Standard substance for spectral analysis of cathode copper and preparation method of standard substance

Abstract

The invention provides a standard substance for cathode copper spectral analysis and a preparation method thereof, and relates to the technical field of analysis and detection. The standard substance for cathode copper spectral analysis takes A-grade copper as a matrix, and contains impurity elements of Pb, Bi, Sb, As, Sn, Ni, Zn, Mn, Cd, Co, Cr, Se, Te, Fe, P, Si, S and Ag, and the total mass fraction of the impurity elements does not exceed 0.0065%. The standard substance for cathode copper spectral analysis is excellent in uniformity and stability, meets related technical requirements, is suitable for spark source atomic emission spectrum analysis of materials such as A-grade copper (Cu-CATH-1) in GB / T 467-2010 cathode copper, and can be used for quality evaluation, calibration of analytical instruments, evaluation and analysis methods, quantity transmission, traceability and the like.

Description

Technical Field

[0001] The invention relates to the technical field of analysis and detection, and in particular to a standard substance for cathode copper spectrum analysis and a preparation method thereof. Background Art

[0002] Copper is one of the non-ferrous metals with excellent comprehensive application performance. It is widely used in electricity, electronics, energy and petrochemicals, machinery and metallurgy, transportation, light industry, emerging industries and other fields. It is second only to aluminum in the consumption of non-ferrous metal materials. In recent years, with the rapid development of the new energy industry, the global copper consumption, including China, will continue to grow. The production scale of cathode copper as a raw material is also expanding, and users' requirements for product quality are getting higher and higher.

[0003] The widespread application of high-performance spark source atomic emission spectrometry analysis technology has made the analysis of cathode copper products faster and more accurate. Among them, standard substances for cathode copper spectral analysis play a vital role. However, according to investigations, there is still a market gap for standard substances for cathode copper spectral analysis in China. Summary of the invention

[0004] The invention provides a cathode copper spectrum analysis standard substance and a preparation method thereof, which are used to fill the gap in the domestic market and meet the component analysis requirements of high-purity copper.

[0005] In a first aspect, the present invention provides a standard substance for cathode copper spectral analysis, which is based on grade A copper and contains impurity elements Pb, Bi, Sb, As, Sn, Ni, Zn, Mn, Cd, Co, Cr, Se, Te, Fe, P, Si, S and Ag, and the total mass fraction of the impurity elements does not exceed 0.0065%.

[0006] In some embodiments of the present invention, the elements in the standard substance are composed as follows: The mass fractions of Pb, Bi, Sb, As, Sn, Ni, Zn, Mn, Cd, Co, Cr, Se, and Te are all 0.00005~0.00015%; the mass fractions of Fe, P, and Si are all 0.0001~0.0003%; the mass fraction of S is 0.0004~0.0007%; the mass fraction of Ag is 0.0005~0.0008%; and the balance is Cu.

[0007] In some embodiments of the present invention, the elements in the standard substance are composed as follows: The mass fractions of Pb, Bi, Sb, Sn, Se, and Te are all 0.0001~0.0003%; the mass fractions of As, Ni, Zn, P, Mn, Cd, Co, and Cr are all 0.0002~0.0004%; the mass fraction of Fe is 0.0003~0.0005%; the mass fraction of S is 0.0007~0.0012%; the mass fraction of Ag is 0.001~0.0015%; the mass fraction of Si is 0.0004~0.0007%; and the balance is Cu.

[0008] In some embodiments of the present invention, the elements in the standard substance are composed as follows: The mass fractions of Pb and Bi are both 0.0003~0.0006%; the mass fractions of Fe, Sb, As, Sn, Ni, Zn and P are both 0.0004~0.0007%; the mass fractions of S, Si, Mn, Co and Cr are both 0.0005~0.001%; ​​the mass fraction of Ag is 0.001~0.002%; the mass fraction of Cd is 0.0001~0.0003%; the mass fractions of Se and Te are both 0.0002~0.0004%; the balance is Cu.

[0009] In some embodiments of the present invention, the elements in the standard substance are composed as follows: The mass fractions of Pb, Fe, Bi, Sb, As, Sn, Ni, Zn and P are all 0.0008~0.0015%; the mass fractions of S, Mn, Co and Cr are all 0.001~0.002%; the mass fraction of Ag is 0.002~0.003%; the mass fraction of Si is 0.0003~0.0008%; the mass fraction of Cd is 0.0002~0.0004%; the mass fractions of Se and Te are all 0.0005~0.001%; ​​and the balance is Cu.

[0010] In some embodiments of the present invention, the elements in the standard substance are composed as follows: The mass fractions of Pb, Fe, Bi, Sb, As, Sn, Ni, Zn, P, Si, Mn, Co, and Cr are all 0.002~0.004%; the mass fractions of S and Ag are all 0.003~0.005%; the mass fractions of Cd, Se, and Te are all 0.001~0.002%; and the balance is Cu.

[0011] In one embodiment of the present invention, the elements in the standard substance are composed as follows: Pb: 0.00009±0.00003%; Fe: 0.00020±0.00003%; Bi: 0.00008±0.00002%; Sb: 0.00007±0.00003%; As: 0.00013± 0.00003%; Sn: 0.00007±0.00002%; Ni: 0.00012±0.00002%; Zn: 0.00006±0.00002%; P: 0.00016±0.00003%; S: 0 .00052±0.00007%; Ag: 0.00071±0.00006%; Si: 0.00016±0.00003%; Mn: 0.00005±0.00002%; Cd: 0.00006±0.00002%; Co: 0.00009±0.00002%; Cr: 0.00007±0.00002%; Se: 0.00007±0.00002%; Te: 0.00008±0.00003%; the balance is Cu.

[0012] In one embodiment of the present invention, the elements in the standard substance are composed as follows: Pb: 0.00020±0.00004%; Fe: 0.00038±0.00004%; Bi: 0.00018±0.00002%; Sb: 0.00025±0.00003%; As: 0.00033 ±0.00004%; Sn: 0.00026±0.00003%; Ni: 0.00034±0.00004%; Zn: 0.00030±0.00003%; P: 0.00030±0.00003%; S: 0.00075±0.00009%; Ag: 0.0012±0.0002%; Si: 0.00056±0.00005%; Mn: 0.00027±0.00002%; Cd: 0.00021±0.00002%; Co: 0.00031±0.00002%; Cr: 0.00034±0.00004%; Se: 0.00012±0.00002%; Te: 0.00013±0.00004%; the balance is Cu.

[0013] In one embodiment of the present invention, the elements in the standard substance are composed as follows: Pb: 0.00041±0.00004%; Fe: 0.00058±0.00004%; Bi: 0.00038±0.00005%; Sb: 0.00053±0.00004%; As: 0.00055 ±0.00005%; Sn: 0.00047±0.00004%; Ni: 0.00061±0.00005%; Zn: 0.00050±0.00003%; P: 0.00044±0.00005%; S: 0.00090±0.00011%; Ag: 0.0020±0.0002%; Si: 0.00069±0.00008%; Mn: 0.00058±0.00003%; Cd: 0.00014±0.00001%; ​​Co: 0.00058±0.00003%; Cr: 0.00055±0.00005%; Se: 0.00033±0.00005%; Te: 0.00033±0.00003%; the balance is Cu.

[0014] In one embodiment of the present invention, the elements in the standard substance are composed as follows: Pb: 0.0013±0.0001%; ​​Fe: 0.0011±0.0001%; ​​Bi: 0.0010±0.0001%; ​​Sb: 0.00096±0.00006%; As: 0.0011±0 .0001%; ​​Sn: 0.0010±0.0001%; ​​Ni: 0.0010±0.0001%; ​​Zn: 0.00092±0.00008%; P: 0.00089±0.00009%; S: 0. 0.0016±0.0002%; Ag: 0.0025±0.0002%; Si: 0.00035±0.00008%; Mn: 0.0014±0.0001%; ​​Cd: 0.00027±0.00002%; Co: 0.0015±0.0001%; ​​Cr: 0.0012±0.0002%; Se: 0.00058±0.00003%; Te: 0.00054±0.00006%; the balance is Cu.

[0015] In one embodiment of the present invention, the elements in the standard substance are composed as follows: Pb: 0.0025±0.0002%; Fe: 0.0029±0.0002%; Bi: 0.0029±0.0002%; Sb: 0.0030±0.0001%; ​​As: 0.0032± 0.0002%; Sn: 0.0029±0.0002%; Ni: 0.0030±0.0002%; Zn: 0.0027±0.0002%; P: 0.0030±0.0002%; S: 0 .0039±0.0003%; Ag: 0.0038±0.0002%; Si: 0.0028±0.0002%; Mn: 0.0028±0.0002%; Cd: 0.0012±0.0001%; ​​Co: 0.0030±0.0002%; Cr: 0.0028±0.0002%; Se: 0.0012±0.0001%; ​​Te: 0.0013±0.0002%; the balance is Cu.

[0016] In a second aspect, the present invention provides a method for preparing the above-mentioned cathode copper spectral analysis standard substance.

[0017] The preparation method provided by the present invention comprises the following steps: S1. According to the elemental composition of the standard substance, calculate and prepare various raw materials: including grade A copper and the single substances or compounds of the remaining elements; S2. Mix and melt various raw materials using a medium frequency induction furnace, wherein the melting temperature is 1200-1280°C; S3, casting the alloy liquid obtained by smelting in step S2 into an ingot, controlling the casting temperature at 1200-1250°C and the casting speed at 90-110 mm / min; performing a preliminary inspection on the ingot after obtaining the ingot; S4, processing the ingots that have passed the initial inspection in step S3 into target specifications, obtaining standard materials for cathode copper spectral analysis, and performing uniformity inspection, stability investigation, fixed value analysis and uncertainty assessment respectively, and then sawing, polishing and marking to obtain finished products.

[0018] Preferably, in step S1, the raw materials are grade A copper, iron sheet, pure nickel, pure cobalt, pure tin, pure antimony, pure bismuth, electrolytic manganese sheet, pure silicon, pure chromium, pure lead, pure sulfur, pure silver, pure selenium, pure tellurium, copper-cadmium alloy, copper-phosphorus alloy, copper-arsenic alloy and copper-zinc alloy.

[0019] Preferably, in step S2, grade A copper, iron sheet, pure nickel and pure cobalt are first mixed, and after they are completely melted, the remaining raw materials are added.

[0020] The invention provides a cathode copper spectral analysis standard substance and a preparation method thereof. The invention obtains a cathode copper spectral analysis standard substance with excellent uniformity and stability through reasonable component design and control of the preparation method. The standard substance meets relevant technical requirements and is suitable for spark source atomic emission spectrometry analysis of materials such as grade A copper (Cu-CATH-1) in GB / T 467-2010 "cathode copper", and can be used for quality evaluation, calibration of analytical instruments, evaluation of analytical methods, quantity value transfer and traceability, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] In order to more clearly illustrate the technical solutions in the present invention or the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0022] Figure 1 This is a metallographic test piece of an ingot slice of SYD2001 provided in an embodiment of the present invention.

[0023] Figure 2 It is a metallographic test piece of an ingot slice of SYD2002 provided in an embodiment of the present invention.

[0024] Figure 3 This is a metallographic test piece of an ingot slice of SYD2003 provided in an embodiment of the present invention.

[0025] Figure 4 It is a metallographic test piece of an ingot slice of SYD2004 provided in an embodiment of the present invention.

[0026] Figure 5 It is a metallographic test piece of an ingot slice of SYD2005 provided in an embodiment of the present invention.

[0027] Figure 6 This is a schematic diagram of the initial uniformity inspection. DETAILED DESCRIPTION

[0028] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0029] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0030] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "specific implementations", or "some specific implementations" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the embodiment of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction.

[0031] If no specific techniques or conditions are specified in the examples, the techniques or conditions described in the literature in the field or the product instructions are used. If no manufacturer is specified for the reagents or instruments used, they are all conventional products that can be purchased through regular channels.

[0032] The main component of cathode copper is copper, and its content is very high. Generally, the pure copper content of cathode copper is above 99.9%, and the copper content of some cathode copper can even reach 99.99% or higher. The main component of the standard material for cathode copper spectral analysis is also copper, containing a small amount of other elements, but some elements are easy to segregate, volatilize, oxidize or burn. Therefore, in order to ensure the accuracy of the analysis, the reasonable design of the element composition in the standard material is a necessary prerequisite for achieving the uniformity of the standard material and the compliance of the components.

[0033] The embodiment of the present invention provides a standard substance for cathode copper spectral analysis, which takes grade A copper as a matrix and contains impurity elements Pb, Bi, Sb, As, Sn, Ni, Zn, Mn, Cd, Co, Cr, Se, Te, Fe, P, Si, S and Ag, and the total mass fraction of the impurity elements does not exceed 0.0065%.

[0034] In order to obtain good uniformity and stability, as an optional embodiment, the composition of each element in the standard substance is as follows: The mass fractions of Pb, Bi, Sb, As, Sn, Ni, Zn, Mn, Cd, Co, Cr, Se, and Te are all 0.00005~0.00015%; the mass fractions of Fe, P, and Si are all 0.0001~0.0003%; the mass fraction of S is 0.0004~0.0007%; the mass fraction of Ag is 0.0005~0.0008%; and the balance is Cu.

[0035] Further preferably, the elements in the standard substance are composed as follows: Pb: 0.00009±0.00003%; Fe: 0.00020±0.00003%; Bi: 0.00008±0.00002%; Sb: 0.00007±0.00003%; As: 0.00013± 0.00003%; Sn: 0.00007±0.00002%; Ni: 0.00012±0.00002%; Zn: 0.00006±0.00002%; P: 0.00016±0.00003%; S: 0 .00052±0.00007%; Ag: 0.00071±0.00006%; Si: 0.00016±0.00003%; Mn: 0.00005±0.00002%; Cd: 0.00006±0.00002%; Co: 0.00009±0.00002%; Cr: 0.00007±0.00002%; Se: 0.00007±0.00002%; Te: 0.00008±0.00003%; the balance is Cu.

[0036] As an optional embodiment, the elements in the standard substance are composed as follows: The mass fractions of Pb, Bi, Sb, Sn, Se, and Te are all 0.0001~0.0003%; the mass fractions of As, Ni, Zn, P, Mn, Cd, Co, and Cr are all 0.0002~0.0004%; the mass fraction of Fe is 0.0003~0.0005%; the mass fraction of S is 0.0007~0.0012%; the mass fraction of Ag is 0.001~0.0015%; the mass fraction of Si is 0.0004~0.0007%; and the balance is Cu.

[0037] Further preferably, the elements in the standard substance are composed as follows: Pb: 0.00020±0.00004%; Fe: 0.00038±0.00004%; Bi: 0.00018±0.00002%; Sb: 0.00025±0.00003%; As: 0.00033 ±0.00004%; Sn: 0.00026±0.00003%; Ni: 0.00034±0.00004%; Zn: 0.00030±0.00003%; P: 0.00030±0.00003%; S: 0.00075±0.00009%; Ag: 0.0012±0.0002%; Si: 0.00056±0.00005%; Mn: 0.00027±0.00002%; Cd: 0.00021±0.00002%; Co: 0.00031±0.00002%; Cr: 0.00034±0.00004%; Se: 0.00012±0.00002%; Te: 0.00013±0.00004%; the balance is Cu.

[0038] As an optional embodiment, the elements in the standard substance are composed as follows: The mass fractions of Pb and Bi are both 0.0003~0.0006%; the mass fractions of Fe, Sb, As, Sn, Ni, Zn and P are both 0.0004~0.0007%; the mass fractions of S, Si, Mn, Co and Cr are both 0.0005~0.001%; ​​the mass fraction of Ag is 0.001~0.002%; the mass fraction of Cd is 0.0001~0.0003%; the mass fractions of Se and Te are both 0.0002~0.0004%; the balance is Cu.

[0039] Further preferably, the elements in the standard substance are composed as follows: Pb: 0.00041±0.00004%; Fe: 0.00058±0.00004%; Bi: 0.00038±0.00005%; Sb: 0.00053±0.00004%; As: 0.00055 ±0.00005%; Sn: 0.00047±0.00004%; Ni: 0.00061±0.00005%; Zn: 0.00050±0.00003%; P: 0.00044±0.00005%; S: 0.00090±0.00011%; Ag: 0.0020±0.0002%; Si: 0.00069±0.00008%; Mn: 0.00058±0.00003%; Cd: 0.00014±0.00001%; ​​Co: 0.00058±0.00003%; Cr: 0.00055±0.00005%; Se: 0.00033±0.00005%; Te: 0.00033±0.00003%; the balance is Cu.

[0040] As an optional embodiment, the elements in the standard substance are composed as follows: The mass fractions of Pb, Fe, Bi, Sb, As, Sn, Ni, Zn and P are all 0.0008~0.0015%; the mass fractions of S, Mn, Co and Cr are all 0.001~0.002%; the mass fraction of Ag is 0.002~0.003%; the mass fraction of Si is 0.0003~0.0008%; the mass fraction of Cd is 0.0002~0.0004%; the mass fractions of Se and Te are all 0.0005~0.001%; ​​and the balance is Cu.

[0041] Further preferably, the elements in the standard substance are composed as follows: Pb: 0.0013±0.0001%; ​​Fe: 0.0011±0.0001%; ​​Bi: 0.0010±0.0001%; ​​Sb: 0.00096±0.00006%; As: 0.0011±0 .0001%; ​​Sn: 0.0010±0.0001%; ​​Ni: 0.0010±0.0001%; ​​Zn: 0.00092±0.00008%; P: 0.00089±0.00009%; S: 0. 0.0016±0.0002%; Ag: 0.0025±0.0002%; Si: 0.00035±0.00008%; Mn: 0.0014±0.0001%; ​​Cd: 0.00027±0.00002%; Co: 0.0015±0.0001%; ​​Cr: 0.0012±0.0002%; Se: 0.00058±0.00003%; Te: 0.00054±0.00006%; the balance is Cu.

[0042] As an optional embodiment, the elements in the standard substance are composed as follows: The mass fractions of Pb, Fe, Bi, Sb, As, Sn, Ni, Zn, P, Si, Mn, Co, and Cr are all 0.002~0.004%; the mass fractions of S and Ag are all 0.003~0.005%; the mass fractions of Cd, Se, and Te are all 0.001~0.002%; and the balance is Cu.

[0043] Further preferably, the elements in the standard substance are composed as follows: Pb: 0.0025±0.0002%; Fe: 0.0029±0.0002%; Bi: 0.0029±0.0002%; Sb: 0.0030±0.0001%; ​​As: 0.0032± 0.0002%; Sn: 0.0029±0.0002%; Ni: 0.0030±0.0002%; Zn: 0.0027±0.0002%; P: 0.0030±0.0002%; S: 0 .0039±0.0003%; Ag: 0.0038±0.0002%; Si: 0.0028±0.0002%; Mn: 0.0028±0.0002%; Cd: 0.0012±0.0001%; ​​Co: 0.0030±0.0002%; Cr: 0.0028±0.0002%; Se: 0.0012±0.0001%; ​​Te: 0.0013±0.0002%; the balance is Cu.

[0044] The cathode copper spectral analysis standard material provided in the embodiment of the present invention is based on grade A copper (Cu-CATH-1), and elements Pb, Fe, Bi, Sb, As, Sn, Ni, Zn, P, Si, Mn, Co, Cr, S, Ag, Cd, Se, and Te are added. In order to avoid segregation and instability of elements, the content range of each element is set within the above range through ratio calculation. Within this setting range, the uniformity and stability of the standard material are better.

[0045] The invention also provides a method for preparing the cathode copper spectrum analysis standard substance.

[0046] In an embodiment of the present invention, the preparation method comprises the following steps: S1. According to the elemental composition of the standard substance, calculate and prepare various raw materials: including grade A copper and the single substances or compounds of the remaining elements; S2. Mix and melt various raw materials using a medium frequency induction furnace, wherein the melting temperature is 1200-1280°C; S3, casting the alloy liquid obtained by smelting in step S2 into an ingot, controlling the casting temperature at 1200-1250°C and the casting speed at 90-110 mm / min; performing a preliminary inspection on the ingot after obtaining the ingot; S4, processing the ingots that have passed the initial inspection in step S3 into target specifications, obtaining standard materials for cathode copper spectral analysis, and performing uniformity inspection, stability investigation, fixed value analysis and uncertainty assessment respectively, and then sawing, polishing and marking to obtain finished products.

[0047] In the above steps, 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 will not melt fully and completely, and the alloying speed will be slow, resulting in uneven liquid phase composition. If the temperature is too high, the elements will be severely burned, which will seriously affect the uniformity of the standard material. The present invention has been experimentally determined to be controlled at 1200~1280℃.

[0048] The casting temperature has a great influence on the uniformity of the standard material. If the temperature is too high, the cooling speed is slow, the liquid phase time is long, and the macro segregation is serious; if the temperature is too low, there will be segregation, the fluidity of the solution is poor, and defects such as pores and inclusions are prone to occur, and the quality of the ingot is poor. The present invention has been experimentally determined to be controlled at 1200-1250°C. The casting speed directly affects the quality of the ingot. If the casting speed is too slow, the time required for solidification is short, the surface quality of the casting is poor, and defects such as pores and cracks are prone to occur inside; if the casting speed is too fast, the time required for solidification is long, and elements such as lead and iron are prone to segregation, making the ingot longitudinally uneven. After testing, it is appropriate to control the casting speed at 90-110mm / min. The specification of the ingot mold in the embodiment of the present invention is Φ120×1500mm.

[0049] Preferably, in step S1, the raw materials are grade A copper, iron sheet, pure nickel, pure cobalt, pure tin, pure antimony, pure bismuth, electrolytic manganese sheet, pure silicon, pure chromium, pure lead, pure sulfur, pure silver, pure selenium, pure tellurium, copper-cadmium alloy, copper-phosphorus alloy, copper-arsenic alloy and copper-zinc alloy.

[0050] Since arsenic, phosphorus, zinc and cadmium are relatively volatile, an intermediate alloy is selected. Specifically, As: 30% copper-arsenic alloy, P: 13% copper-phosphorus alloy, Zn: 35% copper-zinc alloy, Cd: 1.1% copper-cadmium alloy can be selected.

[0051] Preferably, in step S1, when grade A copper is used, the content of elements already contained in the grade A copper is deducted during batching according to the raw material analysis report, so that the batching accuracy is strictly controlled.

[0052] Preferably, in step S2, firstly, grade A copper, iron sheet, pure nickel and pure cobalt are mixed, and after they are completely melted, the remaining raw materials are added. A reasonable order of adding materials is crucial to ensure that the alloy composition meets expectations.

[0053] In order to facilitate the understanding of the cathode copper spectral analysis standard substance provided by the present invention, it is described below through specific examples.

[0054] The equipment used in the following embodiments include: a 200kW vacuum medium-frequency induction furnace, a Φ120×1500mm graphite mold, a sawing machine, a common lathe, and a spark source atomic emission spectrometer.

[0055] This embodiment provides 5 designed cathode copper spectral analysis standard substances, the sample numbers are SYD2001-SYD2005, and their composition designs and target uncertainties are shown in Tables 1 to 5.

[0056] Table 1 SYD2001 composition design and target uncertainty (ω / %)

[0057] Table 2 SYD2002 composition design and target uncertainty (ω / %)

[0058] Table 3 SYD2003 composition design and target uncertainty (ω / %)

[0059] Table 4 SYD2004 composition design and target uncertainty (ω / %)

[0060] Table 5 SYD2005 composition design and target uncertainty (ω / %)

[0061] The preparation method of the above standard substances is as follows: S1. According to the elemental composition of the standard substance, various raw materials are calculated and prepared, including: Grade A copper (Cu-CATH-1), instant iron sheet, pure nickel, pure cobalt, pure tin, pure antimony, pure bismuth, electrolytic manganese sheet, pure silicon, pure chromium, pure lead, pure sulfur, pure silver, pure selenium, pure tellurium, copper-cadmium alloy, copper-phosphorus alloy, copper-arsenic alloy, copper-zinc alloy; and according to the raw material analysis report of Grade A copper, the element content already contained in Grade A copper is deducted.

[0062] S2. Various raw materials are mixed and smelted in a medium frequency induction furnace at a smelting temperature of 1200-1280°C. When mixing, first load the A-grade copper, iron sheet, pure nickel and pure cobalt into the furnace at one time, and put other elements into the charging box after they are prepared. When the raw materials in the furnace are completely melted, start to evacuate. When the vacuum degree reaches the requirement, introduce 0.5MPa argon gas for protection, and then add the remaining raw materials into the melt by turning over the charging box.

[0063] S3, casting the liquid obtained by smelting in step S2 into ingots, the casting temperature is controlled at 1200-1280°C, and the casting speed is controlled at 90-110mm / min; sequential casting is adopted, and two Φ120×1500mm ingots are cast sequentially for each number, and the head defects of the two SYD2001 ingots are cut off by about 100mm, and the tails are cut off by about 200mm and 300mm respectively. The lengths of the two ingots are 1100mm and 1500mm respectively. 1200mm; for SYD12004, the defects at the heads of the two ingots are cut off by about 200mm, and the tails are cut off by about 300mm and 400mm respectively. The lengths of the two ingots are 1000mm and 900mm respectively; for SYD2002, SYD2003 and SYD2005, the defects at the heads of the two ingots are cut off by about 100mm, and the tails are cut off by about 100~200mm. The lengths of the two ingots are about 1200~1300mm.

[0064] After obtaining the ingot, an initial inspection of the ingot is carried out.

[0065] S4, sawing the ingot that passed the initial inspection in step S3 into a small ingot with a length of 250-300 mm, putting it into the heating furnace of the hydraulic press, controlling the temperature between 850°C and 860°C, heating for 2 hours, then transferring it to the extrusion barrel, and extruding it under a pressure of 1500-1600 tons to obtain a Φ40 mm copper rod. After sawing, uniformity inspection, stability investigation, fixed value analysis and uncertainty assessment are carried out. After passing the inspection, the ingot is polished and chamfered, the surface is numbered, and stored in a cool and dark storage room at room temperature. The specification is Φ38*30 mm, packaged, and labeled to obtain a standard substance for cathode copper spectral analysis.

[0066] The following is a detailed introduction to the initial inspection, uniformity test, stability test, constant value analysis and uncertainty assessment of ingots.

[0067] 1. Initial inspection of ingots 1.1 Preparation of ingot specimens The defects at both ends of the finished ingot were cut off with a sawing machine, and then a test piece with a thickness of about 10mm~15mm was taken from the bottom of the first ingot, the head of the second ingot, and the bottom, respectively, and three sample test pieces were obtained for each number.

[0068] 1.2 Microstructure inspection of ingot slices Through low-power inspection of metallographic specimens, it is proved that the ingot structure is dense, uniform, and free of defects such as pores, looseness, and inclusions. One ingot slice is selected for each number as a diagram. The results are as follows: Figures 1 to 5 shown.

[0069] 1.3 Preliminary inspection of the uniformity of ingot samples The uniformity was initially checked using a SPECTROLABM12 spark source atomic emission spectrometer to test the chemical composition segregation of three ingot specimens. Each specimen was excited at three points (in the center, edge, and 1 / 2 radius of the specimen, respectively). Figure 6 As shown, 3×3 analysis data are obtained, and the uniformity is initially checked in turn.

[0070] The calculation and determination methods are as follows: After calculating the standard deviation (s) of 9 measurements of three test pieces, compare it with the repeatability limit (r) of each element in YS / T 464-2019 "Direct Reading Spectroscopic Analysis Method for Cathode Copper" for judgment. r is calculated by linear interpolation. When 1.5 S≤r, the uniformity initial inspection is considered to be qualified; when 1.5 S>r, the uniformity initial inspection is considered to be unqualified.

[0071] The inspection results show that the 1.5 S of the three test pieces of the five samples SYD2001~SYD2005 in the final 9 measurements are all less than the repeatability limit r of each element, indicating that the initial inspection of the uniformity of the ingots of the five samples is qualified.

[0072] 2. Uniformity test 2.1 Uniformity test method According to the provisions of 5.5 of JJF 1343-2022 "Value Determination and Uniformity and Stability Evaluation of Standard Materials", the sampling method should take into account the defects of the preparation method to ensure the representativeness of the uniformity evaluation. The sampling points should be drawn from the parts where the characteristic values ​​to be determined may differ. The distribution of the sampling points should be representative enough for the overall sample. The pure copper standard material selects samples at both ends and the middle of each extruded rod. A total of 20 standard materials are selected and numbered in sequence. The pure copper standard material GBW (E) 020156 and the phosphorus deoxidized copper standard material GBW (E) 020158 are used for calibration on the SPECTROLAB M12 spark source atomic emission spectrometer. After calibration, a uniformity inspection test is performed. Each sample is excited three times, and 3×20 data are obtained for each element. The measurement scheme adopted is as follows: First time: 1–3–5–7–9–11–13–15–17–19–2–4–6–8–10–12–14–16–18–20; Second time: 20–19–18–17–16–15–14–13–12–11–10–9–8–7–6–5–4–3–2–1; The third time: 2–4–6–8–10–12–14–16–18–20–1–3–5–7–9–11–13–15–17–19.

[0073] 2.2 Mathematical statistical model and test results of uniformity The single factor variance method was used to perform statistical processing on the 20 groups of data tested three times. The variance method is a common method used to test uniformity. By comparing the variance between groups and the variance within groups, it is determined whether there is a systematic deviation between the measurement values ​​of each group.

[0074] The statistical model evaluated is: random draw m Each sample was measured repeatedly under the same experimental conditions using a high-precision measurement method. n times, measured m Group precision measurement data: average value ; average value ; ; average value ; Calculate the overall average

[0075] Calculate the sum of squares of deviations between groups

[0076] Calculate the within-group sum of squares of deviations

[0077] Calculating degrees of freedom ;

[0078] Between-group variance s 1 2 = Q 1 / v 1 Within-group variance s 2 2 = Q 2 / v 2 Make statistics F :

[0079] Judgment: According to the significance level and degrees of freedom ,from F The critical value table is found .Compare F and :like , it is considered that there is no significant difference within and between groups and the sample is uniform.

[0080] The uniformity inspection results are shown in Table 6. It can be seen that the F statistical values ​​of the standard substances are all less than the F critical value. Therefore, it can be judged that the cathode copper standard substances (5 types) are uniform and there are no abnormalities.

[0081] Table 6 Uniformity inspection results

[0082] It should be noted that the F statistic value of Pb, Fe, S, Cd, and Co in SYD2001, Cd in SYD2002, and Mn in SYD2004 is less than 0.5, which means that the inter-group fluctuation is smaller than the intra-group fluctuation, indicating that the intra-group fluctuation is larger than the inter-group fluctuation. This situation usually occurs in the uniformity detection of spark source atomic emission spectrometry because this method has poor repeatability. s 1 2 < s 2 2 , a calculation formula with poor repeatability is required to calculate , that is, the formula , as the uniformity uncertainty component.

[0083] 3. Stability test Stability is a basic property of reference materials, which is used to describe the nature of the change of the characteristic values ​​of reference materials over time, that is, to describe the time distribution characteristics of the characteristics of reference materials. Stability includes long-term stability and short-term stability. Since the melting point of copper is 1083.4℃ and the boiling point is 2567℃, the short-term stability of this series of reference materials will not be affected by temperature changes and changes in packaging placement during transportation and severe weather conditions. Therefore, the influence of short-term stability can be ignored for cathode copper reference materials, and the influence of long-term stability can be mainly evaluated.

[0084] 3.1 Long-term stability test method The present invention adopts trend analysis method to evaluate the long-term stability of standard substances. For cathode copper standard substances (5 kinds) stored at room temperature, 2 samples are randomly selected at each time point, each sample is milled into chips, bottled and put into use, and within 12 months, 6 time points are selected according to the principle of dense time intervals first and sparse time intervals later, namely June 14, 2021, July 16, 2021, September 13, 2021, November 15, 2021, February 14, 2022, and June 23, 2022, and the time intervals are 0 month, 1 month, 3 months, 5 months, 8 months, and 12 months, respectively.

[0085] The analysis method adopted in the long-term stability study is spark source atomic emission spectroscopy. The instrument used is the SPECTROLAB spark direct reading spectrometer made by SPECTRO in Germany. For each characteristic value, each piece of standard material is measured three times at a specific time point selected. Without exceeding the repeatability limit of the method, the average of the three measurement values ​​is taken for statistics.

[0086] The stability of the reference material is evaluated using the classical model. The basic linear model for stability evaluation can be expressed as follows: Y = β 0 +β 1 X Where: β 0 —intercept; β 1 — slope; X -time; Y —Characteristic values ​​of candidate reference materials.

[0087] For a stable standard substance, the ideal expectation is that the intercept of the straight line (within the uncertainty range) is equal to the value of the standard substance; at the same time, the slope of the straight line is β 1 Approaching zero.

[0088] Usually, since each time point is extracted p unit samples, repeated measurements, etc., so each X i Will correspond p indivual Y i value; for trend analysis, X i , you can use p Sampling unit Y i average value Regression analysis was performed. The intercept was calculated by using a univariate linear model-linear least squares method. β 0 and slope β 1 Estimate of the true value b 0 and b 1 , and the corresponding standard deviation and .

[0089] b 0 and b 1 The calculation formula is as follows:

[0090]

[0091]

[0092]

[0093] Where: b 1 ——Linear regression slope; b 0 ——Linear regression intercept; X - interval time; Y - characteristic quantity values ​​of candidate reference materials; ——the i-th time point; Y i ——the observed value at the ith time point; ——the average value of all time points; ——the average value of all observations; n——number of measurements; s – standard deviation of each point on the straight line; s ( b 1 )——standard deviation of the slope; Taking the degrees of freedom as n-2, at a 95% confidence level, the t factor is 2.78. If the result satisfies , then the standard substance is considered to be stable during the observation time.

[0094] 3.2 Long-term stability test results The long-term stability test results, judgment conclusions and uncertainty calculation results of each standard substance are listed in Table 7. The test results show that the statistics of each element meet the requirements. , indicating that the slopes of the trend lines of the stability investigation of the cathode copper standard substances (5 kinds) within 12 months are not significant, that is, the characteristic values ​​of each element have not undergone obvious directional changes, and the values ​​are stable during the storage period of 12 months.

[0095] Table 7 Stability test results

[0096] 3.3 Stability monitoring of similar reference materials and standard samples According to the method recommended in JJF 1343-2022 "Value determination, uniformity and stability evaluation of standard materials", the stability of pure copper spectral analysis standard material GBW02114, pure copper standard sample GSB04-2415-2008 T01 and cathode copper spectral analysis standard sample GSB 04-2554-2010 #2 standard sample with similar components and compositions were monitored. The stability results of the standard material for pure copper spectral analysis showed that the standard material had good stability over 15 years. The stability results of the standard samples for pure copper and cathode copper spectral analysis showed that the pure copper standard sample had good stability over 14 years, and the cathode copper standard sample had good stability over 10 years.

[0097] 3.4 Determination of the validity period of reference materials Based on the validity period (15 years) of similar pure copper standard materials with similar preparation processes and composition, the stability test of the series of cathode copper standard materials by this research unit for 12 months, and the extremely stable characteristics of copper itself, the validity period of the cathode copper standard materials (5 numbers) should be determined to be 15 years. Therefore, the validity period of the series of standard materials (5 points) for cathode copper spectral analysis is stipulated as follows: The validity period of the series of standard substances (5 points) for cathode copper spectral analysis is 15 years; Long-term monitoring is carried out on a series of standard substances (5 points) used for cathode copper spectral analysis. The research and development unit will regularly monitor the stability of the standard substances and notify customers in a timely manner if any changes occur.

[0098] 4. Fixed value analysis 4.1 Preparation of reference material samples Sixteen samples of the five numbered cathode copper standard materials provided in this embodiment are randomly selected from each number and processed into chips. A strong magnet bar is used to remove the iron chips mixed in the sample processing. Boil glacial acetic acid (1+4) in a beaker for 2-3 minutes, pour out the acetic acid solution, wash the sample with water and anhydrous ethanol in turn, cool and dry, place it in a desiccator, and cool to room temperature. After being fully mixed, bottle and label, store it in a cool and dark storage room at room temperature as a fixed value analysis sample.

[0099] 4.2 Selection of standard material valuation method This standard material is determined by cooperation among multiple laboratories in accordance with the requirements of JJF1006-1994 "Technical Specifications for Primary Standard Materials". Before the sample is distributed, the laboratory's capabilities are confirmed and an operating instruction is formulated with the following requirements: (1) The cooperative valuation unit shall have a technical person in charge to organize and specifically guide the valuation work, understand the valuation requirements of reference materials, and the analysts shall be technicians with rich experience in component analysis.

[0100] (2) The instruments and equipment used for fixed value analysis (including balances and measuring instruments) have been verified / calibrated by the national metrology verification institution or a calibration institution accredited by CNAS and are within the validity period.

[0101] (3) The standard substances (including standard solutions) used in the fixed value analysis are all national certified standard substances (numbered GBW) and can be traced back to the International System of Units within their validity period.

[0102] (4) The analytical method selected for the fixed value analysis is a method that has been proven to be accurate and reliable in theory and practice, including methods specified in national standards and industry standards, or analytical methods developed by the applicant's unit. Self-developed analytical methods that have been proven to be accurate and reliable may also be used.

[0103] (5) Two samples of each numbered standard substance shall be issued, each sample shall be measured twice independently, and the results of four independent measurements shall be reported.

[0104] (6) The determination result of each element is expressed as mass fraction (w / %). The number of digits retained for each determination result is 0.0xxx%, 0.00xxx%, 0.000xx%. The numerical rounding shall be carried out in accordance with the provisions of GB / T 8170-2008.

[0105] (7) The valuation report may be submitted in accordance with the original reporting format of the valuation unit, and the report shall at least include the name and number of the analytical method, the name and model of the instrument and equipment, etc.

[0106] (8) All calibration work shall be completed within 2 months after receiving the samples and operating instructions. If the data is out of the group after summary, it needs to be re-inspected.

[0107] 4.3 Traceability of measurement value This standard substance is valued by multiple laboratories, and the value setting unit is a qualified national authority and 8 laboratories with good technical capabilities in the industry. The value setting unit has passed CNAS accreditation or CMA qualification certification, has the ability to test standard substances that meet the requirements, and guarantees its traceability.

[0108] The testing equipment and instruments used in the fixed value laboratory have all been verified or calibrated.

[0109] The standard substances used in the test are all nationally certified standard substances.

[0110] The value determination method is the national standard method. The applicant conducted a method study on the analysis method, and other value determination laboratories in the sulfur element out-of-range analysis section conducted method verification.

[0111] 4.4 Technical review and statistical testing of fixed value analysis data Each collaborative analysis and determination unit measures 2 minimum units, and each unit is measured independently twice, providing 4 measurement data. The data are statistically processed in accordance with the provisions of JJF 1343-2022 "Value Determination and Uniformity and Stability Evaluation of Reference Materials", and finally the standard value of the reference material is determined.

[0112] 4.4.1 Outlier Test 4.4.1.1 Outliers within a group Compare the range of the four data in each laboratory's fixed value group with 1.3 times the method repeatability limit (1.3r). When the range is not greater than 1.3r, it is determined that there are no outliers in the group; when the range is greater than 1.3r, further judgment is required on the outliers in the group.

[0113] The test results are: the third group of data of P element of SYD2001, the first group of data of Te element of SYD2002, and the first group of data of P element of SYD2003 are abnormal within the group. Grubbs test was used for the intra-group test, and no abnormalities were found. The final judgment result is: there are no outliers within the group of this series of standard substances (5 numbers).

[0114] 4.4.1.2 Inter-group outlier test Dixon method was used to test whether there was a significant difference between the mean values ​​and to eliminate abnormal values. The measured data were arranged in order from small to large:

[0115]

[0116]

[0117] Calculate value and value. is the critical value. If , and , then it is determined that is an outlier; if , and , then it is determined that is an outlier; if and the values are all less than the value, then all data are retained.

[0118] The results of outlier test are shown in Tables 8 to 12.

[0119] Table 8 Results of Outlier Test among Groups of SYD2001

[0120] Table 9 Results of Outlier Test among Groups of SYD2002

[0121] Table 10 Results of Outlier Test among Groups of SYD2003

[0122] Table 11 Results of Outlier Test among Groups of SYD2004

[0123] Table 12 Results of Outlier Test among Groups of SYD2005

[0124] 4.4.2 Normality Test The Shapiro-Wilk method is used to test the normality of the data distribution. The statistic for the Shapiro-Wilk method is:

[0125] The criterion for this statistic is that when , the measured data are accepted as being normally distributed. is a value related to the number of measurements and the confidence probability. When the statistic W > W0.05, the data are approximately normally distributed and are regarded as normal and retained; when W < W0.01, the normality of the data is poor.

[0126] Test results: Ni and Te elements in SYD2003 were approximately normally distributed, and the other groups were all normally distributed. Considering the limited number of measurements and the closeness of the mean and median values, the approximately normal distribution was treated as a normal distribution.

[0127] 4.4.3 Equal precision test Cochran's method is used to test whether the mean values ​​are of equal precision. First calculate Groups of data The variance of the data, and then calculate the maximum variance and The ratio of the sum of variances:

[0128] According to the significance level , number of data sets , repeated measurement times , check the Cochran test critical value table and get the critical value .

[0129] like , indicating that the average values ​​of each group of data are of equal precision. , indicating that the maximum variance tested is an outlier. The outlier variance indicates that the accuracy of this group of data is worse than that of other groups of data. When calculating the fixed value results with unequal accuracy, the unequal accuracy weighted processing can be considered. When calculating the fixed value results, the unequal accuracy situation can be used.

[0130] The equal precision test of each fixed value element in the standard substances (5 kinds) of the present invention is shown in Tables 13 to 17. The test shows that S in SYD2001; P and Cr in SYD2005 are approximately equal in precision, and the data of each element in the other groups are of equal precision, but through comparison, there is no obvious difference between the fixed value analysis methods, and the maximum range in the data group is less than the reproducibility limit of the fixed value method, so they are all treated as equal precision.

[0131] Table 13 SYD2001 equal precision statistical results

[0132] Table 14 SYD2002 equal precision statistical results

[0133] Table 15 SYD2003 equal precision statistical results

[0134] Table 16 SYD2004 equal precision statistical results

[0135] Table 17 SYD2005 equal precision statistical results

[0136] 5. Uncertainty assessment The mean of the average values ​​of the characteristic quantity fixed value data of each laboratory is taken as the standard value of the characteristic quantity.

[0137] The uncertainty of the reference material value consists of the following three parts: (1) Uncertainty introduced by the value determination process ; (2) Uncertainty introduced by the homogeneity of standard materials ; (3) Uncertainty introduced by the instability of standard materials 。

[0138] The combined uncertainty of the reference material =

[0139] Expanded uncertainty , k is the expansion factor.

[0140] 5.1 Uncertainty introduced by the determination process This standard material adopts the method of multiple value determination, and the uncertainty introduced in the value determination process mainly considers the type A uncertainty. Type A uncertainty is the uncertainty component introduced by the collaborative value determination of multiple parties.

[0141] The Type A uncertainty is:

[0142] Where s is the standard deviation among the laboratories that determine the value; n is the number of collaborative laboratories that determine the value.

[0143] 5.2 Uncertainty introduced by homogeneity of reference materials This type of uncertainty can be statistically evaluated through the uniformity test results. The standard deviation introduced by uniformity is calculated according to the following formula:

[0144]

[0145] Where: is the between-group variance, is the within-group variance; is the sum of squares of between-group deviations, ; is the within-group sum of squares, ; is the degree of freedom, , ; is the number of units; is the number of determinations per cell.

[0146] when hour, Equivalent to the uncertainty component caused by the heterogeneity between groups : = ; When the measurement method for uniformity assessment has poor repeatability, The following formula should be used:

[0147] 5.3 Uncertainty introduced by stability Since copper spectral standard materials have good stability, the influence of short-term stability can be ignored, so only the uncertainty introduced by long-term stability is considered.

[0148] The uncertainty introduced by stability is:

[0149] Where X is the validity period.

[0150] Based on the above tests, the standard values ​​and uncertainties of the five standard substances provided in this example are finally determined as shown in Tables 18 to 22.

[0151] Table 18 SYD2001 standard values ​​and uncertainties (%) (95% confidence level, k =2, n=8)

[0152] Table 19 SYD2002 standard values ​​and uncertainties (%) (confidence level 95%, k =2, n=8)

[0153] Table 20 SYD2003 standard values ​​and uncertainties (%) (confidence level 95%, k =2, n=8)

[0154] Table 21 SYD2004 standard value and uncertainty (%) (confidence level 95%, k=2, n=8)

[0155] Table 22 SYD2005 standard value and uncertainty (%) (confidence level 95%, k=2, n=8)

[0156] The cathode copper spectral analysis standard substances (5 kinds) provided in this embodiment have reasonable composition design, advanced preparation technology, good uniformity and stability, and accurate value determination. They are suitable for quantitative analysis of 18 elements such as Pb, Fe, Bi, Sb, As, Sn, Ni, Zn, P, and S in cathode copper, and can also be used for instrument calibration, measurement method evaluation, and production control of such products.

[0157] In addition, a set of standard substances were randomly selected for curve fitting on the SPECTROLAB S spark source atomic emission spectrometer, and the working curves of each element had good linearity.

[0158] The above five kinds of standard substances were entrusted to the Copper Branch of Yunnan Tin Co., Ltd. and Renshou Huaci Semiconductor Materials Co., Ltd. for testing and trial use. Users all reported that the standard substances have reasonable composition design, stable data, uniform surface samples, and ideal linear working curves, which play an important guiding role in instrument equipment status and production quality monitoring.

[0159] In summary, the standard material provided by the present invention has good uniformity within the confidence interval of 95%, and after 12 months of stability investigation test, the standard material has good stability; after 15 years of stability investigation test of similar domestic pure copper standard material, pure copper standard sample, and cathode copper standard sample, the stability is good, and the validity period of the standard material can be determined to be 15 years with reference to its validity period. The developed standard material meets the relevant technical requirements, is suitable for spark source atomic emission spectrometry analysis of materials such as Class A copper (Cu-CATH-1) in GB / T 467-2010 "Cathode Copper", and can be used for quality evaluation, calibration of analytical instruments, evaluation and analysis methods, value transfer and traceability, etc.

[0160] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A standard substance for cathode copper spectral analysis, characterized in that: It is based on grade A copper and contains impurity elements such as Pb, Bi, Sb, As, Sn, Ni, Zn, Mn, Cd, Co, Cr, Se, Te, Fe, P, Si, S and Ag. The total mass fraction of impurity elements does not exceed 0.0065%.

2. The cathode copper spectral analysis standard substance according to claim 1, characterized in that: The elements in the standard substance are as follows: The mass fractions of Pb, Bi, Sb, As, Sn, Ni, Zn, Mn, Cd, Co, Cr, Se, and Te are all 0.00005~0.00015%; the mass fractions of Fe, P, and Si are all 0.0001~0.0003%; the mass fraction of S is 0.0004~0.0007%; the mass fraction of Ag is 0.0005~0.0008%; and the balance is Cu.

3. The cathode copper spectral analysis standard substance according to claim 1, characterized in that: The elements in the standard substance are as follows: The mass fractions of Pb, Bi, Sb, Sn, Se, and Te are all 0.0001~0.0003%; the mass fractions of As, Ni, Zn, P, Mn, Cd, Co, and Cr are all 0.0002~0.0004%; the mass fraction of Fe is 0.0003~0.0005%; the mass fraction of S is 0.0007~0.0012%; the mass fraction of Ag is 0.001~0.0015%; the mass fraction of Si is 0.0004~0.0007%; and the balance is Cu.

4. The cathode copper spectral analysis standard substance according to claim 1, characterized in that: The elements in the standard substance are as follows: The mass fractions of Pb and Bi are both 0.0003~0.0006%; the mass fractions of Fe, Sb, As, Sn, Ni, Zn and P are both 0.0004~0.0007%; the mass fractions of S, Si, Mn, Co and Cr are both 0.0005~0.001%; ​​the mass fraction of Ag is 0.001~0.002%; the mass fraction of Cd is 0.0001~0.0003%; the mass fractions of Se and Te are both 0.0002~0.0004%; the balance is Cu.

5. The cathode copper spectral analysis standard substance according to claim 1, characterized in that: The elements in the standard substance are as follows: The mass fractions of Pb, Fe, Bi, Sb, As, Sn, Ni, Zn and P are all 0.0008~0.0015%; the mass fractions of S, Mn, Co and Cr are all 0.001~0.002%; the mass fraction of Ag is 0.002~0.003%; the mass fraction of Si is 0.0003~0.0008%; the mass fraction of Cd is 0.0002~0.0004%; the mass fractions of Se and Te are all 0.0005~0.001%; ​​and the balance is Cu.

6. The cathode copper spectral analysis standard substance according to claim 1, characterized in that: The elements in the standard substance are as follows: The mass fractions of Pb, Fe, Bi, Sb, As, Sn, Ni, Zn, P, Si, Mn, Co, and Cr are all 0.002~0.004%; the mass fractions of S and Ag are all 0.003~0.005%; the mass fractions of Cd, Se, and Te are all 0.001~0.002%; and the balance is Cu.

7. The cathode copper spectral analysis standard substance according to claim 1, characterized in that: The elements in the standard substance are as follows: Pb: 0.00009±0.00003%; Fe: 0.00020±0.00003%; Bi: 0.00008±0.00002%; Sb: 0.00007±0.00003%; As: 0.00013±0.00003%; Sn: 0.00007±0.00002%; Ni: 0.00012±0.00002%; Zn: 0.00006±0.00002%; P：0.00016±0.00003%； S：0.00052±0.00007%； Ag: 0.00071±0.00006%; Si: 0.00016±0.00003%; Mn: 0.00005±0.00002%; Cd: 0.00006±0.00002%; Co: 0.00009±0.00002%; Cr: 0.00007±0.00002%; Se: 0.00007±0.00002%; Te: 0.00008±0.00003%; the balance is Cu; or, Pb: 0.00020±0.00004%; Fe: 0.00038±0.00004%; Bi: 0.00018±0.00002%; Sb: 0.00025±0.00003%; As: 0.00033±0.00004%; Sn: 0.00026±0.00003%; Ni: 0.00034±0.00004%; Zn: 0.00030±0.00003%; P：0.00030±0.00003%； S：0.00075±0.00009%； Ag: 0.0012±0.0002%; Si: 0.00056±0.00005%; Mn: 0.00027±0.00002%; Cd: 0.00021±0.00002%; Co: 0.00031±0.00002%; Cr：0.00034±0.00004%； Se: 0.00012±0.00002%; Te: 0.00013±0.00004%; the balance is Cu; or, Pb: 0.00041±0.00004%; Fe: 0.00058±0.00004%; Bi: 0.00038±0.00005%; Sb: 0.00053±0.00004%; As: 0.00055±0.00005%; Sn: 0.00047±0.00004%; Ni: 0.00061±0.00005%; Zn: 0.00050±0.00003%; P：0.00044±0.00005%； S：0.00090±0.00011%； Ag: 0.0020±0.0002%; Si: 0.00069±0.00008%; Mn: 0.00058±0.00003%; Cd: 0.00014±0.00001%; Co: 0.00058±0.00003%; Cr：0.00055±0.00005%； Se: 0.00033±0.00005%; Te: 0.00033±0.00003%; the balance is Cu; or, Pb: 0.0013 ± 0.0001%; Fe: 0.0011±0.0001%; Bi: 0.0010±0.0001%; ​​Sb: 0.00096±0.00006%; As: 0.0011±0.0001%; Sn: 0.0010±0.0001%; Ni: 0.0010±0.0001%; Zn: 0.00092±0.00008%; P：0.00089±0.00009%； S：0.0016±0.0002%； Ag: 0.0025±0.0002%; Si: 0.00035±0.00008%; Mn: 0.0014±0.0001%; Cd: 0.00027±0.00002%; Co: 0.0015±0.0001%; Cr: 0.0012±0.0002%; Se: 0.00058±0.00003%; Te: 0.00054±0.00006%; the balance is Cu; or, Pb: 0.0025 ± 0.0002%; Fe: 0.0029±0.0002%; Bi: 0.0029±0.0002%; Sb: 0.0030±0.0001%; As: 0.0032±0.0002%; Sn: 0.0029±0.0002%; Ni: 0.0030±0.0002%; Zn: 0.0027±0.0002%; P：0.0030±0.0002%； S：0.0039±0.0003%； Ag: 0.0038±0.0002%; Si: 0.0028±0.0002%; Mn: 0.0028±0.0002%; Cd: 0.0012±0.0001%; Co: 0.0030±0.0002%; Cr: 0.0028±0.0002%; Se: 0.0012±0.0001%; Te: 0.0013±0.0002%; the balance is Cu.

8. The method for preparing a standard substance for cathode copper spectral analysis according to any one of claims 1 to 7, characterized in that: The following steps are involved: S1. According to the elemental composition of the standard substance, calculate and prepare various raw materials: including grade A copper and the single substances or compounds of the remaining elements; S2. Mix and melt various raw materials using a vacuum medium frequency induction furnace, wherein the melting temperature is 1200-1280°C; S3, casting the alloy liquid obtained by smelting in step S2 into an ingot, controlling the casting temperature at 1200-1250°C and the casting speed at 90-110 mm / min; performing a preliminary inspection on the ingot after obtaining the ingot; S4, processing the ingots that have passed the initial inspection in step S3 into target specifications, obtaining standard materials for cathode copper spectral analysis, and performing uniformity inspection, stability investigation, fixed value analysis and uncertainty assessment respectively, and then sawing, polishing and marking to obtain finished products.

9. The preparation method according to claim 8, characterized in that: In step S1, the raw materials are grade A copper, iron sheet, pure nickel, pure cobalt, pure tin, pure antimony, pure bismuth, electrolytic manganese sheet, pure silicon, pure chromium, pure lead, pure sulfur, pure silver, pure selenium, pure tellurium, copper-cadmium alloy, copper-phosphorus alloy, copper-arsenic alloy and copper-zinc alloy.

10. The preparation method according to claim 9, characterized in that: In step S2, firstly, grade A copper, iron sheet, pure nickel and pure cobalt are mixed, and after they are completely melted, the remaining raw materials are added.

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