 preparation.
FIG. 7 is a graph showing the variation of friction coefficient of the alloys prepared in example 1, comparative example 1 and comparative example 3.
Detailed Description
Specific embodiments of the present invention will be described in further detail below with reference to the accompanying drawings and examples and comparative examples. The following examples and comparative examples are intended only to more clearly illustrate the technical aspects of the present invention so that those skilled in the art can better understand and utilize the present invention without limiting the scope of the present invention.
The experimental methods, production processes, apparatuses and devices involved in the examples and comparative examples of the present invention, the names and abbreviations thereof all belong to the names conventional in the art, and are clearly and clearly understood in the related fields of use, and the skilled person can understand the conventional process steps according to the names and apply the corresponding devices, and perform according to the conventional conditions or the conditions suggested by the manufacturer.
The various raw materials or reagents used in the examples and comparative examples of the present invention are not particularly limited in source, and are conventional products commercially available.
Among the various raw materials used in the examples of the present invention, the purity of electrolytic copper was 99.9wt.%, and the purity of pure nickel, pure lead, pure tin, and pure zinc was 99.99wt.%.
The AlTiC alloy is an intermediate alloy which is obtained by mixing, pressing and forming 40-50 wt.% of Al powder, 45-55 wt.% of Ti powder and 5-15 wt.% of C powder, carrying out high-temperature self-propagating combustion under vacuum to obtain a self-propagating product, adding the self-propagating product into molten aluminum liquid, diluting until the content of Ti element is 5-5.3 wt.%, and casting.
In other intermediate alloys, the boron content in the copper-boron alloy is 4.62wt.%, and the addition amount of the copper-boron alloy is controlled to be 10.82-43.29 wt.%, so that the boron content in the alloy is 0.05-0.2 wt.%.
The yttrium content in the copper yttrium alloy is 10.07 wt%, the addition amount of the copper yttrium alloy is controlled to be 0.38-0.67 wt%, and the yttrium content in the alloy can be ensured to be 0.04-0.07 wt%.
The phosphorus content in the phosphorus-copper alloy was 14wt.%.
All the raw materials are purchased in a normal manufacturer, and the product components are uniform and the precision is high through inspection.
The alloy or metal except pure nickel, copper-boron alloy and electrolytic copper is wrapped by copper foil paper after weighing, and is preheated in a heat treatment furnace at 120 ℃ to thoroughly remove the moisture in the alloy or metal.
Example 1.
129g of pure nickel, 46.5g of copper-boron alloy and 2915.8g of electrolytic copper are weighed, preheated to 220 ℃ in advance, placed into a crucible preheated to 220 ℃ together, and placed into a smelting furnace heated to 1200 ℃ for smelting.
After the copper alloy is completely melted and boiled, adding 2/3 of 30.7g of phosphorus copper alloy, and deoxidizing and degassing for 5-7 min to remove oxygen in the melt.
16.37g of copper-yttrium alloy, 10.8g of AlTiC alloy, 107g of zinc block, 860g of lead block and 215.2g of tin bean are added into the alloy liquid in sequence every 5-7 min according to the melting point sequence of the alloy elements. Wherein the addition amount of the zinc block is calculated according to the consideration of the burning loss rate of 30 percent. When the alloy is added, the alloy is pressed into the bottom of the alloy liquid by a graphite bell jar.
Stirring for 30s after all the materials are added, and adding the rest 1/3 of the phosphor-copper alloy to fully react oxygen brought in by the materials in the alloy liquid, thereby achieving the effect of thorough deoxidization.
And (3) smelting the alloy liquid uniformly, when the temperature reaches 1200 ℃, discharging and casting the alloy liquid into a metal mold, and opening the mold after 5min to obtain the high-lead tin bronze ZCUPb20Sn5 alloy.
Example 2.
129g of pure nickel, 93.07g of copper-boron alloy and 2852.45g of electrolytic copper are weighed, preheated to 220 ℃ in advance, placed into a crucible preheated to 220 ℃ together, and placed into a smelting furnace heated to 1200 ℃ for smelting.
After the copper alloy is completely melted and boiled, adding 2/3 of 30.7g of phosphorus copper alloy, and deoxidizing and degassing for 5-7 min to remove oxygen in the melt.
According to the melting point sequence of alloy elements, 22.51g of copper yttrium alloy, 21.5g of AlTiC alloy, 107g of zinc block, 860g of lead block and 215.2g of tin bean are added into the alloy liquid in sequence every 5-7 min. When the alloy is added, the alloy is pressed into the bottom of the alloy liquid by a graphite bell jar.
Stirring for 30s after all the materials are added, and adding the rest 1/3 of the phosphor-copper alloy to fully react oxygen brought in by the materials in the alloy liquid, thereby achieving the effect of thorough deoxidization.
And (3) smelting the alloy liquid uniformly, when the temperature reaches 1200 ℃, discharging and casting the alloy liquid into a metal mold, and opening the mold after 5min to obtain the high-lead tin bronze ZCUPb20Sn5 alloy.
Example 3.
129g of pure nickel, 186.15g of copper-boron alloy and 2732.7g of electrolytic copper are weighed, preheated to 220 ℃ in advance, placed into a crucible preheated to 220 ℃ together, and placed into a smelting furnace heated to 1200 ℃ for smelting.
After the copper alloy is completely melted and boiled, adding 2/3 of 30.7g of phosphorus copper alloy, and deoxidizing and degassing for 5-7 min to remove oxygen in the melt.
28.6g of copper-yttrium alloy, 42g of AlTiC alloy, 107g of zinc block, 860g of lead block and 215.2g of tin bean are added into the alloy liquid in sequence every 5-7 min according to the melting point sequence of the alloy elements. When the alloy is added, the alloy is pressed into the bottom of the alloy liquid by a graphite bell jar.
Stirring for 30s after all the materials are added, and adding the rest 1/3 of the phosphor-copper alloy to fully react oxygen brought in by the materials in the alloy liquid, thereby achieving the effect of thorough deoxidization.
And (3) smelting the alloy liquid uniformly, when the temperature reaches 1200 ℃, discharging and casting the alloy liquid into a metal mold, and opening the mold after 5min to obtain the high-lead tin bronze ZCUPb20Sn5 alloy.
The elemental compositions and percentages of the high lead tin bronze ZCUPb20Sn5 alloys prepared in examples 1-3 above are shown in Table 2 below.
The test shows that in the high lead tin bronze ZCUPb20Sn5 alloy prepared in the embodiment, lead mainly exists in a small spherical form. The structure with spherical morphology has better performance, fine grains in the structure, more uniform dendrite distribution and no lead segregation. The metallographic pictures are shown in figures 1-3.
In order to further distinguish the morphology and the size of the lead particles with different sizes and shapes, the size evaluation of the lead particles is carried out by referring to the graphite particle size evaluation software, and the specific evaluation result is shown in figure 1.
Different colors are chosen in fig. 1 to distinguish between different ranges of lead particles. The yellow particles are smallest particles, represent lead particles with the diameter ranging from 0 mu m to 15 mu m, the pink particles represent lead particles with the diameter ranging from 15 mu m to 30 mu m, the blue particles represent lead particles with the diameter ranging from 30 mu m to 60 mu m, the green particles represent lead particles with the diameter ranging from 60 mu m to 120 mu m, the red particles represent lead particles with the diameter ranging from 120 mu m to 250 mu m, and the blue-green particles represent lead particles with the diameter more than or equal to 250 mu m. In the figure, (a), (B) and (c) represent the structure to which 0.05wt.%, 0.1wt.%, and 0.2wt.% of the novel grain refiner AlTiC-B-Y+3wt.% Ni was added, respectively.
In fig. 2, (a), (B) and (c) are SEM morphology of the alloy after addition of 0.05wt.%, 0.1wt.%, 0.2wt.% of the new grain refiner AlTiC-B-Y and 3wt.% Ni, respectively. It can be seen from the figure that the alloy structure is uniformly distributed, and the dendrite walls are in fine equiaxed crystal distribution.
In fig. 3, (a) and (B) are respectively 0.05wt.% of AlTiC-B-Y+Ni3 wt.% of alloy structure and 0.1wt.% of AlTiC-B-Y+Ni3 wt.% of alloy structure, and it can be seen that the alloy structure after adding the novel grain refiner and nickel is uniformly distributed, and dendrites are uniformly distributed in equiaxed crystal.
The mechanical properties of the high lead tin bronze ZCUPb20Sn5 alloy prepared in the above example are shown in Table 3. It can be seen that the addition of the novel grain refiner can refine grains and improve the mechanical property, and the tensile strength, the hardness and the elongation of the alloy are greatly improved within the range of 0.05 to 0.2wt percent of the addition amount.
Compared with the standard data in table 1, at an addition of 0.05wt.%, the tensile strength 253.66MPa of the alloy at room temperature exceeded 58.5% of the national standard 160MPa, the hardness 78HB exceeded 41.8% of the national standard 55HB, and the elongation 17.2% exceeded 1.8 times of the national standard 6%.
Under the conditions of a load of 250N, a linear speed of 3.610m/s and a PV value of 126MPa ∙ m/s, the friction and wear performance of the high-lead tin bronze ZCUPb20Sn5 alloy prepared by the embodiment is tested, and the dry friction coefficient is 0.07-0.11 and is relatively low.
The data show that the high-lead tin bronze ZCUPb20Sn5 alloy prepared by the invention not only can refine and even tissue, lead particles are tiny and evenly distributed, and lead segregation is eliminated, but also can improve the mechanical property and frictional wear property of the alloy material, and the high-quality alloy material is obtained.
Comparative example 1.
According to the elemental composition of the above alloys of examples 1 to 3, a high lead tin bronze ZCUPb20Sn5 alloy was prepared without the addition of nickel and a novel grain refiner.
3118.57g of electrolytic copper is weighed, preheated to 220 ℃ in advance, placed into a crucible preheated to 220 ℃, and placed into a smelting furnace heated to 1200 ℃ for smelting.
After the copper alloy is completely melted and boiled, adding 2/3 of 30.7g of phosphorus copper alloy, and deoxidizing and degassing for 5-7 min to remove oxygen in the melt.
According to the order of the melting point, 107g of zinc block, 860g of lead block and 215.2g of tin bean are added into the alloy liquid in sequence every 5-7 min. When the alloy is added, the alloy is pressed into the bottom of the alloy liquid by a graphite bell jar.
Stirring for 30s after all the materials are added, and adding the rest 1/3 of the phosphor-copper alloy to fully react oxygen brought in by the materials in the alloy liquid, thereby achieving the effect of thorough deoxidization.
And (3) smelting the alloy liquid uniformly, when the temperature reaches 1200 ℃, discharging and casting the alloy liquid into a metal mold, and opening the mold after 5min to obtain the high-lead tin bronze ZCUPb20Sn5 alloy.
Through tests, in the high-lead tin bronze ZCUPb20Sn5 alloy prepared in the example, lead mainly exists in a block shape, the shape distribution is uneven, large lead particles are more, dendrites are more obvious, grains in a structure are coarse, and the segregation phenomenon of lead exists. The golden phase diagram is shown in figure 4.
The mechanical property test results of the alloy are shown in Table 4, the tensile strength of the alloy is 200MPa which exceeds 25% of the national standard, the hardness of the alloy is 61HB which exceeds 10.9% of the national standard, and the elongation of the alloy is 13.85% which exceeds 1.2 times of the national standard at room temperature.
Furthermore, the friction coefficient under the same test conditions reaches 0.23-0.32, which is obviously higher than that of the alloy prepared by the example.
The test results prove that the comparative example has coarse grains in the structure and lead segregation phenomenon because nickel and a novel grain refiner are not added, and the mechanical property of the comparative example exceeds the national standard, but the comparative example is not high compared with the example, and has larger friction coefficient.
Comparative example 2.
According to the elemental composition of the above-described alloys of examples 1 to 3, a high lead tin bronze ZCUPb20Sn5 alloy was prepared without adding a novel grain refiner and with the addition of 2wt.% nickel.
86g of pure nickel and 3032.57g of electrolytic copper are weighed, preheated to 220 ℃ in advance, put into a crucible preheated to 220 ℃ together, and put into a smelting furnace heated to 1200 ℃ for smelting.
After the copper alloy is completely melted and boiled, adding 2/3 of 30.7g of phosphorus copper alloy, and deoxidizing and degassing for 5-7 min.
According to the order of the melting point, 107g of zinc block, 860g of lead block and 215.2g of tin bean are added into the alloy liquid in sequence every 5-7 min. When the alloy is added, the alloy is pressed into the bottom of the alloy liquid by a graphite bell jar.
Stirring for 30s after all the materials are added, adding the rest 1/3 of the phosphor copper alloy, smelting the alloy liquid uniformly, when the temperature reaches 1200 ℃, discharging and casting into a metal mold, and opening the mold and taking out the piece after 5min to prepare the high-lead tin bronze ZCUPb20Sn5 alloy.
Comparative example 3.
According to the elemental composition of the above-described alloys of examples 1 to 3, a high lead tin bronze ZCUPb20Sn5 alloy was prepared without adding a novel grain refiner and with the addition of 3wt.% nickel.
129g of pure nickel and 2989.53g of electrolytic copper are weighed, preheated to 220 ℃ in advance, put into a crucible preheated to 220 ℃ together, and put into a smelting furnace heated to 1200 ℃ for smelting.
After the copper alloy is completely melted and boiled, adding 2/3 of 30.7g of phosphorus copper alloy, and deoxidizing and degassing for 5-7 min.
According to the order of the melting point, 107g of zinc block, 860g of lead block and 215.2g of tin bean are added into the alloy liquid in sequence every 5-7 min. When the alloy is added, the alloy is pressed into the bottom of the alloy liquid by a graphite bell jar.
Stirring for 30s after all the materials are added, adding the rest 1/3 of the phosphor copper alloy, smelting the alloy liquid uniformly, when the temperature reaches 1200 ℃, discharging and casting into a metal mold, and opening the mold and taking out the piece after 5min to prepare the high-lead tin bronze ZCUPb20Sn5 alloy.
According to tests, compared with the case of no nickel, the lead particles in comparative examples 2 and 3 are small and round, are uniformly distributed, have good performance, have fine grains in a structure and basically have no segregation phenomenon of lead due to the addition of 2 to 3wt.% of nickel. The golden phase diagram is shown in fig. 5 and 6.
The mechanical properties test results of Table 4 show that the nickel content is in the range of 2 to 3wt.%, the hardness, tensile strength and elongation are all increased over those without nickel addition. When the nickel content is 3 wt%, the tensile strength is 221.15MPa at room temperature, exceeds 38.2% of the national standard, the hardness is 78.12HB, exceeds 42.04% of the national standard, and the elongation is 14.85% and exceeds 1 time of the national standard. Compared with comparative example 1, the mechanical properties are improved, wherein the tensile strength is improved by 10.6%, the hardness is improved by 28.1%, and the elongation is increased by 7.2%.
Therefore, the effect of refining the lead particles is relatively weaker than that of adding the novel grain refiner, although the structure can be refined by adding only metallic nickel without adding the novel grain refiner.
Also, the dry friction coefficient is smaller at a nickel content of 2 to 3wt.% than when no nickel is added, wherein the friction coefficient at a nickel content of 3wt.% is 0.18 to 0.25, lower than that of comparative example 1.
FIG. 7 further shows friction curves for the alloys of example 1, comparative example 1, and comparative example 3 at a PV value of 126 MPa.m/s. It can be seen from the figure that the coefficient of friction of the alloy after addition of the novel grain refiner and nickel is much lower than that of the alloys of comparative examples 1 and 3.
The mixed addition of the high nickel and the novel AlTiC-B-Y grain refiner can refine lead particles, lead particles are fine and uniformly distributed, lead segregation is reduced, the structure is more refined and uniform, and the mechanical property and friction property of the alloy material are improved, so that the alloy material can meet the antifriction and wear resistance under the condition of high PV (more than or equal to 100MPa ∙ m/s).
The above embodiments of the invention are not intended to be exhaustive or to limit the invention to the precise forms disclosed. Various changes, modifications, substitutions and alterations may be made by those skilled in the art without departing from the principles and spirit of the invention, and it is intended that the invention encompass all such changes, modifications and alterations as fall within the scope of the invention.
Claims (9)
1. A high-strength wear-resistant high-lead tin bronze material consists of the following components in percentage by weight: 19 to 21wt.% of Pb, 4.5 to 5.5wt.% of Sn, 1.5 to 2.5wt.% of Zn, 0.05 to 0.1wt.% of P, 2 to 3wt.% of Ni, 0.05 to 0.2wt.% of AlTiC alloy, 0.05 to 0.2wt.% of B, 0.04 to 0.07wt.% of Y, and the balance of copper; the AlTiC alloy is an intermediate alloy obtained by mixing, pressing and forming 40-50 wt.% of Al powder, 45-55 wt.% of Ti powder and 5-15 wt.% of C powder, performing high-temperature self-propagating combustion under vacuum to obtain a self-propagating product, adding the self-propagating product into molten aluminum liquid, diluting until the content of Ti element is 5-5.3 wt.%, and casting.
2. The preparation method of the high-strength wear-resistant high-lead tin bronze material comprises the steps of smelting electrolytic copper, copper-boron alloy and pure nickel which are required to be subtracted from the amount of copper carried in each added intermediate alloy according to the proportion content, adding 2/3 of the proportion content of phosphorus-copper alloy, carrying out first deoxidation and degassing treatment on alloy liquid, adding the proportion content of AlTiC alloy, copper-yttrium alloy, zinc, lead and tin, finally adding the rest 1/3 of the proportion content of phosphorus-copper alloy, carrying out deoxidation and degassing treatment again, heating the alloy liquid to 1200 ℃ and discharging and casting to obtain the high-lead tin bronze material.
3. The method for producing a high-strength wear-resistant high-lead tin bronze material according to claim 2, characterized in that stirring treatment is accompanied in the melting process of the alloy liquid.
4. The method for producing a high-strength wear-resistant high-lead tin bronze material according to claim 2, characterized in that pure nickel and copper-boron alloy are preheated to 220 ℃ or more and melted together with electrolytic copper preheated to the same temperature.
5. The method for preparing the high-strength wear-resistant high-lead tin bronze material according to claim 2, wherein after the first deoxidation and degassing treatment of the alloy liquid, the AlTiC alloy and the copper yttrium alloy with the proportioning contents are added, and then the zinc, the lead and the tin with the proportioning contents are sequentially added according to the melting point sequence of alloy elements.
6. The method for producing a high-strength wear-resistant high-lead tin bronze material according to claim 2, characterized in that after each addition of one alloy or metal, another alloy or metal is added at intervals of 5 to 7 minutes.
7. The method for producing a high-strength wear-resistant high-lead tin bronze material according to claim 6, wherein the alloy liquid is sufficiently stirred after each addition of an alloy or metal.
8. The method for producing a high-strength and wear-resistant high-lead tin bronze material according to claim 2, characterized in that the alloy liquid is subjected to stirring treatment for not less than 30 seconds before the remaining phosphor-copper alloy is added.
9. The method for preparing the high-strength wear-resistant high-lead tin bronze material according to claim 2, wherein the deviation of the tapping casting temperature of the alloy liquid at 1200 ℃ is not more than 20 ℃.
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