Silicon brass, tin bronze and beryllium bronze spectral analysis standard substance and preparation method

Abstract

The present application relates to a kind of standard substance technical field, specifically to a kind of silicon brass, tin bronze and beryllium bronze spectral analysis standard substance and preparation method, the chemical composition composition and content range of the standard substance are as follows: Zn:0.0003~16%;Sn:0.0001~6%;P:0.002~0.04%;Mn:0.0004~0.02%;Fe:0.02~0.07%;Ni:0.001~6%;Si:0.0005~3.6%;Ag:0.001~0.003%;Cu:80~97%;Pb:0.0005~0.005%;Sb:0.0002~0.003%;As:0.0001~0.0003%;Mg:0.004~0.007%;Cr:0.01~0.02%;Co:0.001~2.8%;Al:0.0003~0.05%;Be:0.6~2.1%;Ti:0.07~0.09%;Zr:0.01~0.03%.The component design and preparation process of the silicon brass, tin bronze and beryllium bronze spectral analysis standard substance of the present application are reasonable, after uniformity test and stability investigation, standard substance uniformity and stability are good.

Description

Technical Field

[0001] This invention relates to the technical field of silicon brass, tin bronze and beryllium bronze standard materials, specifically to a silicon brass, tin bronze and beryllium bronze spectral analysis standard material and its preparation method. Background Technology

[0002] Currently, common copper alloy standard materials on the market include silicon brass, tin bronze, and beryllium bronze. Silicon brass HSi80-3 is widely used in ship parts and water pipe fittings. Tin bronze Cu6Ni6Sn, with the addition of nickel and tin, improves the alloy's strength, corrosion resistance, and oxidation resistance, and is used in precision machinery and automotive parts. Beryllium bronze TBe0.6-2.5 (C17500) is a supersaturated solid solution copper-based alloy used to manufacture welding electrode materials, wear-resistant and corrosion-resistant workpieces, etc. Beryllium bronze TBe1.9 contains small amounts of nickel and titanium; the addition of titanium refines the as-cast state, improves the alloy's microstructure uniformity, and gives the alloy low elastic hysteresis and high fatigue strength. Beryllium bronze TBe1.9 is used in high-performance springs, especially in automobiles, aerospace, and precision machinery.

[0003] The National Institute of Standards and Technology (NIST) of the United States developed beryllium bronze spectral standard materials SRM1121, SRM1122, and SRM1123, with Be contents of 1.89%, 1.75%, and 0.46%, respectively. Shenyang Nonferrous Metals Processing Plant developed beryllium bronze spectral standard samples BYG195021~BYG195025 in 1977, and Shenyang Zhunyuan Technology Co., Ltd. developed cast tin bronze spectral standard sample GSB04-2707-2011 in 2011.

[0004] Currently, the market lacks primary standard materials for spectral analysis such as silicon brass HSi80-3, tin bronze Cu6Ni6Sn, and beryllium bronze TBe2, TBe0.6-2.5, and TBe1.9, which brings many difficulties to measurement, calibration, and quality control management, and cannot adequately meet the needs of enterprise production and development. Therefore, it is necessary to develop spectral analysis standard materials for silicon brass, tin bronze, and beryllium bronze to better calibrate instruments, evaluate measurement methods, and assign values ​​to materials, thereby better serving enterprise production and ensuring the accuracy of test data. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a standard reference material for the spectral analysis of silicon brass, tin bronze, and beryllium bronze, along with its preparation method. This standard reference material has a reasonable composition design and preparation process, good uniformity and stability, and contains a wide range of quantifying elements. It can be widely used in the analysis and testing of silicon brass, tin bronze, and beryllium bronze.

[0006] This invention is achieved through the following technical solution:

[0007] This invention provides a standard reference for the spectral analysis of silicon brass, tin bronze, and beryllium bronze. The chemical composition and content range of this standard reference are as follows: Zn: 0.0003~16%; Sn: 0.0001~6%; P: 0.002~0.04%; Mn: 0.0004~0.02%; Fe: 0.02~0.07%; Ni: 0.001~6%; Si: 0.0005~3.6%; Ag: 0.001~0.003%; Cu : 80~97%; Pb: 0.0005~0.005%; Sb: 0.0002~0.003%; As: 0.0001~0.0003%; Mg: 0.004~0.007%; Cr: 0 .01~0.02%; Co: 0.001~2.8%; Al: 0.0003~0.05%; Be: 0.6~2.1%; Ti: 0.07~0.09%; Zr: 0.01~0.03%.

[0008] The spectral analysis standard materials for silicon brass, tin bronze, and beryllium bronze of this invention consist of five standard materials, including one silicon brass point (numbered ZBY929), one tin bronze point (numbered ZBY930), and three beryllium bronze points (numbered ZBY3302a, ZBY3304a, and ZBY3305). Specifically, the spectral analysis standard materials for silicon brass, tin bronze, and beryllium bronze consist of the following five standard materials:

[0009] (1) ZBY929 (silicon brass), the mass percentage of each component is as follows: Zn: 15.94±0.08%; Sn: 0.0011±0.0003%; P: 0.005±0.001%; ​​Mn: 0.0005±0.0001%; ​​Fe: 0.022±0.003%; Ni: 0.0011±0.0002%; Si: 3.56±0.05%; Ag: 0.0010±0.0002%; As: 0.00014±0.00005%; Sb: 0.0002±0.0001%; ​​Cu: 80.34±0.10%; Pb: 0.0005±0.0001%;

[0010] (2) ZBY930 (tin bronze), the mass percentage of each component is as follows: Zn: 0.090±0.005%; Sn: 5.80±0.10%; P: 0.0031±0.0004%; Mn: 0.018±0.002%; Fe: 0.062±0.004%; Ni: 5.96±0.04%; Si: 0.0005±0.0001%; ​​Sb: 0.0022±0.0007%; Co: 0.0058±0.0003%; Al: 0.0003±0.0001%; ​​Cu: 88.06±0.10%; Pb: 0.0042±0.0005%;

[0011] (3) ZBY3302a (beryllium bronze), the mass percentages of each component are as follows: Zn: 0.0012±0.0002%; Sn: 0.0006±0.0001%; ​​P: 0.028±0.003%; Mn: 0.0024±0.0003%; Fe: 0.057±0.004%; Ni: 0.596±0.005%; Si: 0.046±0.003%; Mg: 0.0047±0.0005%; Cr: 0.010±0.003%; Ag: 0.0017±0.0002%; As: 0.0002±0.0001%; ​​Sb: 0.0003±0.0001%; ​​Co: 0.0011±0.0002%; Al: 0.042±0.003%; Be : 2.00±0.03%; Cu: 97.27±0.10%; Pb: 0.0006±0.0001%; ​​Zr: 0.029±0.004%;

[0012] (4) ZBY3304a (beryllium bronze), the mass percentages of each component are: Zn: 0.0004±0.0001%; ​​Sn: 0.0002±0.0001%; ​​P: 0.014±0.002%; Mn: 0.0010± 0.0001%; ​​Fe: 0.026±0.003%; Ni: 0.052±0.004%; Si: 0.021±0.003%; Mg: 0.0059±0.0006%; Cr: 0.013±0.002%; Ag: 0.0025±0.0003%; Sb: 0.0005%±0.0001%; ​​Co: 2.78±0.04%; Al: 0.016±0.002%; Be: 0.685±0.004%; Cu: 96.33±0.09%; Pb: 0.0004±0.0001%; ​​Zr: 0.020±0.003%;

[0013] (5) ZBY3305 (beryllium bronze), the mass percentage of each component is as follows: Zn: 0.0010±0.0002%; P: 0.033±0.003%; Mn: 0.0027±0.0002%; Fe: 0.068±0.005%; Ni: 0.49±0.02%; Si: 0.046±0.004%; Mg: 0.0069±0.0004%; Cr: 0.018±0.002%; Ag: 0. 0019±0.0003%; As: 0.00015±0.00004%; Sb: 0.0003±0.0001%; ​​Co: 0.0016±0.0004%; Al: 0.041±0.00 3%; Be: 2.01±0.03%; Cu: 97.24±0.10%; Pb: 0.0004±0.0001%; ​​Ti: 0.081±0.008%; Zr: 0.012±0.002%.

[0014] This invention also provides a method for preparing spectral analysis standard materials of silicon brass, tin bronze, and beryllium bronze, comprising the following steps:

[0015] S1. Investigation phase: Collect physicochemical property data of target samples and determine the composition range and uncertainty requirements of standard substances.

[0016] S2. Component design: Based on the survey data, at least 3 different component gradients are designed using orthogonal experimental design, with the component content difference between each group not less than 5%.

[0017] S3. Prepare raw materials according to the design range and verify the composition to ensure that the main components are within the design range; the raw materials include: high-purity electrolytic copper; alloying elements: pure silicon, #2 pure zinc, pure nickel, pure cobalt, pure metals Fe, Cr, Al, Mg, Sn, Ag, Pb, Mn, Sb; wherein: Cu, Pb, Zn, Ni, Mn, Si, Sb, Co, Sn, Ag are added in pure metal or non-metal form; Cu is high-purity electrolytic copper (ω Cu =99.95%), Si is pure silicon (ω Si =99.9%), Zn is #2 pure zinc (ω Zn =99.95%), Sn, Ag, Pb, Mn, Sb, and Co all have a purity of ω=99.9%; master alloys: Cu-4%Be, Cu-3%Fe, and Cu-3%P; deoxidizer: phosphorus copper, covering agent: borax.

[0018] S4. Charging and smelting:

[0019] S41. Melting silicon brass / tin bronze: In a 250kg medium-frequency induction furnace, first load 4 / 5 of the total electrolytic copper with Cu-Fe master alloy, Ni, and Si into the furnace at once; after complete melting, add the remaining electrolytic copper to cool down, and then add Zn; after Zn melts, add Mn, Pb, Sn, Ag, and Co in sequence; before furnace analysis, add Sb and Cu-P master alloy, and control the melting temperature at 1100~1500℃.

[0020] S42. Smelting Beryllium Bronze: Add electrolytic copper to a 250kg medium-frequency induction furnace, melt it, and then heat it to 1100℃~1250℃; add 0.1%~0.3% phosphorus copper for deoxidation to reduce Cu2O inclusions; add Cu-4%Be master alloy to prevent pure beryllium volatilization (beryllium vapor is highly toxic), stir for 10min~15min to ensure uniformity; then add Ni, Co, Fe, Cr, Al, and Mg in sequence, stirring until the composition is uniform; purge with argon gas to remove gas, cover the melt with borax, skim off the slag, and let it stand. Note: Copper needs to be preheated to remove surface oxides; due to its high toxicity and activity, beryllium is added in the form of Cu-Be master alloy to reduce the risk of volatilization and oxidation, and to reduce the difficulty of smelting.

[0021] S5. Casting and Molding: Silicon brass is cast at a temperature controlled between 1150 and 1200℃, and tin bronze is cast at a temperature controlled between 1050 and 1100℃. A direct water-cooled crystallizer is used, employing hydraulic semi-continuous casting with a water pressure of 0.03 MPa to 0.05 MPa. The casting speed is 6 to 7 meters per hour, yielding silicon brass ingots and tin bronze ingots with diameters of 180 × 1200 mm. Beryllium bronze is cast using hydraulic semi-continuous casting at a temperature controlled between 1050 and 1100℃ to avoid overheating of the melt and resulting in grain coarsening; rapid water cooling is used to prevent segregation, yielding beryllium bronze ingots with diameters of 120 mm.

[0022] S6. Processing: Silicon brass / tin bronze ingots are extruded into Φ40mm copper rods using a 2000-ton hydraulic press, and then processed into Φ40×30mm silicon brass and tin bronze spectral blocks; beryllium bronze ingots are hot-forged at 750℃~850℃ to obtain Φ40×3000mm rods, and after annealing heat treatment, they are processed into Φ40×30mm beryllium bronze spectral blocks.

[0023] The beneficial effects of this invention are:

[0024] The standard reference materials prepared in this invention were compared with similar domestic and international standard reference materials with similar elemental contents. The comparative data shows that the method used for value determination analysis of these standard reference materials is accurate and reliable. The uncertainties of each element are close to those of similar foreign standard reference materials, and the uncertainties of some elements are even better than those of similar foreign standard reference materials. The silicon brass, tin bronze, and beryllium bronze standard reference materials of this invention contain HSi80-3 for silicon brass, Cu6Ni6Sn for tin bronze, and TBe2, TBe0.6-2.5, and TBe1.9 for beryllium bronze, filling the gap in domestic silicon brass and Cu6Ni6Sn tin bronze standard reference materials and reaching the international leading level for similar standard reference materials. The silicon brass, tin bronze, and beryllium bronze standard reference materials have a wide range of applications and a large number of elements with defined values. Values ​​have been defined for 19 elements, including major and trace elements, and they are widely used in the analysis and testing of silicon brass, tin bronze, and beryllium bronze. Attached Figure Description

[0025] Figure 1 This is the spectrometer working curve for the Zn component in the silicon brass spectral analysis standard material of this invention.

[0026] Figure 2 This is the spectrometer operating curve for the Sn component in the silicon brass spectral analysis standard material of this invention.

[0027] Figure 3 The spectrometer operating curve is shown for the P component in the silicon brass spectral analysis standard material of this invention.

[0028] Figure 4 This is the spectrometer working curve for the Mn component in the silicon brass spectral analysis standard material of this invention.

[0029] Figure 5 The spectrometer operating curves are for the Fe component in the silicon brass spectral analysis standard material of this invention.

[0030] Figure 6 The spectrometer operating curves are for the Ni content in the silicon brass spectral analysis standard material of this invention.

[0031] Figure 7 The spectrometer operating curves are for the Si component in the silicon brass spectral analysis standard material of this invention.

[0032] Figure 8 This is the spectrometer working curve for the Pb component in the silicon brass spectral analysis standard material of this invention.

[0033] Figure 9 The spectrometer operating curve is shown for the Sb component in the silicon brass spectral analysis standard material of this invention.

[0034] Figure 10 The spectrometer operating curve is shown for the As component in the silicon brass spectral analysis standard material of this invention.

[0035] Figure 11 This is the spectrometer working curve for the Zn component in the tin bronze spectral analysis standard material of this invention.

[0036] Figure 12 This is the spectrometer working curve for the Sn component in the tin bronze spectral analysis standard material of this invention.

[0037] Figure 13 This is the spectrometer working curve of the P component in the tin bronze spectral analysis standard material of this invention.

[0038] Figure 14 This is the spectrometer working curve for the Al component in the tin bronze spectral analysis standard material of this invention.

[0039] Figure 15 This is the spectrometer working curve for the Fe component in the tin bronze spectral analysis standard material of this invention.

[0040] Figure 16 This is the spectrometer working curve for the Ni component in the tin bronze spectral analysis standard material of this invention.

[0041] Figure 17 This is the spectrometer working curve for the Fe component in the beryllium bronze spectral analysis standard material of this invention.

[0042] Figure 18 This is the spectrometer working curve for the Ni component in the beryllium bronze spectral analysis standard material of this invention.

[0043] Figure 19 This is the spectrometer working curve for the Si component in the beryllium bronze spectral analysis standard material of this invention.

[0044] Figure 20 This is the spectrometer working curve for the Mg component in the beryllium bronze spectral analysis standard material of this invention.

[0045] Figure 21 This is the spectrometer working curve for the Al component in the beryllium bronze spectral analysis standard material of this invention.

[0046] Figure 22 This is the spectrometer operating curve for the Be component in the beryllium bronze spectral analysis standard material of this invention. Detailed Implementation

[0047] To clearly illustrate the technical features of this solution, the following detailed implementation method will be used to explain the solution.

[0048] Example 1: A standard reference for the spectral analysis of silicon brass, tin bronze, and beryllium bronze. The chemical composition and content range of this standard reference are as follows: Zn: 0.0003~16%; Sn: 0.0001~6%; P: 0.002~0.04%; Mn: 0.0004~0.02%; Fe: 0.02~0.07%; Ni: 0.001~6%; Si: 0.0005~3.6%; Ag: 0.001~0.003%; C u: 80~97%; Pb: 0.0005~0.005%; Sb: 0.0002~0.003%; As: 0.0001~0.0003%; Mg: 0.004~0.007%; Cr: 0.01~0.02%; Co: 0.001~2.8%; Al: 0.0003~0.05%; Be: 0.6~2.1%; Ti: 0.07~0.09%; Zr: 0.01~0.03%.

[0049] In this embodiment, the spectral analysis standard materials for silicon brass, tin bronze, and beryllium bronze consist of a total of 5 standard materials, including 1 silicon brass point, numbered ZBY929; 1 tin bronze point, numbered ZBY930; and 3 beryllium bronze points, numbered ZBY3302a, ZBY3304a, and ZBY3305.

[0050] Specifically, the spectral analysis standard materials for silicon brass, tin bronze, and beryllium bronze consist of the following five standard materials:

[0051] (1) ZBY929 (silicon brass), the mass percentage of each component is as follows: Zn: 15.94±0.08%; Sn: 0.0011±0.0003%; P: 0.005±0.001%; ​​Mn: 0.0005±0.0001%; ​​Fe: 0.022±0.003%; Ni: 0.0011±0.0002%; Si: 3.56±0.05%; Ag: 0.0010±0.0002%; As: 0.00014±0.00005%; Sb: 0.0002±0.0001%; ​​Cu: 80.34±0.10%; Pb: 0.0005±0.0001%;

[0052] (2) ZBY930 (tin bronze), the mass percentage of each component is as follows: Zn: 0.090±0.005%; Sn: 5.80±0.10%; P: 0.0031±0.0004%; Mn: 0.018±0.002%; Fe: 0.062±0.004%; Ni: 5.96±0.04%; Si: 0.0005±0.0001%; ​​Sb: 0.0022±0.0007%; Co: 0.0058±0.0003%; Al: 0.0003±0.0001%; ​​Cu: 88.06±0.10%; Pb: 0.0042±0.0005%;

[0053] (3) ZBY3302a (beryllium bronze), the mass percentages of each component are as follows: Zn: 0.0012±0.0002%; Sn: 0.0006±0.0001%; ​​P: 0.028±0.003%; Mn: 0.0024±0.0003%; Fe: 0.057±0.004%; Ni: 0.596±0.005%; Si: 0.046±0.003%; Mg: 0.0047±0.0005%; Cr: 0.010±0.003%; Ag: 0.0017±0.0002%; As: 0.0002±0.0001%; ​​Sb: 0.0003±0.0001%; ​​Co: 0.0011±0.0002%; Al: 0.042±0.003%; Be : 2.00±0.03%; Cu: 97.27±0.10%; Pb: 0.0006±0.0001%; ​​Zr: 0.029±0.004%;

[0054] (4) ZBY3304a (beryllium bronze), the mass percentages of each component are: Zn: 0.0004±0.0001%; ​​Sn: 0.0002±0.0001%; ​​P: 0.014±0.002%; Mn: 0.0010± 0.0001%; ​​Fe: 0.026±0.003%; Ni: 0.052±0.004%; Si: 0.021±0.003%; Mg: 0.0059±0.0006%; Cr: 0.013±0.002%; Ag: 0.0025±0.0003%; Sb: 0.0005%±0.0001%; ​​Co: 2.78±0.04%; Al: 0.016±0.002%; Be: 0.685±0.004%; Cu: 96.33±0.09%; Pb: 0.0004±0.0001%; ​​Zr: 0.020±0.003%;

[0055] (5) ZBY3305 (beryllium bronze), the mass percentage of each component is as follows: Zn: 0.0010±0.0002%; P: 0.033±0.003%; Mn: 0.0027±0.0002%; Fe: 0.068±0.005%; Ni: 0.49±0.02%; Si: 0.046±0.004%; Mg: 0.0069±0.0004%; Cr: 0.018±0.002%; Ag: 0. 0019±0.0003%; As: 0.00015±0.00004%; Sb: 0.0003±0.0001%; ​​Co: 0.0016±0.0004%; Al: 0.041±0.00 3%; Be: 2.01±0.03%; Cu: 97.24±0.10%; Pb: 0.0004±0.0001%; ​​Ti: 0.081±0.008%; Zr: 0.012±0.002%.

[0056] Example 2: A method for preparing spectral analysis standard materials of silicon brass, tin bronze, and beryllium bronze, comprising the following steps:

[0057] S1. Investigation phase: Collect physicochemical property data of target samples and determine the composition range and uncertainty requirements of standard substances.

[0058] S2. Component design: Based on the survey data, at least 3 different component gradients are designed using orthogonal experimental design, with the component content difference between each group not less than 5%.

[0059] S3. Prepare raw materials according to the design range and verify the composition to ensure that the main components are within the design range; the raw materials include: high-purity electrolytic copper; alloying elements: pure silicon, #2 pure zinc, pure nickel, pure cobalt, pure metallic Fe, Cr, Al, Mg, Sn, Ag, Pb, Mn, Sb. Cu, Pb, Zn, Ni, Mn, Si, Sb, Co, Sn, and Ag are added in pure metallic or non-metallic form. Cu is high-purity electrolytic copper (ω... Cu =99.95%), Si is pure silicon (ω Si =99.9%), Zn is #2 pure zinc (ω Zn =99.95%), Sn, Ag, Pb, Mn, Sb, and Co all have a purity of ω=99.9%; Master alloys: Cu-4%Be, Cu-3%Fe, and Cu-3%P. Deoxidizer: phosphorus copper; Covering agent: borax.

[0060] S4. Charging and smelting:

[0061] S41. Melting Silicon Brass / Tin Bronze: In a 250kg medium-frequency induction furnace, first load 4 / 5 of the total electrolytic copper along with Cu-Fe master alloy, Ni, and Si into the furnace at once; after complete melting, add the remaining electrolytic copper to cool, then add Zn; after Zn melts, add Mn, Pb, Sn, Ag, and Co in sequence; before furnace pre-analysis, add Sb and Cu-P master alloy. The melting temperature needs to consider the dual effects of high-melting-point elements and easily oxidized volatile elements. If the temperature is too low, the metal melting is insufficient and incomplete, the alloying rate is slow, resulting in non-uniform liquid phase composition. If the temperature is too high, element loss is severe, gas absorption tendency is high, and there are many oxide inclusions, seriously affecting the homogeneity of the sample. The smelting temperature of silicon brass is controlled at 1100~1500℃, while the smelting temperature of tin bronze is controlled at 1100℃~1300℃ depending on the stage. After adding electrolytic copper and nickel plates, the temperature is raised to 1250℃~1300℃. After the copper and nickel are completely melted, the temperature is lowered to 1100℃~1150℃, and tin is added (to avoid high-temperature oxidation loss). Then, 0.2%~0.5% phosphorus copper is added for deoxidation, and the mixture is stirred and allowed to stand to remove slag. A small amount of borax (0.1%~0.3%) is then added to form slag and remove impurities. The residence time of the alloy liquid in the high-temperature zone also affects the sample quality. If the residence time is too short, the alloying elements will not diffuse sufficiently, resulting in uneven alloy liquid; if the residence time is too long, the tendency to absorb gas is high, and burn-off and oxidation are severe. The alloy liquid of silicon brass / tin bronze is kept at 1100~1300℃ for 1~1.5 hours, during which pre-furnace analysis and composition adjustment are performed. Pre-furnace analysis and testing were performed using photoelectric emission spectrometer and plasma emission spectrometer. The furnace was then opened after the composition met the requirements.

[0062] S42. Smelting Beryllium Bronze: Add electrolytic copper to a 250kg medium-frequency induction furnace, melt it, and then heat it to 1100℃~1250℃; add 0.1%~0.3% phosphorus copper for deoxidation to reduce Cu2O inclusions; add Cu-4%Be master alloy to prevent pure beryllium volatilization (beryllium vapor is highly toxic), and stir for 10min~15min to ensure uniformity. Then add Ni, Co, Fe, Cr, Al, and Mg in sequence, stirring until the composition is uniform; purge with argon gas to remove gas, cover the melt with borax, skim off the slag, and let it stand. Note: Copper needs to be preheated to remove surface oxides; beryllium, due to its high toxicity and activity, is added in the form of Cu-Be master alloy to reduce the risk of volatilization and oxidation, and to reduce the difficulty of smelting.

[0063] S5. Casting and Molding: Silicon brass is cast at a temperature controlled between 1150 and 1200℃, and tin bronze is cast at a temperature controlled between 1050 and 1100℃. A direct water-cooled crystallizer is used, employing hydraulic semi-continuous casting with a water pressure of 0.03 MPa to 0.05 MPa. The casting speed is 6 to 7 meters per hour, yielding silicon brass ingots and tin bronze ingots with diameters of 180 × 1200 mm. Beryllium bronze is cast using hydraulic semi-continuous casting at a temperature controlled between 1050 and 1100℃ to avoid overheating of the melt and resulting in grain coarsening; rapid water cooling is used to prevent segregation, yielding beryllium bronze ingots with diameters of 120 mm.

[0064] S6. Processing: Silicon brass / tin bronze ingots are extruded into Φ40mm copper rods using a 2000-ton hydraulic press, and then processed into Φ40×30mm silicon brass and tin bronze spectral blocks. Beryllium bronze ingots are hot-forged at 750℃~850℃ to obtain Φ40×3000mm rods, which are then processed into Φ40×30mm beryllium bronze spectral blocks after annealing heat treatment. Annealing heat treatment includes solid-liquid treatment and aging treatment; solution treatment: holding at 780℃~820℃ for 1~2 hours to completely dissolve beryllium into the copper matrix; water quenching, cooling rate >100℃ / s, to form a supersaturated solid solution. Aging treatment: holding at 300℃~350℃ for 2~4 hours to improve hardness and strength; annealing of the beryllium bronze to eliminate internal stress and purify the microstructure.

[0065] The silicon brass, tin bronze and beryllium bronze spectral analysis standard materials prepared in Example 2 were subjected to homogeneity testing, stability investigation and value determination analysis, and the analysis data were summarized and processed.

[0066] I. Uniformity Test

[0067] Longitudinal sectioning test: To check the longitudinal segregation of the standard material sample blocks, one sample was selected from each furnace, and the axis was non-destructively dissected using wire cutting. The samples were then excited at equal intervals, and the average and range values ​​were statistically analyzed. The results showed that the ranges at both the beginning and end of the test were less than the allowable error or repeatability r of the corresponding analytical method.

[0068] Initial uniformity inspection: A 10 mm sample was taken from each end of the round bar. Using a Spectro Lab M11 spectrometer, traces were taken with specialized standard materials. Complete standardization was performed using imported silicon brass, tin bronze, and beryllium bronze standard materials, followed by type standardization using standard materials of similar content and grade. Measurements were then taken three times in parallel along an equilateral triangle on each surface, with spectral dots marked accordingly. Uniformity segregation was checked using photoelectric emission spectroscopy, and the range method was used for statistical analysis. The segregation test data are shown in Table 1. The results show that the ranges at both ends are less than the repeatability r of the corresponding analytical method, indicating that the initial ingot inspection is qualified.

[0069] Table 1. Segregation test of the spectral analysis standard material of this invention (%)

[0070]

[0071] Metallographic examination: A full-section circular specimen was taken from both the head and tail of the bar for low-magnification examination. The specimens were examined according to the specifications of GB / T 13298-2015 "Metallic Microstructure Examination Method". The results showed that the silicon brass, tin bronze, and beryllium bronze bars had normal and uniform microstructures, free from defects such as porosity, cracks, and inclusions. Homogeneity test: Following the technical specifications of the standard material, 20 samples were selected from the finished product blocks, numbered sequentially, and analyzed in a random order.

[0072] For three different locations on the cross-section of each sample, the following steps were performed on a Spectro Lab M11 photoelectric emission spectrometer (Germany): first, traces were created using dedicated standard materials; then, complete standardization was performed using imported silicon brass, tin bronze, and beryllium bronze standard materials; finally, type standardization was performed using standard materials of similar content and grade; and the homogeneity was tested using photoelectric emission spectroscopy analysis method (YS / T 482-2022). The test results were statistically analyzed using the variance method. The statistical results of the homogeneity test F-values ​​are shown in Table 2. Statistical analysis showed that the F-values ​​for all elements were less than F0. α(0.05) The value indicates that the uniformity test is satisfactory.

[0073] Table 2. Homogeneity test F-values ​​(F values) of the spectral analysis standard materials of this invention 0.05 =1.84)

[0074]

[0075] II. Stability Test

[0076] The stability of the standard material was investigated multiple times over two years using the photoelectric emission spectroscopy method according to YS / T 482-2022. The results were statistically tested for stability using linear fitting. If the slope |b1| < t α，（n-2） If ×s(b1), the slope is not significant, indicating that the sample is stable. In the formula, b1 is the slope of the fitted line, s(b1) is the uncertainty of the slope, and t... α，（n-2） The student distribution has n-2 degrees of freedom and a certain confidence level. The stability test values ​​from February 2023 to February 2025 were calculated, and the results show that the stability test data are consistent over the two years, indicating good sample stability. Furthermore, comparing the stability test results with the uncertainty of the final value, the difference between two measurements for all stability test items did not exceed the uncertainty of the final value. According to ISO Guide 35, if the following conditions are met: In the formula: X CRM This represents the characteristic value of CRM. The measured observations are given, k is the coverage factor, and the confidence level is 95%. Let k=2, uCRM The uncertainty of the characteristic value, This refers to measurement uncertainty. Ideally, measurement uncertainty is much smaller than characteristic value uncertainty. Characteristic value uncertainty is generally greater than measurement uncertainty. Considering only characteristic value uncertainty is more informative. Therefore, we compare the absolute value of the difference between the observed value and the characteristic value with the characteristic value uncertainty. If the difference is less than or close to the characteristic value uncertainty, then the material can be considered sufficiently stable, and its stability is proven.

[0077] Compare the spectral measurements of this reference material from February 2023 to February 2025 with the standard values, and determine the absolute value of the maximum difference. The uncertainties are all less than or equal to a constant value, and the stability uncertainty u is calculated. t The smaller size indicates good stability. Based on similar reference materials, the shelf life of this reference material is set at fifteen years. The research and development unit will continue to monitor and assess its stability to ensure its continued effectiveness.

[0078] III. Constant Value Analysis

[0079] The standard reference materials prepared in this embodiment were prepared in accordance with the requirements of JJF 1006-1994 "Technical Specifications for Primary Standard Reference Materials" and JJF1343-2022 "Value Determination and Homogeneity and Stability Assessment of Standard Reference Materials". In addition to our own unit, we invited domestic and international units with certain testing capabilities to participate in the value determination analysis, and selected one or more accurate and reliable analytical methods to collaborate on the value determination analysis. Sample request forms were sent to each unit, specifying the reporting time of the test results. The latest national standard analytical methods and classical absolute value determination methods were used, and the methods used had to be validated and confirmed. Four data points were reported for each element (using the same method), and the range of the four data points in each group should be less than the precision of the corresponding analytical method. The value determination methods for the spectroscopic standard reference materials developed in this project all adopted multiple national standard methods and reliable methods with different principles—gravimetric methods, photometric methods, extraction separation photometric methods, AAS, ICP-AES, ICP-MS, and titration methods, etc. In the standard reference value determination analysis of this embodiment, when measuring each parameter, fully validated methods such as national standards were prioritized. During the analysis and measurement process, working curves were created using reference materials and standard solutions. Simultaneously, published national first-class standard materials were used for quality monitoring. The measurement results were compared with the standard values ​​of the standard materials, indirectly verifying the reliability of the analytical method. All laboratories invited for the standard reference value determination analysis had many years of experience in developing and determining standard materials.

[0080] IV. Data Summary and Processing

[0081] Each collaborating analytical unit submitted four independent data points. The range was checked for outliers within each group according to the repeatability (r) of the method in the national standard. The average value of the data was then calculated. The Cochrane criterion was used to verify the equal precision of the results across groups, and the conclusion was satisfactory. The Shapiro-Wilke method was used to examine whether the average values ​​conformed to a normal distribution, and the conclusion was satisfactory. The Grubbs method was used to check for outliers in the average values, and the conclusion was satisfactory. The acceptance values ​​and uncertainties of the standard materials used for the spectral analysis of copper and silicon brass, tin bronze, and beryllium bronze are shown in Table 3.

[0082] Table 3. Accepted values ​​and uncertainties (%) of spectral analysis standard materials for silicon brass, tin bronze, and beryllium bronze

[0083]

[0084] Note: 1. The number of measurement groups is 8; 2. The uncertainty in the table is the expanded uncertainty, and the coverage factor is 2.

[0085] Users were invited to test the uniformity and accuracy of the assigned components on a photoelectric emission spectrometer (PAES). Results showed that the standard materials exhibited good uniformity and accurate values. Linearity was assessed using a German Spectro Lab M11 PES spectrometer, and fitting curves were generated for the silicon brass, tin bronze, and beryllium bronze standard materials using spectral standard materials with approximate matrix composition.

[0086] Specifically, the following curves were plotted: Silicon brass standard material ZBY929 was fitted with GSB04-2355-2008 (ZBY924(H80), ZBY925(H85)) and GBW(E)020229 (ZBY925a(H85)); tin bronze standard material ZBY930 was fitted with GSB04-2707-2001 (1#~6#) and GBW(E)020174 (ZBY915), GBW(E)020175 (ZBY915a); and beryllium bronze standard materials ZBY3302a, ZBY3304a, and ZBY3305 were fitted with beryllium bronze standard samples BYG195021~BYG195025. The working curves plotted for the standard materials are attached. Figure 1-22 .

[0087] The linear correlation coefficients for the spectral analysis standards of silicon brass, tin bronze, and beryllium bronze are as follows: Silicon brass: Zn wavelength 472.2 mm, correlation coefficient: 0.9995; Sn wavelength 175.8 mm, correlation coefficient: 0.9992; P wavelength 178.3 mm, correlation coefficient: 0.9988; Mn wavelength 294.9 mm, correlation coefficient: 0.9998; Fe wavelength 238.2 mm, correlation coefficient: 0.9997; Ni wavelength 231.6 mm, correlation coefficient: 0.9981; Si wavelength 288.2 mm, correlation coefficient: 0.9999; Pb wavelength 283.3 mm, correlation coefficient: 0.9998; Sb wavelength 187.1 mm, correlation coefficient: 0.9987; As wavelength 189.0 mm, correlation coefficient: 0.9954. Tin bronze: Zn wavelength 206.2 mm, correlation coefficient: 0.9997; Sn wavelength 317.5 mm, correlation coefficient: 0.9967; P wavelength 178.3 mm, correlation coefficient: 0.9984; Al wavelength 309.3 mm, correlation coefficient: 0.9997; Fe wavelength 271.4 mm, correlation coefficient: 0.9991; Ni wavelength 300.2 mm, correlation coefficient: 0.9998. Beryllium bronze: Fe wavelength 238.2 mm, correlation coefficient: 0.9990; Ni wavelength 300.2 mm, correlation coefficient: 0.9986; Si wavelength 288.2 mm, correlation coefficient: 0.9999; Mg wavelength 285.2 mm, correlation coefficient: 1.0000; Al wavelength 309.3 mm, correlation coefficient: 1.0000; Be wavelength 177.6 mm, correlation coefficient: 0.9996.

[0088] The silicon brass standard reference exhibits good linearity for Zn, Sn, P, Mn, Fe, Ni, Si, Pb, Sb, and As; the tin bronze standard reference shows good linearity for Zn, Sn, P, Al, Fe, and Ni; and the beryllium bronze standard reference shows good linearity for Fe, Ni, Si, Mg, Al, and Be. Comparative experiments were conducted using similar domestic and international standard references with comparable elemental content. The comparative data shows that the method used for value determination analysis of this standard reference is accurate and reliable, and the uncertainties of each element are close to those of similar international standard references, with some elements showing better uncertainties than those of similar international standard references. This fills the gap in domestic silicon brass and Cu6Ni6Sn tin bronze standard references, reaching an internationally leading level among similar standard references. Data comparison is shown in Table 4.

[0089] Table 4-1 Comparison with similar spectral analysis standard materials at home and abroad (%)

[0090]

[0091] Table 4-2 Comparison with similar spectral analysis standard materials at home and abroad (%)

[0092]

[0093] The above analysis shows that the silicon brass, tin bronze, and beryllium bronze spectral standard materials prepared in this embodiment have reasonable composition design and preparation process. After homogeneity testing and stability studies, the standard materials exhibit good homogeneity and stability. The standard values ​​determined by multiple laboratories using accurate and reliable analytical methods based on different principles are accurate and reliable. The development of these standard materials complies with the requirements of JJF 1006-1994 "Technical Specifications for Primary Standard Materials", JJF 1343-2022 "Assignment of Standard Values ​​and Evaluation of Homogeneity and Stability", and ISO Guideline 35.

[0094] Of course, the above description is not limited to the examples given above. The above embodiments and accompanying drawings are only used to illustrate the technical solutions of the present invention and are not intended to limit the present invention. The present invention has been described in detail with reference to preferred embodiments. Those skilled in the art should understand that any changes, modifications, additions or substitutions made by those skilled in the art within the scope of the present invention do not depart from the spirit of the present invention and should also fall within the scope of protection of the claims of the present invention.

Claims

1. A method for preparing spectral analysis standard materials of silicon brass, tin bronze, and beryllium bronze, characterized in that: The chemical composition and content range of this standard reference are as follows: Zn: 0.0003~16%; Sn: 0.0001~6%; P: 0.002~0.04%; Mn: 0.0004~0.02%; Fe: 0.02~0.07%; Ni: 0.001~6%; Si: 0.0005~3.6%; Ag: 0.001~0.003%; Cu: 80~97%; Pb: 0.0005~0.005%; Sb: 0.0002~0.003%; As: 0.0001~0.0003%; Mg: 0.004~0.007%; Cr: 0.01~0.02%; Co: 0.001~2.8%; Al: 0.0003~0.05%; Be: 0.6~2.1%; Ti: 0.07~0.09%; Zr: 0.01~0.03%; Includes the following steps: S1. Investigation phase: Collect physicochemical property data of target samples and determine the composition range and uncertainty requirements of standard substances; S2. Component Design: Based on the survey data, at least 3 different component gradients are designed using orthogonal experimental design, with the component content difference between each group not less than 5%; S3. Prepare raw materials according to the design range of the ingredients, and conduct ingredient verification to ensure that the main ingredients are within the design range; the raw materials include: High-purity electrolytic copper; Alloying elements: pure silicon, #2 pure zinc, pure nickel, pure cobalt, pure metals Fe, Cr, Al, Mg, Sn, Ag, Pb, Mn, Sb; Master alloys: Cu-4%Be, Cu-3%Fe, and Cu-3%P; Deoxidizer: Phosphorus copper; Covering agent: Borax; S4. Charging and smelting: S41, Smelted Silicon Brass / Tin Bronze: In the medium-frequency induction furnace, 4 / 5 of the total electrolytic copper is first loaded into the furnace along with Cu-Fe master alloy, Ni, and Si. After complete melting, the remaining electrolytic copper is added to cool the furnace, followed by Zn. After Zn melts, Mn, Pb, Sn, Ag, and Co are added in sequence. Before furnace analysis, Sb and Cu-P master alloy are added, and the melting temperature is controlled at 1100~1500℃. S42, Smelting beryllium bronze: Add electrolytic copper to the medium-frequency induction furnace, melt it, and then heat it to 1100℃~1250℃; add 0.1%~0.3% phosphorus copper for deoxidation, add Cu-4%Be master alloy, and stir evenly; then add Ni, Co, Fe, Cr, Al, and Mg in sequence, and stir until the composition is uniform; purge with argon gas to remove gas, cover the melt with borax, remove the slag, and let it stand. S5. Casting and molding: Silicon brass was poured at a temperature of 1150~1200℃, and tin bronze was poured at a temperature of 1050~1100℃. The pouring speed was 6~7 meters / hour, and Φ180×1200mm silicon brass ingots and tin bronze ingots were obtained respectively. Beryllium bronze was poured at a temperature controlled between 1050 and 1100℃; it was then rapidly water-cooled to obtain a Φ120mm beryllium bronze ingot. S6. Processing: Silicon brass / tin bronze ingots are extruded into Φ40mm copper rods using a 2000-ton hydraulic press, and then processed into Φ40×30mm silicon brass spectral blocks and tin bronze spectral blocks; Beryllium bronze ingots are hot-forged at 750℃~850℃ to obtain Φ40×3000mm bars, which are then heat-treated and processed into Φ40×30mm beryllium bronze spectral blocks.

2. The method for preparing the standard reference materials for spectral analysis of silicon brass, tin bronze, and beryllium bronze according to claim 1, characterized in that: The standard reference material consists of the following five standard reference materials: (1) Silicon brass ZBY929, the mass percentage of each component is: Zn: 15.94±0.08%; Sn: 0.0011±0.0003%; P: 0.005±0.001%; ​​Mn: 0.0005± 0.0001%; Fe: 0.022±0.003%; Ni: 0.0011±0.0002%; Si: 3.56±0.05%; Ag: 0.0010 ± 0.0002%; As: 0.00014±0.00005%; Sb: 0.0002±0.0001%; ​​Cu: 80.34±0.10%; Pb: 0.0005±0.0001%; (2) Tin bronze ZBY930, the mass percentage of each component is: Zn: 0.090±0.005%; Sn: 5.80±0.10%; P: 0.0031±0.0004%; Mn: 0.018±0.002%; Fe: 0.062±0.004%; Ni: 5.96±0.04%; Si: 0.0005±0.0001%; ​​Sb: 0.0022±0.0007%; Co: 0.0058±0.0003%; Al: 0.0003±0.0001%; ​​Cu: 88.06±0.10; Pb: 0.0042 ± 0.0005%; (3) Beryllium bronze ZBY3302a, the mass percentage of each component is: Zn: 0.0012±0.0002%; Sn: 0.0006±0.0001%; P :0.028±0.003%; Mn: 0.0024±0.0003%; Fe: 0.057±0.004%; Ni: 0.596±0.005%; Si: 0.046±0.003%; Mg: 0.0047±0.0005%; Cr: 0.010±0.003%; Ag: 0.0017 ± 0.0002%; As: 0.0002±0.0001%; ​​Sb: 0.0003±0.0001%; Co: 0.0011±0.0002%; Al: 0.042±0.003%; Be: 2.00±0.03%; Cu: 97.27±0.10%; Pb: 0.0006±0.0001%; Zr：0.029±0.004%； (4) Beryllium bronze ZBY3304a, the mass percentage of each component is: Zn: 0.0004±0.0001%; Sn: 0.0002±0.0001%; P: 0.014±0.002%; Mn: 0.0010± 0.0001%; Fe: 0.026±0.003%; Ni: 0.052±0.004%; Si: 0.021±0.003%; Mg: 0.0059±0.0006%; Cr: 0.013±0.002%; Ag: 0.0025±0.0003%; Sb: 0.0005%±0.0001%; Co: 2.78±0.04%; Al: 0.016±0.002%; Be: 0.685±0.004%; Cu: 96.33±0.09%; Pb: 0.0004±0.0001%; Zr ：0.020±0.003%； (5) Beryllium bronze ZBY3305, the mass percentage of each component is: Zn: 0.0010±0.0002%; P: 0.033±0.003%; Mn: 0.0027±0.0002%; Fe: 0.068±0.005%; Ni: 0.49±0.02%; Si: 0.046±0.004%; Mg: 0.0069±0.0004%; Cr: 0.018±0.002%; Ag: 0.0019 ± 0.0003%; As: 0.00015±0.00004%; Sb: 0.0003±0.0001%; Co: 0.0016±0.0004%; Al: 0.041±0.003%; Be: 2.01±0.03%; Cu: 97.24±0.10%; Pb: 0.0004±0.0001%; Ti: 0.081±0.008%; Zr: 0.012±0.002%.

3. The method for preparing the standard reference materials for spectral analysis of silicon brass, tin bronze, and beryllium bronze according to claim 1, characterized in that: In step S41, after adding electrolytic copper and nickel, the temperature is raised to 1250~1300℃ and completely melted. After that, the temperature is lowered to 1100~1150℃ and Sn is added, along with 0.2%~0.5% phosphorus copper for deoxidation.

4. The method for preparing the standard reference materials for spectral analysis of silicon brass, tin bronze, and beryllium bronze according to claim 1, characterized in that: In step S41, the melting temperature of silicon brass is controlled at 1100~1500℃, and the melting temperature of tin bronze is controlled at 1100~1300℃.

5. The method for preparing the standard reference materials for spectral analysis of silicon brass, tin bronze, and beryllium bronze according to claim 1, characterized in that: In step S41, the molten silicon brass / tin bronze alloy is kept at a constant temperature of 1100~1300℃ for 1~1.5h, during which pre-furnace analysis and composition adjustment are performed.

6. The method for preparing the standard reference materials for spectral analysis of silicon brass, tin bronze, and beryllium bronze according to claim 1, characterized in that: In step S6, the heat treatment includes solution treatment and aging treatment; wherein: Solution treatment: Hold at 780℃~820℃ for 1~2 hours, then water quench, with a cooling rate >100℃ / s; Aging treatment: Keep warm at 300℃~350℃ for 2~4 hours.

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