Tool steel standard substance for spectral analysis and preparation method thereof

Abstract

This invention relates to the field of spectroscopic analysis technology, specifically to a tool steel spectroscopic analysis standard material and its preparation method. The chemical composition and content range of the standard material are as follows: C: 0.80~1.50%; Si: 0.24~0.35%; Mn: 0.10~0.40%; P: 0.010~0.025%; S: 0.0005~0.0040%; Cr: 4.0~12.0%; Ni: 0.08~0.30%; Cu: 0.02~0.10%; Co: 0.02~4.90%; Ti: 0.002~0.006%; Mo The standard material prepared by this invention has a wide gradient range and many fixed elements, filling the gap in standard materials for high-speed tool steel W6Mo5Cr4V2Co5.

Description

Technical Field

[0001] This invention relates to the field of spectroscopic analysis technology, specifically to a tool steel spectroscopic analysis standard material and its preparation method. Background Technology

[0002] With the rapid development of high-end equipment manufacturing, tool steel, as a core material for manufacturing key components such as precision molds, cutting tools, and high-speed rolls, has its chemical composition precisely controlled, directly affecting material properties (such as hardness, wear resistance, and red hardness). Spectroscopic analysis techniques, such as spark spectroscopy (OES) and X-ray fluorescence spectroscopy (XRF), have become important means of quality control in the tool steel production process due to their rapid, efficient, and multi-element simultaneous detection capabilities.

[0003] The National Institute of Standards and Technology (NIST) has developed spectral standard materials for tool steel, including SRM50c, SRM132b, SRM1157, and SRM1772.

[0004] Fushun Steel Plant developed spectral standard materials GBW01211~GBW01216 for carbon steel and carbon tool steel, and assigned values ​​to 14 components, which are carbon steel with low chromium content (<0.5%) and T7, T10 and T13 carbon tool steel.

[0005] The Shandong Provincial Metallurgical Research Institute developed a single-point spectral standard material GBW01393 for mold steel 4Cr5MoSiV1, and determined the values ​​of 15 components. The W content was low (0.0080%).

[0006] Currently, there are no primary standard materials for tool steels such as W6Mo5Cr4V2, W6Mo5Cr4V2Co5, Cr12Mo1V1, and Cr6WV ​​on the market. There is also a lack of spectral analysis standard materials for W6Mo5Cr4V2Co5. The lack of standard materials for high-speed tool steel and alloy tool steel brings many difficulties to measurement and quality management, and cannot adequately meet the needs of enterprise production and development. Therefore, it is necessary to develop a series of spectral analysis standard materials for tool steel to better serve enterprise production and ensure the accuracy of test data. Summary of the Invention

[0007] To address the shortcomings of existing technologies, this invention provides a standard reference for the spectral analysis of tool steel and its preparation method. This standard reference has a wide gradient range and a large number of elements with fixed values, and can be widely used in the analysis, testing, and quality monitoring of tool steel.

[0008] This invention is achieved through the following technical solution:

[0009] A tool steel spectral analysis standard material is provided, the chemical composition and content range of which are as follows:

[0010] C: 0.80~1.50%; Si: 0.24~0.35%; Mn: 0.10~0.40%; P: 0.010~0.025%; S: 0.0005~0.0040%; Cr: 4.0~12.0%; Ni :0.08~0.30%; Cu: 0.02~0.10%; Co: 0.02~4.90%; Ti: 0.002~0.006 %; Mo: 0.03~5.0%; W: 0.20~6.10%; Al: 0.01~0.03%; Sn: 0.001~0.010%; As: 0.005~0.020%; V: 0.20~1.90%; Nb: 0.0003~0.040% ; Zn: 0.0002~0.0030%; B: 0.0003~0.0005%; N: 0.020~0.030%; Te: 0.0010~0.0020%; Ce: 0.0003~0.020%; La: 0.0003~0.0005%.

[0011] As one of the proposed solutions, the standard reference material, designated ZBG604, has the following chemical composition and content range:

[0012] C: 0.931±0.008%; Si: 0.261±0.004%; Mn: 0.342±0.004%; P: 0.019±0.002%; S: 0.0005 ±0.0001%; ​​Cr: 4.03±0.04%; Ni: 0.261±0.003%; Cu: 0.073±0.004%; Co: 4.87±0.05%; Ti :0.0027±0.0002%; Mo: 4.95±0.04%; W: 6.06±0.04%; Als: 0.024±0.002%; Alt: 0.025±0 .002%; As: 0.0061±0.0004%; V: 1.85±0.03%; Nb: 0.039±0.004%; Zn: 0.0020±0.0002%.

[0013] As one possible approach, the chemical composition and content range of this standard substance are as follows:

[0014] C: 0.908±0.006%; Si: 0.307±0.005%; Mn: 0.282±0.003%; P: 0.020±0.002%; S: 0.0005±0.0001%; ​​Cr: 3.96±0 .04%; Ni: 0.234±0.002%; Cu: 0.071±0.004%; Co: 4.82±0.05%; Ti: 0.0026±0.0002%; Mo: 4.84±0.04%; W: 5.9 8±0.04%; Als: 0.020±0.002%; Alt: 0.021±0.002%; Sn: 0.0030±0.0005%; As: 0.0056±0.0005%; V: 1.85±0.0 3%; Nb: 0.025±0.003%; Zn: 0.0024±0.0002%; B: 0.0004±0.0001%; ​​Ce: 0.012±0.002%; La: 0.0003±0.0001%.

[0015] As one possible approach, the chemical composition and content range of this standard substance are as follows:

[0016] C: 0.836±0.007%; Si: 0.263±0.003%; Mn: 0.270±0.003%; P: 0.024±0.002%; S: 0.0031±0.0003%; Cr: 3.99±0.03%; Ni: 0.316±0.003%; Cu: 0.091±0.004%; Co: 0.303±0.002%; Ti: 0.0024±0.0003%; Mo: 4.64±0.03%; W: 5.83±0.04%; Als: 0.029±0.002%; Alt: 0.030±0.002%; Sn: 0.0056±0.0004%; As: 0.0067±0.0004%; V: 1.76±0.02%; Nb: 0.025±0 .004%; Zn: 0.0023±0.0002%; B: 0.0003±0.0001%; ​​Te: 0.0013±0.0003%; Ce: 0.016±0.002%; La: 0.0003±0.0001%.

[0017] As one possible approach, the chemical composition and content range of this standard substance are as follows:

[0018] C: 1.44±0.04%; Si: 0.242±0.002%; Mn: 0.385±0.003%; P: 0.020±0.002%; S: 0.0009±0.0001%; ​​Cr: 1 1.69±0.06%; Ni: 0.126±0.002%; Cu: 0.025±0.003%; Co: 0.047±0.004%; Ti: 0.0028±0.0002%; Mo: 0. 790±0.004%; W: 0.197±0.005%; Als: 0.014±0.002%; Alt: 0.015±0.002%; Sn: 0.0009±0.0001%; ​​V: 0. 245±0.003%; Nb: 0.0016±0.0002%; Zn: 0.0002±0.0001%; ​​B: 0.0003±0.0001%; ​​Ce: 0.0005±0.0001%.

[0019] As one possible approach, the chemical composition and content range of this standard substance are as follows:

[0020] C: 1.08±0.03%; Si: 0.351±0.003%; Mn: 0.132±0.003%; P: 0.013±0.002%; S: 0.0038±0.0003%; Cr: 6.17±0.0 3%; Ni: 0.082±0.003%; Cu: 0.065±0.003%; Co: 0.024±0.003%; Ti: 0.0057±0.0003%; Mo: 0.029±0.002%; W: 1. 40±0.02%; Als: 0.0095±0.0004%; Alt: 0.011±0.002%; Sn: 0.011±0.002%; As: 0.016±0.003%; V: 0.543±0.00 4%; Nb: 0.0003±0.0001%; ​​Zn: 0.0005±0.0001%; ​​B: 0.0003±0.0001%; ​​N: 0.022±0.003%; Ce: 0.0003±0.0001%.

[0021] This invention also provides a method for preparing a standard reference for the spectral analysis of tool steel, comprising the following steps:

[0022] S1, prepared with the following composition: C: 0.80~1.50%; Si: 0.24~0.35%; Mn: 0.10~0.40%; P: 0.010~0.025%; S: 0.0005~0.0040%; Cr: 4.0~12.0%; Ni: 0.08~0.30%; Cu: 0.02~0.10%; Co: 0.02~4.90%; Ti: 0.002~0.006%; Mo: 0.03~5.0%; W: 0.20~6.10%; Al: 0.01~0.03%; Sn: 0.001~0.010%; As: 0.005~0.020%. Alloy materials with the following percentages as raw materials were used: V: 0.20~1.90%; Nb: 0.0003~0.040%; Zn: 0.0002~0.0030%; B: 0.0003~0.0005%; N: 0.020~0.030%; Te: 0.0010~0.0020%; Ce: 0.0003~0.020%; La: 0.0003~0.0005%. These materials were then fed into an alkaline medium-frequency induction furnace for melting until completely melted. The carbon content of the furnace charge was controlled to be ≥0.6%. Samples were taken for analysis after the melt was cleared.

[0023] S2. Decarburization by oxygen blowing at ≥1560℃, with a decarburization amount ≥0.2%, and carbon content observed by spark and secondary sampling for analysis;

[0024] S3. After slag removal, add 0.2% aluminum blocks for pre-deoxidation, and use graphite powder diffusion deoxidation to form white slag or weak carbide slag, and then perform a third sampling analysis.

[0025] S4. Add alloy to adjust the composition, and add aluminum shavings to maintain the white slag;

[0026] S5, Refined:

[0027] High-speed tool steel and alloy tool steel are refined once at a melting temperature of 1500℃~1600℃.

[0028] Adjust the melting temperature to 1600℃~1700℃ for secondary refining of high-speed tool steel;

[0029] The alloy tool steel was then refined in a secondary process by adjusting the melting temperature to 1520℃~1650℃.

[0030] S6. Add silicon-calcium powder for deoxidation before tapping. Control the tapping temperature of high-speed tool steel at 1630℃~1680℃ and alloy tool steel at 1590℃~1640℃. Insert 0.1% aluminum block for final deoxidation.

[0031] S7. Steel ingots were cast using a Φ203mm small cross-section steel ingot mold and a pouring method. The casting temperature for high-speed tool steel was 1450℃~1550℃, and for alloy tool steel it was 1450℃~1530℃. The steel ingots underwent preliminary inspection, including composition control and segregation testing.

[0032] S8. After the surface of the steel ingot is peeled off, the high-speed tool steel ingot is forged into a forging blank after being held at 1100℃~1200℃, and the alloy tool steel ingot is forged into a forging blank after being held at 1000℃~1100℃.

[0033] S9. After polishing, the forged billet is held at 1050℃~1100℃ for 1 hour and then hot-rolled into a Φ45mm round bar; the round bar is then made into a Φ40×30mm spectral block to obtain a block-shaped spectral analysis standard material.

[0034] S10. After performing homogeneity tests and value determination analyses on the block-shaped spectral analysis standard material prepared in step S9, the finished product is packaged.

[0035] Preferably, in step S8, the steel ingot is forged using hammering, upsetting, and drawing processes respectively, with a single cross-sectional area deformation of >35%, a total forging ratio of ≥6, and a final forging of 70-80mm billet; after forging, it is air-cooled.

[0036] Furthermore, in step S10, during the fixed value analysis, the fixed value sample is prepared first: randomly select round bars that have passed the uniformity test, cut three sections of the bar from the head, middle and tail, peel off the outer skin, grind the shavings to the bar diameter Φ15mm, control the grinding speed and shavings particle size, mix evenly, and package the prepared fixed value sample into a bottle.

[0037] The beneficial effects of this invention are:

[0038] This invention developed spectral standard materials GBW01248 and GBW01249 for alloy steel, GBW(E)010458 for high-speed tool steel W6Mo5Cr4V2, and GBW(E)010492 for alloy tool steel 3Cr2W8V, filling the gap in domestic standard materials for high-speed tool steel W6Mo5Cr4V2Co5. Values ​​were assigned to 12 components of high-speed tool steel and 14 components of alloy tool steel. These standard materials have high contents of chromium, tungsten, molybdenum, vanadium, and cobalt, all indicating high-speed and alloy tool steels with special compositions and properties. Comparative experiments were conducted with similar domestic and international standard materials with similar elemental contents. The comparative data shows that the method used for value assignment analysis of these standard materials is accurate and reliable. The uncertainties of each element are close to those of similar foreign standard materials, and the uncertainties of some elements are even better than those of similar foreign standard materials.

[0039] The series of standard reference materials of this invention are characterized by: a wide gradient range, including five tool steels; and a large number of defined elements, with values ​​assigned to 24 elements, both major and trace, making them widely applicable for the analysis, testing, and quality monitoring of tool steels. Attached Figure Description

[0040] Figure 1 This is the spectrometer working curve for the C component in the standard material for the spectral analysis of tool steel of this invention.

[0041] Figure 2 This is the spectrometer working curve for the Si composition in the standard material for the spectral analysis of tool steel of this invention.

[0042] Figure 3 This is the spectrometer working curve for the Mn component in the tool steel spectral analysis standard material of this invention.

[0043] Figure 4 This is the spectrometer working curve for the P component in the standard material for the spectral analysis of tool steel of this invention.

[0044] Figure 5 This is the spectrometer working curve for the S component in the tool steel spectral analysis standard material of this invention.

[0045] Figure 6 This is the spectrometer working curve for the Cr component in the standard material for the spectral analysis of tool steel of this invention.

[0046] Figure 7 This is the spectrometer working curve for the Ni component in the standard material for the spectral analysis of tool steel of this invention.

[0047] Figure 8 This is the spectrometer working curve for the Cu component in the standard material for the spectral analysis of tool steel of this invention.

[0048] Figure 9 This is the spectrometer working curve for the Co component in the standard material for the spectral analysis of tool steel of this invention.

[0049] Figure 10 This is the spectrometer working curve for the Ti component in the standard material for the spectral analysis of tool steel of this invention.

[0050] Figure 11 This is the spectrometer working curve for the Mo component in the standard material for the spectral analysis of tool steel of this invention.

[0051] Figure 12 This is the spectrometer working curve for the W component in the tool steel spectral analysis standard material of this invention.

[0052] Figure 13 This is the spectrometer working curve for the Al component in the standard material for the spectral analysis of tool steel of this invention.

[0053] Figure 14 This is the spectrometer working curve for the V component in the tool steel spectral analysis standard material of this invention. Detailed Implementation

[0054] To clearly illustrate the technical features of this solution, the following detailed implementation method will be used to explain the solution. Example 1:

[0055] A standard reference for the spectral analysis of tool steel, the chemical composition and content range of which are as follows: C: 0.80~1.50%; Si: 0.24~0.35%; Mn: 0.10~0.40%; P: 0.010~0.025%; S: 0.0005~0.0040%; Cr: 4.0~12.0%; Ni: 0.08~0.30%; Cu: 0.02~0.10%; Co: 0.02~4.90%; Ti: 0.002~0.006%. %; Mo: 0.03~5.0%; W: 0.20~6.10%; Al: 0.01~0.03%; Sn: 0.001~0.010%; As: 0.005~0.020%; V: 0.20~1.90%; Nb: 0.0003~0.040%; Zn: 0.0002~0.0030%; B: 0.0003~0.0005%; N: 0.020~0.030%; Te: 0.0010~0.0020%; Ce : 0.0003~0.020%; La: 0.0003~0.0005%.

[0056] In this embodiment, the standard reference materials for the spectral analysis of tool steel mainly consist of the following five standard reference materials, numbered in order as follows: ZBG604 (W6Mo5Cr4V2Co5), ZBG604a (W6Mo5Cr4V2Co5), ZBG609 (W6Mo5Cr4V2), ZBG610 (Cr12Mo1V1) and ZBG612 (Cr6WV).

[0057] Specifically, the content of each component in each standard reference material:

[0058] ZBG604 (W6Mo5Cr4V2Co5) has the following mass percentages of components: C: 0.931±0.008%; Si: 0.261±0.004%; Mn: 0.342±0.004%; P: 0.019±0.002%; S: 0.0005±0.0001%; ​​Cr: 4.03±0.04%; Ni: 0.261±0.003%; Cu: 0.073±0.004%. Co: 4.87±0.05%; Ti: 0.0027±0.0002%; Mo: 4.95±0.04%; W: 6.06±0.04%; Als: 0.024±0.002%; Alt : 0.025±0.002%; As: 0.0061±0.0004%; V: 1.85±0.03%; Nb: 0.039±0.004%; Zn: 0.0020±0.0002%.

[0059] ZBG604a (W6Mo5Cr4V2Co5) has the following mass percentages of components: C: 0.908±0.006%; Si: 0.307±0.005%; Mn: 0.282±0.003%; P: 0.020±0.002%; S: 0.0005±0.0001%; ​​Cr: 3.96±0.04%; Ni: 0.234±0.002%; Cu: 0.071±0.004%; Co: 4.82±0.05%; Ti: 0.0026±0.0002%; Mo : 4.84±0.04%; W: 5.98±0.04%; Als: 0.020±0.002%; Alt: 0.021±0.002%; Sn: 0.0030±0.0005%; As: 0.0056±0.0005%; V : 1.85±0.03%; Nb: 0.025±0.003%; Zn: 0.0024±0.0002%; B: 0.0004±0.0001%; ​​Ce: 0.012±0.002%; La: 0.0003±0.0001%.

[0060] ZBG609 (W6Mo5Cr4V2) has the following mass percentages of components: C: 0.836±0.007%; Si: 0.263±0.003%; Mn: 0.270±0.003%; P: 0.024±0.002%; S: 0.0031±0.0003%; Cr: 3.99±0.03%; Ni: 0.316±0.003%; Cu: 0.091±0.004%; Co: 0.303±0.002%; Ti: 0.0024±0.0003%; Mo: 4.64±0.03%. %; W: 5.83±0.04%; Als: 0.029±0.002%; Alt: 0.030±0.002%; Sn: 0.0056±0.0004%; As: 0.0067±0.0004%; V: 1.76±0.02%; Nb : 0.025±0.004%; Zn: 0.0023±0.0002%; B: 0.0003±0.0001%; ​​Te: 0.0013±0.0003%; Ce: 0.016±0.002%; La: 0.0003±0.0001%.

[0061] ZBG610 (Cr12Mo1V1) has the following mass percentages of components: C: 1.44±0.04%; Si: 0.242±0.002%; Mn: 0.385±0.003%; P: 0.020±0.002%; S: 0.0009±0.0001%; ​​Cr: 11.69±0.06%; Ni: 0.126±0.002%; Cu: 0.025±0.003%; Co: 0.047±0.004%; Ti: 0.0028 ±0.0002%; Mo: 0.790±0.004%; W: 0.197±0.005%; Als: 0.014±0.002%; Alt: 0.015±0.002%; Sn: 0.0009±0.000 1%; V: 0.245±0.003%; Nb: 0.0016±0.0002%; Zn: 0.0002±0.0001%; ​​B: 0.0003±0.0001%; ​​Ce: 0.0005±0.0001%.

[0062] ZBG612 (Cr6WV) has the following mass percentages of components: C: 1.08±0.03%; Si: 0.351±0.003%; Mn: 0.132±0.003%; P: 0.013±0.002%; S: 0.0038±0.0003%; Cr: 6.17±0.03%; Ni: 0.082±0.003%; Cu: 0.065±0.003%; Co: 0.024±0.003%; Ti: 0.0057±0.0003%; Mo: 0.029 ±0.002%; W: 1.40±0.02%; Als: 0.0095±0.0004%; Alt: 0.011±0.002%; Sn: 0.011±0.002%; As: 0.016±0.003%; V: 0.54 3±0.004%; Nb: 0.0003±0.0001%; ​​Zn: 0.0005±0.0001%; ​​B: 0.0003±0.0001%; ​​N: 0.022±0.003%; Ce: 0.0003±0.0001%. Example 2:

[0063] A method for preparing a standard reference for the spectral analysis of tool steel includes the following steps:

[0064] S1, prepared with the following composition: C: 0.80~1.50%; Si: 0.24~0.35%; Mn: 0.10~0.40%; P: 0.010~0.025%; S: 0.0005~0.0040%; Cr: 4.0~12.0%; Ni: 0.08~0.30%; Cu: 0.02~0.10%; Co: 0.02~4.90%; Ti: 0.002~0.006%; Mo: 0.03~5.0%; W: 0.20~6.10%; Al: 0.01~0.03%; Sn: 0.001~0.003% The following formulation materials, containing 0.010%; As: 0.005~0.020%; V: 0.20~1.90%; Nb: 0.0003~0.040%; Zn: 0.0002~0.0030%; B: 0.0003~0.0005%; N: 0.020~0.030%; Te: 0.0010~0.0020%; Ce: 0.0003~0.020%; La: 0.0003~0.0005%, are added to an alkaline medium-frequency induction furnace for melting until completely melted. The carbon content of the furnace charge is controlled to be ≥0.6%. Samples are taken for analysis after melting.

[0065] S2. Decarbonize by oxygen blowing at ≥1560℃, with a decarbonization amount ≥0.2%. Observe the carbon content by spark and take a second sample for analysis.

[0066] S3. After slag removal, add 0.2% aluminum blocks for pre-deoxidation, and use graphite powder diffusion deoxidation to form white slag or weak carbide slag, and then perform a third sampling analysis.

[0067] S4. Add alloy to adjust the composition and add aluminum shavings to maintain the white slag.

[0068] S5, Refined:

[0069] High-speed tool steel and alloy tool steel are refined once at a melting temperature of 1500℃~1600℃.

[0070] The high-speed tool steel is refined twice by adjusting the melting temperature to 1600℃~1700℃; the alloy tool steel is refined twice by adjusting the melting temperature to 1520℃~1650℃.

[0071] S6. Before tapping, add silicon-calcium powder for deoxidation. For high-speed tool steel, control the tapping temperature to 1630℃~1680℃, and for alloy tool steel, control it to 1590℃~1640℃. Insert 0.1% aluminum blocks for final deoxidation.

[0072] S7. Steel ingots were obtained by casting using a Φ203mm small cross-section steel ingot mold and a bottom casting method. The casting temperature for high-speed tool steel was 1450℃~1550℃, and for alloy tool steel it was 1450℃~1530℃. The steel ingots were subjected to preliminary inspection, including composition control and segregation inspection.

[0073] S8. After peeling the surface of the steel ingot, the high-speed tool steel ingot is forged into a forging blank after being held at 1100℃~1200℃, and the alloy tool steel ingot is forged into a forging blank after being held at 1000℃~1100℃. The forging process adopts hammer, upsetting and drawing processes to forge the steel ingot separately. The deformation of the cross-sectional area in a single forging is >35%, the total forging ratio is ≥6, and the final forging blank is 70~80mm. After forging, it is air-cooled.

[0074] S9. After polishing, the forged billet is held at 1050℃~1100℃ for 1 hour and then hot rolled in the 350 unit rolling mill to produce a Φ45mm round bar; the round bar is then made into a Φ40×30mm spectral block to obtain a block-shaped spectral analysis standard material.

[0075] S10. After performing homogeneity tests and value determination analyses on the block-shaped spectral analysis standard material prepared in step S9, the finished product is packaged.

[0076] In the fixed value analysis, the fixed value sample is prepared first: randomly select round bars that have passed the uniformity test, cut three sections of bars from the head, middle and tail, peel off the outer skin, grind the shavings to the bar diameter Φ15mm, control the grinding speed and shavings particle size, mix evenly, and package into bottles.

[0077] The data verification and analysis are as follows:

[0078] I. Homogeneity Test of Standard Reference Materials

[0079] To examine the longitudinal segregation of the smallest unit (sample block) of the standard material, a representative sample was selected from each steel grade, and the axis was non-destructively dissected using wire cutting. The samples were then excited at equal intervals, and their average and range values ​​were statistically analyzed. The results showed that the ranges at both the beginning and end of the sample were less than the allowable error or repeatability of the corresponding analytical method.

[0080] A 10mm sample was taken from each end of a 900mm round bar. Using a Spectro Lab M11 spectrometer (spectrometer measurement range shown in Table 1), the samples were first traced using a dedicated standard reference, then fully standardized using an imported steel standard reference, and finally standardized using a tool steel standard reference with similar content and grade. Homogeneity segregation was tested using photoelectric emission spectroscopy (GB / T4336 and GB / T 11170), and statistical analysis was performed using the range method (segregation test data shown in Table 2). 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.

[0081] The prepared block sample is discharged between the electrode and a spark source, generating plasma in a high-temperature, inert atmosphere. When the atoms of the analyte are excited, electrons transition between different energy levels within the atom. Characteristic spectral lines are generated when transitioning from a higher energy level to a lower energy level. The spectral intensities of the characteristic spectral lines of the selected analyte and internal standard are measured. Based on the relationship between the spectral line intensity (or intensity ratio) of the analyte in the sample and its concentration, the content of the analyte is calculated using a calibration curve.

[0082] Table 1. Measurement range (%) of the spectrometer for standard materials used in the spectral analysis of tool steel

[0083]

[0084] Table 2 Segregation Test of Standard Materials for Spectroscopic Analysis of Tool Steel (%)

[0085]

[0086] According to the technical specifications of the standard material, 20 samples were selected from the finished block samples, numbered sequentially, and the analysis order was determined by random numbers.

[0087] Uniformity was tested at three different locations on the cross-section of each sample using a Spectro Lab M11 photoelectric emission spectrometer.

[0088] The test results were statistically analyzed using the variance method.

[0089] Statistical analysis showed that the F-values ​​of all elements were less than F. α(0.05) The value indicates that the uniformity test is satisfactory.

[0090] The statistical results of the uniformity test F-values ​​of the tool steel spectral standard material prepared by the preparation method of the present invention are shown in Table 3 below.

[0091] Table 3. Homogeneity test F-values ​​(F values) of spectral standard materials for tool steel 0.05 =1.84)

[0092]

[0093] II. Stability Test

[0094] The stability of the standard material was investigated multiple times over two years using photoelectric emission spectroscopy methods according to GB / T 4336 and GB / T 11170. The results were statistically tested for stability using linear fitting. The stability values ​​from the five stability tests from 2022 to 2024 were calculated (the results are shown in Table 4). The results show that the stability test data over the two years are consistent and the sample has good stability.

[0095] Furthermore, comparing the stability test results with the uncertainty of the final value, the difference between the 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 This represents the characteristic value of CRM. Let k be the measured observation value, k be the coverage factor, and the confidence level be 95%. Let k=2. The uncertainty of the characteristic value, This refers to the measurement uncertainty.

[0096] Ideally, the measurement uncertainty is much smaller than the uncertainty of the characteristic value.

[0097] The spectral measurements of the standard material from December 2022 to December 2024 were compared with the standard values ​​(results shown in Table 4). The absolute values ​​of the maximum differences were all less than or equal to the uncertainty of the given value, and the calculated stability uncertainty was also within acceptable limits. u t The smaller value indicates good stability.

[0098] Table 4. Results of the stability study of standard reference materials for tool steel spectral analysis (%)

[0099]

[0100]

[0101]

[0102]

[0103]

[0104] Note: In the table, b1 is the slope of the fitted line, s(b1) is the uncertainty of the slope, and t α,（n-2） A t-distribution with n-2 degrees of freedom and a certain confidence level; |X CRM -X meas | represents the absolute value of the difference between the measured value and the standard value.

[0105] III. Constant Value Analysis

[0106] The standard substances prepared in this invention were collaboratively analyzed and valued by qualified analytical units in the industry. Each unit submitted four independent data points, with the range calculated according to the r-value or allowable difference in the national standard method. The groups were checked for outliers, and the average value was calculated. The Cochrane criterion was used to verify the equal precision of the results from each group, 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.

[0107] The certified values ​​and uncertainties of the spectral analysis standard materials for tool steel are shown in Table 6.

[0108] The uniformity and accuracy of the fixed-value components were tested on a photoelectric emission spectrometer, and the results showed that the standard material performed well.

[0109] Linearity was investigated using a Spectro Lab M11 photoelectric emission spectrometer (Germany). Fitting curves were plotted between five tool steel standard materials and ten standard materials of high-speed tool steels GBW(E)010458 (ZBG233), GBW01694 (ZBG025), and GSBH40088-1996 (6#, 7#, 8#). The results, as shown in Table 5, indicate that, except for a few components, the linear relationships of the working curves for 14 components (C, Si, Mn, P, S, Cr, Ni, Cu, Co, Ti, Mo, W, Al, and V) are good. The working curves for each component are shown in Table 5. Figures 1-14 As shown.

[0110] Table 5. Linearity and Consistency Assessment of Standard Materials for Spectral Analysis of Tool Steel: Linear Correlation Coefficients

[0111]

[0112] Table 6. Accepted values ​​and uncertainties (%) of standard reference materials for spectral analysis of tool steel

[0113]

[0114] Note: 1. The number of measurement groups is 8. 2. The uncertainty in the table is the expanded uncertainty, and the coverage factor is k=2.

[0115] Table 7-1 Comparison with similar spectral analysis standard materials at home and abroad (%)

[0116]

[0117] Table 7-2 Comparison with similar spectral analysis standard materials at home and abroad (%)

[0118]

[0119] In summary, the "Tool Steel Spectral Analysis Standard Material" developed in this invention has a reasonable design and preparation process. After homogeneity testing and stability investigation, the standard material exhibits 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 characteristics of this series of standard materials are: a wide gradient range, including five tool steels; a large number of elements for determination, with values ​​assigned to 24 elements (major and trace elements), filling the gap in standard materials for high-speed tool steel W6Mo5Cr4V2Co5. It can be widely used in the analysis, testing, and quality control of tool steels. The development of this standard material complies with the requirements of JJF 1006-1994 "Technical Specification for Primary Standard Materials", JJF 1343-2022 "Assignment of Values ​​and Evaluation of Homogeneity and Stability of Standard Materials", and ISO Guideline 35, as shown in Tables 7-1 and 7-2.

[0120] Of course, the above description is not limited to the examples above. Technical features not described in this invention can be implemented by or using existing technology, and will not be repeated here. The above embodiments and drawings are only used to illustrate the technical solutions of this invention and are not intended to limit this invention. This 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 this invention do not depart from the spirit of this invention and should also fall within the scope of protection of the claims of this invention.

Claims

1. A tool steel spectral analysis standard material, characterized in that: The chemical composition and content range of this standard reference are as follows: C: 0.80~1.50%; Si: 0.24~0.35%; Mn: 0.10~0.40%; P: 0.010~0.025%. S: 0.0005~0.0040%; Cr: 4.0~12.0%; Ni: 0.08~0.30%; Cu: 0.02~0.10%; Co: 0.02~4.90%; Ti: 0.002~0.006%; Mo: 0.03~5.0%; W：0.20~6.10% ； Al ： 0.01~0.03% ； Sn: 0.001~0.010%; As: 0.005~0.020%; V: 0.20~1.90%; Nb: 0.0003~0.040%; Zn: 0.0002~0.0030%; B：0.0003~0.0005%； N ：0.020~0.030%； Te: 0.0010~0.0020%; Ce: 0.0003~0.020%; La: 0.0003~0.0005%; The preparation method of the tool steel spectral analysis standard material includes the following steps: S1. Prepare the formula materials and put them into an alkaline medium-frequency induction furnace for melting until completely melted. Control the carbon content of the furnace charge to be ≥0.6%. Take samples for analysis after melting. S2. Decarburization by oxygen blowing at ≥1560℃, with a decarburization amount ≥0.2%, and carbon content observed by spark and secondary sampling for analysis; S3. After slag removal, add 0.2% aluminum blocks for pre-deoxidation, and use graphite powder diffusion deoxidation to form white slag or weak carbide slag, and then perform a third sampling analysis. S4. Add alloy to adjust the composition, and add aluminum shavings to maintain the white slag; S5, Refined: The tool steel is refined once at a melting temperature of 1500℃~1600℃, and then refined a second time depending on the type of tool steel. For high-speed tool steel, adjust the melting temperature to 1600℃~1700℃ and carry out secondary refining; For alloy tool steel, adjust the melting temperature to 1520℃~1650℃ and carry out secondary refining; S6. Add silicon-calcium powder for deoxidation before tapping. Control the tapping temperature of high-speed tool steel at 1630℃~1680℃ and alloy tool steel at 1590℃~1640℃. Insert 0.1% aluminum block for final deoxidation. S7. Steel ingots are obtained by casting using a Φ203mm small cross-section steel ingot mold and the pouring method. The casting temperature for high-speed tool steel is 1450℃~1550℃, and for alloy tool steel it is 1450℃~1530℃. The steel ingots are subjected to preliminary inspection, including composition control and segregation inspection. S8. After the steel ingot is peeled off, it is forged at different temperatures depending on the type of tool steel. High-speed tool steel ingots are forged to obtain forging blanks after being held at 1100℃~1200℃, and alloy tool steel ingots are forged to obtain forging blanks after being held at 1000℃~1100℃. S9. After polishing, the forged billet is held at 1050℃~1100℃ for 1 hour and then hot-rolled into a Φ45mm round bar; the round bar is then made into a Φ40×30mm spectral block to obtain a block-shaped spectral analysis standard material. S10. After performing homogeneity tests and value determination analyses on the block-shaped spectral analysis standard material prepared in step S9, the finished product is packaged.

2. The tool steel spectral analysis standard material according to claim 1, characterized in that: In step S8, the steel ingot is forged using hammer, upsetting, and drawing processes respectively, with a single cross-sectional area deformation of >35% and a total forging ratio of ≥6, and finally forged into a 70-80mm forging billet; after forging, it is air-cooled.

3. The tool steel spectral analysis standard material according to claim 1, characterized in that: In step S10, during the fixed value analysis, the fixed value sample is prepared first: randomly select round bars that have passed the uniformity test, cut three sections of the bar from the head, middle and tail, peel off the outer skin, grind the shavings to the bar diameter Φ15mm, control the grinding speed and shavings particle size, mix evenly, and package the prepared fixed value sample into a bottle.

4. A standard reference for the spectral analysis of tool steel, characterized in that: The chemical composition and content range of this standard reference are as follows: C: 0.931±0.008%; Si: 0.261±0.004%; Mn: 0.342±0.004%; P: 0.019±0.002%; S: 0.0005±0.0001%; ​​Cr: 4.03±0.04%; Ni: 0.261±0.003%; Cu: 0.073±0.004%; Co: 4.87±0.05%; Ti: 0.0027±0.0002%; Mo: 4.95±0.04%; W: 6.06±0.04%; Als: 0.024±0.002%; Alt: 0.025±0.002%; As: 0.0061±0.0004%; V: 1.85±0.03%; Nb: 0.039±0.004%; Zn: 0.0020±0.0002%; The preparation method of the tool steel spectral analysis standard material includes the following steps: S1. Prepare the formula materials and put them into an alkaline medium-frequency induction furnace for melting until completely melted. Control the carbon content of the furnace charge to be ≥0.6%. Take samples for analysis after melting. S2. Decarburization by oxygen blowing at ≥1560℃, with a decarburization amount ≥0.2%, and carbon content observed by spark and secondary sampling for analysis; S3. After slag removal, add 0.2% aluminum blocks for pre-deoxidation, and use graphite powder diffusion deoxidation to form white slag or weak carbide slag, and then perform a third sampling analysis. S4. Add alloy to adjust the composition, and add aluminum shavings to maintain the white slag; S5, Refined: The tool steel is first refined at a melting temperature of 1500℃~1600℃, and then a second refining is carried out at a melting temperature of 1600℃~1700℃. S6. Add silicon-calcium powder for deoxidation before tapping. Control the tapping temperature of high-speed tool steel at 1630℃~1680℃ and insert 0.1% aluminum blocks for final deoxidation. S7. Steel ingots are obtained by casting using a Φ203mm small cross-section steel ingot mold and the pouring method. The casting temperature of high-speed tool steel is 1450℃~1550℃. The steel ingots are subjected to preliminary inspection, including composition control and segregation inspection. S8. After the steel ingot surface is peeled off, it is forged into a forging billet after being held at 1100℃~1200℃. S9. After polishing, the forged billet is held at 1050℃~1100℃ for 1 hour and then hot-rolled into a Φ45mm round bar; the round bar is then made into a Φ40×30mm spectral block to obtain a block-shaped spectral analysis standard material. S10. After performing homogeneity tests and value determination analyses on the block-shaped spectral analysis standard material prepared in step S9, the finished product is packaged.

5. A standard reference for the spectral analysis of tool steel, characterized in that: The chemical composition and content range of this standard reference are as follows: C: 0.908±0.006%; Si: 0.307±0.005%; Mn: 0.282±0.003%; P: 0.020±0.002%; S: 0.0005±0.0001%; ​​Cr: 3.96±0.04%; Ni: 0.234±0.002%; Cu: 0.071±0.004%; Co: 4.82±0.05%; Ti: 0.0026±0.0002%; Mo: 4.84±0.04%; W: 5.98±0.04%; Als: 0.020±0.002%; Alt: 0.021±0.002%; Sn: 0.0030±0.0005%; As: 0.0056 ± 0.0005%; V: 1.85±0.03%; Nb: 0.025±0.003%; Zn: 0.0024±0.0002%; B：0.0004±0.0001%； Ce: 0.012±0.002%; La: 0.0003±0.0001%; The preparation method of the tool steel spectral analysis standard material includes the following steps: S1. Prepare the formula materials and put them into an alkaline medium-frequency induction furnace for melting until completely melted. Control the carbon content of the furnace charge to be ≥0.6%. Take samples for analysis after melting. S2. Decarburization by oxygen blowing at ≥1560℃, with a decarburization amount ≥0.2%, and carbon content observed by spark and secondary sampling for analysis; S3. After slag removal, add 0.2% aluminum blocks for pre-deoxidation, and use graphite powder diffusion deoxidation to form white slag or weak carbide slag, and then perform a third sampling analysis. S4. Add alloy to adjust the composition, and add aluminum shavings to maintain the white slag; S5, Refined: The tool steel is first refined at a melting temperature of 1500℃~1600℃, and then a second refining is carried out at a melting temperature of 1600℃~1700℃. S6. Add silicon-calcium powder for deoxidation before tapping. Control the tapping temperature of high-speed tool steel at 1630℃~1680℃ and insert 0.1% aluminum blocks for final deoxidation. S7. Steel ingots are obtained by casting using a Φ203mm small cross-section steel ingot mold and the pouring method. The casting temperature of high-speed tool steel is 1450℃~1550℃. The steel ingots are subjected to preliminary inspection, including composition control and segregation inspection. S8. After the steel ingot surface is peeled off, it is forged into a forging billet after being held at 1100℃~1200℃. S9. After polishing, the forged billet is held at 1050℃~1100℃ for 1 hour and then hot-rolled into a Φ45mm round bar; the round bar is then made into a Φ40×30mm spectral block to obtain a block-shaped spectral analysis standard material. S10. After performing homogeneity tests and value determination analyses on the block-shaped spectral analysis standard material prepared in step S9, the finished product is packaged.

6. A standard reference for the spectral analysis of tool steel, characterized in that: The chemical composition and content range of this standard reference are as follows: C: 0.836±0.007%; Si: 0.263±0.003%; Mn: 0.270±0.003%; P: 0.024±0.002%; S: 0.0031±0.0003%; Cr: 3.99±0.03%; Ni: 0.316±0.003%; Cu: 0.091±0.004%; Co: 0.303±0.002%; Ti: 0.0024±0.0003%; Mo: 4.64±0.03%; W: 5.83±0.04%; Als: 0.029±0.002%; Alt: 0.030±0.002%; Sn: 0.0056±0.0004%; As: 0.0067 ± 0.0004%; V: 1.76±0.02%; Nb: 0.025±0.004%; Zn: 0.0023±0.0002%; B：0.0003±0.0001%； Te: 0.0013±0.0003%; Ce: 0.016±0.002%; La: 0.0003±0.0001%; The preparation method of the tool steel spectral analysis standard material includes the following steps: S1. Prepare the formula materials and put them into an alkaline medium-frequency induction furnace for melting until completely melted. Control the carbon content of the furnace charge to be ≥0.6%. Take samples for analysis after melting. S2. Decarburization by oxygen blowing at ≥1560℃, with a decarburization amount ≥0.2%, and carbon content observed by spark and secondary sampling for analysis; S3. After slag removal, add 0.2% aluminum blocks for pre-deoxidation, and use graphite powder diffusion deoxidation to form white slag or weak carbide slag, and then perform a third sampling analysis. S4. Add alloy to adjust the composition, and add aluminum shavings to maintain the white slag; S5, Refined: The tool steel is first refined at a melting temperature of 1500℃~1600℃, and then a second refining is carried out at a melting temperature of 1600℃~1700℃. S6. Add silicon-calcium powder for deoxidation before tapping. Control the tapping temperature of high-speed tool steel at 1630℃~1680℃ and insert 0.1% aluminum blocks for final deoxidation. S7. Steel ingots are obtained by casting using a Φ203mm small cross-section steel ingot mold and the pouring method. The casting temperature of high-speed tool steel is 1450℃~1550℃. The steel ingots are subjected to preliminary inspection, including composition control and segregation inspection. S8. After the steel ingot surface is peeled off, it is forged into a forging billet after being held at 1100℃~1200℃. S9. After polishing, the forged billet is held at 1050℃~1100℃ for 1 hour and then hot-rolled into a Φ45mm round bar; the round bar is then made into a Φ40×30mm spectral block to obtain a block-shaped spectral analysis standard material. S10. After performing homogeneity tests and value determination analyses on the block-shaped spectral analysis standard material prepared in step S9, the finished product is packaged.

7. A standard reference for the spectral analysis of tool steel, characterized in that: The chemical composition and content range of this standard reference are as follows: C: 1.44±0.04%; Si: 0.242±0.002%; Mn: 0.385±0.003%; P: 0.020±0.002%; S: 0.0009±0.0001%; ​​Cr: 11.69±0.06%; Ni: 0.126±0.002%; Cu: 0.025±0.003%; Co: 0.047±0.004%; Ti: 0.0028±0.0002%. Mo: 0.790±0.004%; W: 0.197±0.005%; Als: 0.014±0.002%; Alt: 0.015±0.002%; Sn: 0.0009±0.0001%; V: 0.245±0.003%; Nb: 0.0016±0.0002%; Zn: 0.0002±0.0001%; B：0.0003±0.0001%； Ce: 0.0005±0.0001%; The preparation method of the tool steel spectral analysis standard material includes the following steps: S1. Prepare the formula materials and put them into an alkaline medium-frequency induction furnace for melting until completely melted. Control the carbon content of the furnace charge to be ≥0.6%. Take samples for analysis after melting. S2. Decarburization by oxygen blowing at ≥1560℃, with a decarburization amount ≥0.2%, and carbon content observed by spark and secondary sampling for analysis; S3. After slag removal, add 0.2% aluminum blocks for pre-deoxidation, and use graphite powder diffusion deoxidation to form white slag or weak carbide slag, and then perform a third sampling analysis. S4. Add alloy to adjust the composition, and add aluminum shavings to maintain the white slag; S5, Refined: The tool steel is first refined at a melting temperature of 1500℃~1600℃, and then a second refining is carried out at a melting temperature of 1520℃~1650℃. S6. Add silicon-calcium powder for deoxidation before tapping. For alloy tool steel, add 0.1% aluminum blocks for final deoxidation at 1590℃~1640℃. S7. Steel ingots are obtained by casting using a Φ203mm small cross-section steel ingot mold and the pouring method. The alloy tool steel is cast at 1450℃~1530℃. The steel ingots are subjected to preliminary inspection, including composition control and segregation inspection. S8. After peeling off the surface of the steel ingot, it is forged into a forging billet after being held at 1000℃~1100℃. S9. After polishing, the forged billet is held at 1050℃~1100℃ for 1 hour and then hot-rolled into a Φ45mm round bar; the round bar is then made into a Φ40×30mm spectral block to obtain a block-shaped spectral analysis standard material. S10. After performing homogeneity tests and value determination analyses on the block-shaped spectral analysis standard material prepared in step S9, the finished product is packaged.

8. A tool steel spectral analysis standard material, characterized in that: The chemical composition and content range of this standard reference are as follows: C: 1.08±0.03%; Si: 0.351±0.003%; Mn: 0.132±0.003%; P: 0.013±0.002%; S: 0.0038±0.0003%; Cr: 6.17±0.03%; Ni: 0.082±0.003%; Cu: 0.065±0.003%; Co: 0.024±0.003%; Ti: 0.0057±0.0003%; Mo: 0.029±0.002%; W: 1.40±0.02%; Als: 0.0095±0.0004%. Alt: 0.011±0.002%; Sn: 0.011±0.002%; As: 0.016 ± 0.003%; V: 0.543±0.004%; Nb: 0.0003±0.0001%; Zn: 0.0005±0.0001%; B：0.0003±0.0001%； N: 0.022±0.003%; Ce: 0.0003±0.0001%; The preparation method of the tool steel spectral analysis standard material includes the following steps: S1. Prepare the formula materials and put them into an alkaline medium-frequency induction furnace for melting until completely melted. Control the carbon content of the furnace charge to be ≥0.6%. Take samples for analysis after melting. S2. Decarburization by oxygen blowing at ≥1560℃, with a decarburization amount ≥0.2%, and carbon content observed by spark and secondary sampling for analysis; S3. After slag removal, add 0.2% aluminum blocks for pre-deoxidation, and use graphite powder diffusion deoxidation to form white slag or weak carbide slag, and then perform a third sampling analysis. S4. Add alloy to adjust the composition, and add aluminum shavings to maintain the white slag; S5, Refined: The tool steel is first refined at a melting temperature of 1500℃~1600℃, and then a second refining is carried out at a melting temperature of 1520℃~1650℃. S6. Add silicon-calcium powder for deoxidation before tapping. For alloy tool steel, add 0.1% aluminum blocks for final deoxidation at 1590℃~1640℃. S7. Steel ingots are obtained by casting using a Φ203mm small cross-section steel ingot mold and the pouring method. The alloy tool steel is cast at 1450℃~1530℃. The steel ingots are subjected to preliminary inspection, including composition control and segregation inspection. S8. After peeling off the surface of the steel ingot, it is forged into a forging billet after being held at 1000℃~1100℃. S9. After polishing, the forged billet is held at 1050℃~1100℃ for 1 hour and then hot-rolled into a Φ45mm round bar; the round bar is then made into a Φ40×30mm spectral block to obtain a block-shaped spectral analysis standard material. S10. After performing homogeneity tests and value determination analyses on the block-shaped spectral analysis standard material prepared in step S9, the finished product is packaged.

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