Method for preparing GH4169 trace element ultramicro-region uniform standard substance by adopting solution adding method

Abstract

The invention relates to the technical field of analysis and detection, in particular to a method for preparing a GH4169 trace element ultramicro-region uniform standard substance by adopting a solution adding method. Comprising the following steps: adding a trace element solution with a target component ratio into GH4169 alloy matrix powder preheated at the temperature of more than 100 DEG C to obtain high-temperature alloy trace element micro-area uniform standard substance powder containing trace elements. The standard alloy substance containing the trace elements is obtained by adding the trace element solution with the target component proportion into the GH4169 alloy matrix powder preheated at the temperature higher than 100 DEG C, the dispersion uniformity of the trace elements is better, and the microscale (10 microns) uniformity can be achieved; the defects that in the prior art, low-melting-point trace elements are poor in dispersion uniformity and cannot reach the uniformity of the microscale (10 microns) are overcome, and the problems that in the prior art, the low-melting-point trace elements are poor in dispersion uniformity and cannot reach the uniformity of the microscale (10 microns) are solved.

Description

Technical Field

[0001] The present invention relates to the technical field of analysis and detection, and in particular to a method for preparing a GH4169 trace element ultrafine region uniform standard substance by adopting a solution addition method. Background Art

[0002] The wrought superalloy GH4169 contains trace elements such as P, B, As, Se, Sn, Pb, and Sn. The content of these harmful elements and inclusions severely impacts the alloy's performance, and its purity significantly influences its reliability. Trace element detection in wrought superalloy GH4169 typically requires a GH4169 superalloy reference material, which contains known trace elements. Therefore, the preparation of GH4169 superalloy reference material with accurately known trace elements is crucial for trace element detection in wrought superalloy GH4169.

[0003] The existing preparation methods for trace element reference materials of GH4169 high-temperature alloys mainly rely on traditional casting methods, with a selective homogenization heat treatment system used to eliminate component segregation. This method has the following drawbacks: First, trace elements are extremely difficult to add, especially low-melting-point trace elements such as As, Se, Sn, Pb, and Sn. Adding them uniformly is also extremely difficult, and it is impossible to achieve uniformity at the microscale (10 μm). Due to this poor uniformity, existing reference material preparation technologies cannot meet the precision requirements of micro-area composition analysis equipment such as secondary ion mass spectrometry, electron probe, and micro-area X-ray fluorescence.

[0004] On the other hand, high-temperature alloy ingots will produce serious composition segregation during the solidification process; therefore, the micro-area distribution (about 10μm and above) of the key trace elements P and B in GH4169G and the content of trace elements such as As, Se, Sn, Pb, Sn that affect the purification of the alloy have increasingly higher requirements. The existing technology can only achieve micro-area uniformity within a range of 20μm in horizontal and vertical dimensions. Summary of the Invention

[0005] In view of the above analysis, the present invention aims to provide a method for preparing GH4169 trace element ultrafine area uniform standard material by solution addition method, which solves at least one of the problems existing in the prior art, such as poor dispersion uniformity of low-melting point trace elements, inability to achieve uniformity at the microscopic scale (10 μm), and inability to meet the requirements of micro-area component analysis equipment such as secondary ion mass spectrometry, electron probe, and micro-area X-ray fluorescence.

[0006] The purpose of the present invention is mainly achieved through the following technical solutions:

[0007] A method for preparing GH4169 trace element ultrafine region uniform standard substance by solution addition method comprises:

[0008] A trace element solution with a target composition ratio is added to a GH4169 alloy matrix powder preheated at a temperature greater than 100° C. to obtain a high-temperature alloy trace element micro-area uniform standard material powder containing the trace elements.

[0009] Preferably, the heating temperature of the GH4169 alloy matrix powder is 110°C to 150°C.

[0010] Preferably, the mass volume ratio of the GH4169 alloy matrix powder to the trace element solution is 10-30:1-10 g / ml.

[0011] Preferably, the high-temperature alloy trace element micro-area uniform standard material powder containing trace elements needs to be ball-milled to improve the uniformity of the trace elements.

[0012] Preferably, the ball milling mixing is performed in a sealed environment under an inert gas at 200° C. to 300° C.

[0013] Preferably, the mixing speed of the ball milling is 350 r / min to 500 r / min, and the mixing time is 1 h to 2 h.

[0014] Preferably, the method for preparing GH4169 trace element ultrafine region uniform standard substance by solution addition method comprises:

[0015] S1: Select GH4169 superalloy powder with target particle size as the matrix powder;

[0016] S2: adding a trace element solution with a target composition ratio to a GH4169 alloy matrix powder preheated at greater than 100° C. to obtain a high-temperature alloy trace element micro-area uniform standard material powder preform containing the trace elements;

[0017] S3: vacuum degassing the standard substance powder preform;

[0018] S4: hot isostatic pressing the standard substance powder preform that has undergone vacuum degassing;

[0019] S5: Isothermal forging is performed on the standard material powder preform that has completed the hot isostatic pressing treatment to cause plastic deformation, thereby obtaining a finished forging of the GH4169 high-temperature alloy trace element micro-area uniform standard material.

[0020] Preferably, the hot isostatic pressing temperature in step S4 is 1100°C to 1180°C.

[0021] Preferably, the particle size of the matrix powder in step S1 ranges from 15 μm to 25 μm.

[0022] A GH4169 high-temperature alloy trace element micro-area uniform standard material is prepared by the above-mentioned preparation method of GH4169 trace element ultra-micro-area uniform standard material using solution addition method, which can achieve microscopic scale (10μm) uniformity with a uniformity distribution range of 0.73% to 1.82%.

[0023] Compared with the prior art, the present invention can achieve at least one of the following beneficial effects:

[0024] (1) The present invention obtains a standard alloy material containing trace elements by adding a trace element solution with a target composition ratio to a GH4169 alloy matrix powder preheated at more than 100°C. The trace elements have better dispersion uniformity and can achieve uniformity at a microscale (10 μm), overcoming the defects of the prior art of poor dispersion uniformity of low-melting-point trace elements and inability to achieve uniformity at a microscale (10 μm). The RSD distribution range is 0.73% to 1.82%, which can meet the requirements of micro-area component analysis equipment such as secondary ion mass spectrometry, electron probe, and micro-area X-ray fluorescence.

[0025] (2) The present invention greatly shortens the ball milling time by ball milling and mixing in a sealed environment of inert gas at 200°C to 300°C. The ball milling time is shortened to 1 / 8 to 1 / 10 of the original time, thereby improving the ball milling efficiency while ensuring the stability of the structure such as the trace element crystal particle size.

[0026] (3) The present invention obtains a standard alloy material containing the trace element Cd by adding a trace element solution with a target composition ratio to a GH4169 alloy matrix powder preheated at a temperature greater than 100°C. In the standard alloy material, Cd is in the form of a stable high-valent Cd oxide or hydroxide (for example, cadmium oxide, a brownish-red to brownish-black amorphous powder or cubic crystal fine crystals with a melting point of 900°C and a boiling point of 1385°C). Therefore, Cd loss can be greatly reduced during subsequent heat treatment, thereby improving the uniformity of Cd in the GH4169 alloy standard material.

[0027] (4) The present invention controls the hot isostatic pressing temperature so that the trace substances react with the matrix substances in the matrix powder to generate complex new compounds, which can avoid the segregation at the microscale (10μm) in the subsequent heat treatment molding process and ensure the uniformity of trace elements at the microscale (10μm).

[0028] (5) The present invention can achieve microscopic uniform deformation of the GH4169 high-temperature alloy trace element micro-area uniform standard material through isothermal forging, making the powder finer, the organizational structure more uniform, and the component distribution more uniform, which is beneficial to improving the uniformity of trace elements at the microscopic scale (10μm).

[0029] (6) The present invention can prepare a standard alloy material containing the trace element Cd by adding a trace element solution with a target composition ratio to a GH4169 alloy matrix powder preheated at more than 100°C, ball milling and mixing in a sealed environment under an inert gas at 200°C to 300°C, controlling the hot isostatic pressing temperature and isothermal forging, and the trace element Cd in the standard alloy material can be uniform at a microscopic scale (10μm).

[0030] Other features and advantages of the present invention will be described in the following description, and some advantages may become apparent from the description or be understood through practice of the present invention. The purposes and other advantages of the present invention may be realized and obtained through the embodiments of the description and the contents particularly pointed out in the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 This is a metallographic image of the GH4169 trace element ultrafine region uniform standard material prepared in Example 1 of the present invention;

[0032] Figure 2 This is the metallographic image of the GH4169 trace element ultrafine region uniform standard material prepared in Comparative Example 1 of the present invention. DETAILED DESCRIPTION

[0033] The preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings, wherein the accompanying drawings constitute a part of the present invention and are used together with the embodiments of the present invention to illustrate the principles of the present invention, but are not intended to limit the present invention.

[0034] The applicant's research found that trace elements are extremely difficult to add, especially low-melting-point trace elements such as As, Se, Sn, Pb, and Sn. They are also extremely difficult to add evenly, and it is impossible to achieve uniformity at the microscale (10μm). Due to poor uniformity, existing reference material preparation technology cannot meet the accuracy requirements of micro-area composition analysis equipment such as secondary ion mass spectrometry, electron probe, and micro-area X-ray fluorescence.

[0035] In addition, high-temperature alloy ingots will produce serious composition segregation during the solidification process; therefore, the micro-area distribution (about 10μm and above) of the key trace elements P and B in GH4169G and the content of trace elements such as As, Se, Sn, Pb, Sn that affect the purification of the alloy have increasingly higher requirements for micro-area analysis size. The existing technology can only achieve micro-area uniformity within a range of 20μm in horizontal and vertical dimensions.

[0036] In one aspect, the present invention discloses a method for preparing GH4169 trace element ultrafine region uniform standard material by using a solution addition method, comprising:

[0037] A trace element solution with a target composition ratio is added to a GH4169 alloy matrix powder preheated at a temperature greater than 100° C. to obtain a high-temperature alloy trace element micro-area uniform standard material powder containing the trace elements.

[0038] During implementation, the trace element solution is added to the GH4169 alloy powder, the water in the solution evaporates instantly, and the trace elements in the solute state quickly crystallize to form solid particles uniformly dispersed in the GH4169 matrix alloy powder.

[0039] It should be noted that when the trace element solution is added to the GH4169 alloy powder, the water in the solution evaporates instantly, and various trace elements crystallize rapidly at the same time. Compared with the method of directly adding solid trace elements in the prior art, the problem of uneven dispersion of various trace elements in the solid phase is avoided; compared with the method of first preparing a high-concentration sample and then dispersing the high-concentration sample in the matrix alloy powder in the prior art, the method of the present invention does not require alloy preparation, avoids the volatilization loss of low-melting-point trace elements during the preparation of the high-concentration sample alloy, and thus has higher accuracy and quantitative precision.

[0040] Compared with the prior art, the present invention obtains a standard alloy material containing trace elements by adding a trace element solution with a target composition ratio to a GH4169 alloy matrix powder preheated at more than 100°C. The trace elements have better dispersion uniformity and can achieve uniformity at a microscale (10μm). This overcomes the defects of the prior art in that low-melting-point trace elements have poor dispersion uniformity and cannot achieve uniformity at a microscale (10μm), and can meet the requirements of micro-area component analysis equipment such as secondary ion mass spectrometry, electron probe, and micro-area X-ray fluorescence.

[0041] The applicant further discovered that compared with ordinary high-temperature alloys, the Cd content in GH4169 alloy is of particular concern. As a trace element, Cd has a boiling point of 765°C and is easily azeotropically volatilized when preparing high-temperature alloy standard materials. It was found that the Cd content in standard materials prepared by casting technology is greatly affected by processes such as processing temperature, which ultimately leads to poor distribution uniformity of Cd in various regions.

[0042] It should be noted that the present invention obtains a standard alloy material containing the trace element Cd by adding a trace element solution with a target composition ratio to a GH4169 alloy matrix powder preheated at more than 100°C. In the standard alloy material, Cd is in the form of a stable high-valent Cd oxide or hydroxide (for example, cadmium oxide, a brownish-red to brownish-black amorphous powder or cubic crystal fine crystals with a melting point of 900°C and a boiling point of 1385°C). Therefore, Cd loss can be greatly reduced during subsequent heat treatment, thereby improving the uniformity of Cd in the GH4169 alloy standard material.

[0043] Specifically, the heating temperature of the GH4169 alloy matrix powder is 110°C to 150°C, and can be 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C or 150°C.

[0044] It should be noted that the heating temperature of the alloy matrix powder affects the volatilization rate of the trace element solution, which in turn affects the grain size and dispersion uniformity of the trace element crystallization, and thus affects the final grain size and dispersion uniformity of the trace elements in the alloy powder; if the heating temperature is too high, the volatilization rate is fast, the grain size of the trace element crystallization is too large, and the dispersion uniformity decreases; if the heating temperature is too low, the solvent cannot be fully volatilized, and the trace elements cannot be fully crystallized.

[0045] Specifically, the mass volume ratio of the GH4169 alloy matrix powder to the trace element solution is 10-30:1-10 g / ml, which can be 1:1 g / ml, 2:1 g / ml, 3:1 g / ml, 4:1 g / ml, 5:1 g / ml, 6:1 g / ml, 7:1 g / ml, 8:1 g / ml, 9:1 g / ml, 10:1 g / ml, 11:1 g / ml, 12:1 g / ml, 13:1 g / ml ml, 14:1g / ml, 15:1g / ml, 16:1g / ml, 17:1g / ml, 18:1g / ml, 19:1g / ml, 20:1g / ml, 21:1g / ml, 22: 1g / ml, 23:1g / ml, 24:1g / ml, 25:1g / ml, 26:1g / ml, 27:1g / ml, 28:1g / ml, 19:1g / ml or 30:1g / ml.

[0046] It should be noted that the mass-to-volume ratio of GH4169 alloy matrix powder to trace element solution also affects the volatilization rate of the trace element solution, and thus affects the grain size and dispersion uniformity of the trace element crystallization, and thus affects the final grain size and dispersion uniformity of the trace elements in the alloy powder; if the volume ratio is too large, the volatilization rate is fast, the grain size of the trace element crystallization is too large, and the dispersion uniformity decreases; if the volume ratio is too small, the solvent cannot fully volatilize and the trace elements cannot fully crystallize.

[0047] Preferably, the high-temperature alloy trace element micro-area uniform standard material powder containing trace elements needs to be further ball-milled to improve the uniformity of the trace elements.

[0048] Specifically, the ball milling mixing is performed at room temperature, with a mixing speed of 150 r / min to 300 r / min and a mixing time of 15 h to 30 h.

[0049] Specifically, the mixing speed is 150 r / min, 160 r / min, 170 r / min, 180 r / min, 190 r / min, 200 r / min, 210 r / min, 220 r / min, 230 r / min, 240 r / min, 250 r / min, 260 r / min, 270 r / min, 280 r / min, 290 r / min or 300 r / min.

[0050] Specifically, the mixing time is 15 h, 16 h, 17 h, 18 h, 19 h, 20 h, 21 h, 22 h, 23 h, 24 h, 25 h, 26 h, 27 h, 28 h, 29 h or 30 h.

[0051] It should be noted that the mixing speed of ball milling is 150r / min~250r / min, which can provide sufficient shear force without changing the structure such as the trace element crystal particle size, so that the trace element crystals are more fully dispersed in the alloy powder; if the mixing time is too short, insufficient mixing time will lead to insufficient dispersion time of the system, making it difficult to achieve the requirements of sufficient mass transfer and dispersion; if the mixing time is too long, the proportion of trace element crystal cross-linking and agglomeration will be greatly increased, which is not conducive to maintaining the original particle size and other structures.

[0052] Preferably, the ball milling mixing is carried out in a sealed environment under an inert gas at 200° C. to 300° C., with a mixing speed of 350 r / min to 500 r / min and a mixing time of 1 h to 2 h.

[0053] Specifically, the ball milling temperature may be 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, or 300°C.

[0054] The mixing speed is 350r / min, 360r / min, 370r / min, 380r / min, 390r / min, 400r / min, 410r / min, 420r / min, 430r / min, 440r / min, 450r / min, 460r / min, 470r / min, 480r / min, 490r / min or 500r / min.

[0055] The mixing time is 1 h, 1.1 h, 1.2 h, 1.3 h, 1.4 h, 1.5 h, 1.6 h, 1.7 h, 1.8 h, 1.9 h or 2 h.

[0056] It should be noted that the mass transfer and dispersion speeds are greatly improved at high temperatures, and the mixing time requirement is greatly shortened; at the same time, the possibility of trace element crystallization, cross-linking and agglomeration is greatly increased, and a higher mixing speed helps to destroy the trace element crystallization, cross-linking and agglomeration.

[0057] Compared with the prior art, the present invention greatly shortens the ball milling time by ball milling and mixing in a sealed environment of inert gas at 200°C to 300°C. The ball milling time is shortened to 1 / 8 to 1 / 10 of the original time, thereby improving the ball milling efficiency while ensuring the stability of the structure such as the trace element crystal particle size.

[0058] Specifically, the preparation method of GH4169 trace element ultrafine region uniform standard material using the solution addition method includes:

[0059] S1: Select GH4169 superalloy powder with target particle size as the matrix powder;

[0060] S2: adding a trace element solution with a target composition ratio to a GH4169 alloy matrix powder preheated at greater than 100° C. to obtain a high-temperature alloy trace element micro-area uniform standard material powder preform containing the trace elements;

[0061] S3: vacuum degassing the standard substance powder preform;

[0062] S4: hot isostatic pressing the standard substance powder preform that has undergone vacuum degassing;

[0063] S5: Isothermal forging is performed on the standard material powder preform that has completed the hot isostatic pressing treatment to cause plastic deformation, thereby obtaining a finished forging of the GH4169 high-temperature alloy trace element micro-area uniform standard material.

[0064] Specifically, in step S1 , the particle size of the matrix powder ranges from 15 μm to 25 μm.

[0065] The particle size of the matrix powder is 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm or 25 μm.

[0066] It should be noted that a powder particle size that is too large will lead to a reduction in the contact area between particles, thereby affecting the mixing uniformity of the powder; while a powder particle size that is too small will increase the specific surface area, making it difficult to homogenize the alloy in subsequent processes; in order to ensure uniformity at the microscopic scale (10μm), the present invention needs to limit the matrix powder particle size range to 15μm to 25μm.

[0067] Specifically, the trace elements are one or more of B, P, S, As, Se, Sn, Sb, La, Ce and Y.

[0068] Specifically, the trace element solution can be prepared by dissolving a standard trace element substance, a standard trace element salt, or a standard trace element oxide to prepare a solution, or by purchasing a standard solution of an existing substance to further prepare a target trace element solution.

[0069] Preferably, the trace element solution is a standard solution containing multiple trace elements.

[0070] During implementation, a single standard solution of each trace element can be prepared by dissolving a standard single substance of the trace element, a standard salt of the trace element or a standard oxide of the trace element as a raw material, and then the single standard solutions are mixed to prepare a standard solution containing multiple trace elements;

[0071] Alternatively, a standard solution containing multiple trace elements can be prepared by mixing the purchased single standard solutions of the trace elements.

[0072] Alternatively, a standard solution containing multiple trace elements can be prepared by mixing a purchased single standard solution of the trace element with a single standard solution of other trace elements prepared from a standard substance.

[0073] It should be noted that the content of trace elements in the standard substance can be adjusted as needed by adjusting the concentration of trace elements in the trace element solution.

[0074] For example, to facilitate calculation, a standard solution can be prepared by the above method in which the content of each trace element meets the following requirements: B, 0.0001%; ​​P, 0.0001%; ​​As, 0.0001%; ​​Se, 0.0001%; ​​Sn, 0.0001%; ​​Sb, 0.0001%; ​​La, 0.0001%; ​​Ce, 0.0001%; ​​Y, 0.0001%.

[0075] Specifically, the vacuum degassing temperature is 300°C, 320°C, 340°C, 350°C, 360°C, 370°C, 380°C, 390°C, 400°C, 410°C, 420°C, 430°C, 440°C, 450°C, 480°C, 490°C, 500°C, 510°C, 520°C, 530°C, 540°C, 550°C, 580°C, 590°C or 600°C.

[0076] Specifically, the vacuum degassing temperature in step S3 is 300°C to 600°C, and the vacuum degassing pressure is 10 -3 Pa~10 - 1 Pa.

[0077] It should be noted that appropriate degassing temperature and pressure ensure the diffusion of trace elements in the matrix powder. Excessively high temperature and pressure can cause the trace elements to decompose and be lost. Excessively low temperature and pressure during this stage can lead to insufficient melting of the alloy, affecting the fluidity of the trace elements in the alloy and thus affecting homogenization.

[0078] Specifically, the hot isostatic pressing temperature in step S4 is 1100°C to 1180°C. Preferably, the hot isostatic pressing temperature is 1100°C to 1150°C.

[0079] Specifically, the hot isostatic pressing temperature in step S4 may be 1100°C, 1110°C, 1120°C, 1130°C, 1140°C, 1150°C, 1160°C, 1170°C or 1180°C.

[0080] It should be noted that the hot isostatic pressing process is not only a physical change but also a complex chemical change. Trace substances react with the matrix substances in the matrix powder to form complex new compounds. Controlling the hot isostatic pressing temperature can avoid segregation at the microscale (10μm) in the subsequent heat treatment molding process and ensure the uniformity of trace elements at the microscale (10μm).

[0081] Compared with the existing technology, the present invention controls the hot isostatic pressing temperature so that trace substances react with matrix substances in the matrix powder to form complex new compounds, which can avoid segregation at the microscale (10μm) in the subsequent heat treatment molding process and ensure the uniformity of trace elements at the microscale (10μm).

[0082] Specifically, in step S4, the hot isostatic pressing pressure is 120 MPa to 180 MPa, and the hot isostatic pressing time is 2 h to 6 h.

[0083] It should be noted that appropriate degassing temperature and pressure ensure the diffusion of trace elements in the matrix powder. Excessively high temperature and pressure can cause the trace elements to decompose and be lost. Excessively low temperature and pressure during this stage can lead to insufficient melting of the alloy, affecting the fluidity of the trace elements in the alloy and thus affecting homogenization.

[0084] Specifically, the isothermal forging temperature in step S5 is 1000℃~1300℃, which can be 1000℃, 1020℃, 1050℃, 1060℃, 1080℃, 1100℃, 1120℃, 1150℃, 1160℃, 1180℃, 1200℃, 1220℃, 1250℃, 1260℃, 1280℃ or 1300℃.

[0085] Specifically, the average isothermal forging rate in step S5 is 0.03 mm / s to 0.06 mm / s, and can be 0.03 mm / s, 0.04 mm / s, 0.04 mm / s, 0.05 mm / s or 0.06 mm / s.

[0086] Specifically, the isothermal forging deformation in step S5 is 65% to 80%, and can be 65%, 68%, 70%, 72%, 75%, 78% or 80%.

[0087] It should be noted that isothermal parameters ensure that trace elements diffuse further into the matrix without loss under suitable stable conditions. This temperature and extrusion rate are appropriate for the alloy type to ensure that the alloy composition is homogenized within the plastic range. Excessive deformation will cause the alloy to crack, while too little deformation will not fully destroy the original grain boundaries, affecting the homogenization of trace elements.

[0088] Compared with the prior art, the present invention can achieve microscopic uniform deformation of the GH4169 high-temperature alloy trace element micro-area uniform standard material through isothermal forging, making the powder finer, the organizational structure more uniform, and the component distribution more uniform, which is beneficial to improving the uniformity of trace elements at the microscopic scale (10μm).

[0089] On the other hand, the present invention also discloses a GH4169 high-temperature alloy trace element micro-area uniform standard material, which is prepared by the above preparation method and can achieve microscopic scale (10μm) uniformity with a uniformity distribution range of 0.73% to 1.82%.

[0090] Specifically, the powder particle size of the GH4169 high-temperature alloy trace element micro-area uniform standard material is ≤5 μm.

[0091] The standard substance prepared by the present invention can be used for trace element detection of GH4169 high-temperature alloy.

[0092] In order to further illustrate the technical solution of the present invention, the following examples and comparative examples are further provided:

[0093] Example 1

[0094] On the one hand, this embodiment discloses a method for preparing GH4169 trace element ultrafine region uniform standard material using a solution addition method, comprising the following steps:

[0095] S1: Selecting a GH4169 superalloy powder having a target particle size as a base powder; the mass percentages of the constituent elements in the GH4169 superalloy are as follows: C: 0.060 wt%, Cr: 16.00 wt%, Co: 13.10 wt%, Al: 2.10 wt%, Nb: 0.70 wt%, W: 4.00 wt%, Mo: 4.00 wt%, Ti: 3.70 wt%, Zr: 0.040 wt%, and the balance is Ni. The GH4169 superalloy base powder is sieved to obtain a particle size of 15 μm to 20 μm.

[0096] S2: Adding a trace element solution with a target composition ratio to a GH4169 alloy matrix powder preheated at greater than 100°C to obtain a high-temperature alloy trace element micro-area uniform standard material powder preform containing trace elements; the trace elements B, P, As, Se, Sn, Sb, La, Ce and Y are prepared by mixing commercially available standard solutions with a purity greater than 99.99%, and the concentrations of the standard solutions of each element are B: 0.0001%, P: 0.0001%, As: 0.0001%, Se: 0.0001%; ​​Sn: 0.0001%; ​​Sb: 0.0001%; ​​La: 0.0001%, Ce: 0.0001%, and Y: 0.0001%.

[0097] The heating temperature of GH4169 alloy matrix powder was 150°C, and the mass volume ratio of matrix powder to trace element solution was 10:1 g / ml;

[0098] The high-temperature alloy trace element micro-area uniform standard material powder containing trace elements needs to be further ball-milled to improve the uniformity of the trace elements; the ball-milling mixing is a sealed environment mixing under an argon atmosphere at 200°C, with a mixing speed of 350r / min and a mixing time of 2h.

[0099] S3: The standard substance powder preform is heated at 300°C and degassing pressure of 10 -3 Pa vacuum degassing treatment.

[0100] S4: The standard substance powder preform that has completed the vacuum degassing treatment is subjected to hot isostatic pressing; the heating temperature is 1150° C., the pressure is 120 MPa, and the hot isostatic pressing time is 5 hours.

[0101] S5: Isothermal forging is performed on the standard material powder preform that has completed the hot isostatic pressing treatment to cause plastic deformation, thereby obtaining a forged product of the GH4169 high-temperature alloy trace element micro-area uniform standard material;

[0102] The isothermal forging temperature is 1000°C, the average isothermal forging rate is 0.03mm / s to 0.06mm / s, the isothermal forging deformation is 65% to 80%, and the shape of the forging of the powder high-temperature alloy trace element micro-area uniform standard material is a rectangular parallelepiped with a length of 10mm, a width of 10mm, and a height of 1mm.

[0103] On the other hand, this example also discloses a GH4169 trace element ultrafine region uniform standard material, which was prepared by the above method. A total of 8 parallel samples were prepared, and the macroscopic composition of some key elements added, P, As, Se, Ag, Cd, and Te, was compared and analyzed by inductively coupled isotropic mass spectrometry, as shown in Table 1:

[0104] Table 1 Comparative analysis of uniformity of key elements added to GH4169 in Example 1 (μg / g)

[0105]

[0106] From the measured data in Table 1, it can be seen that the RSD distribution range of the samples prepared in Example 1 is 0.73% to 1.78%, and the macroscopic uniformity is relatively high.

[0107] Figure 1 This is a scanning electron microscope photo of the uniform standard material of trace elements in the micro area of ​​GH4169 high temperature alloy in this embodiment. Figure 1 The black chain-like rings shown represent the primary particle boundaries formed by the alloy powder particles. The distribution of the primary particle boundaries is discontinuous, and the powder particle size has been crushed to 3μm to 5μm. This indicates that the precipitate phase in the standard material prepared in this example is uniformly distributed, and the formation of larger precipitates is reduced, ensuring the uniformity of trace elements at the microscale (10μm). The uncertainty of the micro-area uniform trace element standard material prepared in this example for impurities above 0.1μg / g is less than 30%, laying the foundation for the quantitative analysis of trace element micro-area composition in GH4169 superalloy. It can also be applied to a series of analytical techniques for micro-area control elements, establishing a benchmark for in-situ micro-area control analysis.

[0108] Example 2

[0109] In one aspect, this embodiment discloses a method for preparing a GH96 trace element ultrafine region uniform standard substance using a solution addition method, comprising the following steps:

[0110] S1: GH4169 superalloy powder with a target particle size is selected as a base powder. The mass percentages of the constituent elements in the GH4169 superalloy are as follows: C: 0.060 wt%, Cr: 16.00 wt%, Co: 13.10 wt%, Al: 2.10 wt%, Nb: 0.70 wt%, W: 4.00 wt%, Mo: 4.00 wt%, Ti: 3.70 wt%, Zr: 0.040 wt%, and the balance is Ni. The GH4169 superalloy base powder is sieved to obtain a particle size of 20 μm to 25 μm.

[0111] S2: Adding a trace element solution with a target composition ratio to a GH4169 alloy matrix powder preheated at greater than 100°C to obtain a high-temperature alloy trace element micro-area uniform standard material powder preform containing trace elements; the trace elements B, P, As, Se, Sn, Sb, La, Ce and Y are prepared by mixing commercially available standard solutions with a purity greater than 99.99%, and the concentrations of the standard solutions of each element are B: 0.0005%, P: 0.0005%, As: 0.0005%, Se: 0.0005%; Sn: 0.0005%; Sb: 0.00015%; La: 0.0005%, Ce: 0.0005%, Y: 0.0005%.

[0112] The heating temperature of GH4169 alloy matrix powder was 150°C, and the mass volume ratio of matrix powder to trace element solution was 5:1 g / ml;

[0113] The high-temperature alloy trace element micro-area uniform standard material powder containing trace elements needs to be further ball-milled to improve the uniformity of the trace elements; the ball-milling mixing is a sealed environment mixing under an argon atmosphere at 300°C, with a mixing speed of 450r / min and a mixing time of 1h.

[0114] S3: The standard substance powder preform is heated at 400°C and a degassing pressure of 10 -2 Pa vacuum degassing treatment.

[0115] S4: The standard substance powder preform that has completed the vacuum degassing treatment is subjected to hot isostatic pressing; the heating temperature is 1100° C., the pressure is 130 MPa, and the hot isostatic pressing time is 4 hours.

[0116] S5: Isothermal forging is performed on the standard material powder preform that has completed the hot isostatic pressing treatment to cause plastic deformation, thereby obtaining a forged product of the GH4169 high-temperature alloy trace element micro-area uniform standard material;

[0117] The isothermal forging temperature was 1000°C, the average isothermal forging rate was 0.03 mm / s, and the isothermal forging deformation was 65%. The forging of the powder superalloy trace element micro-area uniform standard material was a rectangular parallelepiped with a length of 10 mm, a width of 10 mm, and a height of 1 mm. The original shape of the forging was cylindrical with a diameter of 15 cm and a height of 18 cm. The isothermal forging deformation was measured in the height direction of the forging, meaning that after deformation, the height of the forging was 5.76 cm.

[0118] A total of 8 parallel samples were prepared according to the above method, and the macroscopic components of some key elements P, As, Se, Ag, Cd, and Te added were compared and analyzed by inductively coupled isotropic mass spectrometry. The RSD distribution range of the samples was determined to be 0.75% to 1.82% according to the same method as Example 1, and the macroscopic uniformity was high.

[0119] Figure 2 This is a scanning electron microscope photo of the uniform standard material of trace elements in the micro area of ​​GH4169 high temperature alloy in this embodiment. Figure 2 The black chain-like rings shown represent the primary particle boundaries formed by the alloy powder particles. The distribution of the primary particle boundaries is discontinuous, and the powder particle size has been crushed to 3μm to 5μm. This indicates that the precipitate phase in the standard material prepared in this example is uniformly distributed, and the formation of larger precipitates is reduced, ensuring the uniformity of trace elements at the microscale (10μm). The uncertainty of the micro-area uniform trace element standard material prepared in this example for impurities above 0.1μg / g is less than 30%, laying the foundation for the quantitative analysis of trace element micro-area composition in GH4169 superalloy. It can also be applied to a series of analytical techniques for micro-area control elements, establishing a benchmark for in-situ micro-area control analysis.

[0120] Example 3

[0121] This embodiment discloses a method for preparing GH4169 trace element ultrafine region uniform standard material by solution addition method. Compared with Example 1, the difference is that the ball milling mixing is carried out at room temperature, the mixing speed is 150 r / min, and the mixing time is 30 h. The rest is the same as Example 1.

[0122] A total of 8 parallel samples were prepared according to the above method, and the macroscopic components of some key elements P, As, Se, Ag, Cd, and Te added were compared and analyzed by inductively coupled isotropic mass spectrometry. The RSD distribution range of the samples was determined to be 0.78% to 1.77% according to the same method as in Example 1. The macroscopic uniformity was high and there was no significant difference from that in Example 1, indicating that the rapid ball milling at high temperature in Example 1 achieved almost the same effect as the slow ball milling at room temperature in Example 3.

[0123] Example 4

[0124] This example discloses a method for preparing a GH4169 trace element ultrafine region uniform standard material using a solution addition method. This method differs from Example 1 in that the mixing speed is 200 r / min. Eight parallel samples were prepared using the same method as Example 1. The macroscopic composition of the added key elements, P, As, Se, Ag, Cd, and Te, was compared and analyzed using inductively coupled isotropic mass spectrometry. The RSD distribution range of the samples was determined to be 2.62% to 5.05%, a significantly larger range than in Example 1.

[0125] Example 5

[0126] This example discloses a method for preparing a GH4169 trace element ultrafine region uniform standard material using a solution addition method. This method differs from Example 1 in that the ball milling mixing time is 3 hours. Eight parallel samples were prepared using the same method as Example 1. The macroscopic composition of the added key elements P, As, Se, Ag, Cd, and Te was compared and analyzed using inductively coupled isotropic mass spectrometry. The RSD distribution range of the samples was determined to be 2.86% to 6.68%, a significantly larger range than that of Example 1.

[0127] Example 6

[0128] This example discloses a method for preparing a GH4169 trace element ultrafine region uniform standard material using a solution addition method. This method differs from Example 1 in that the hot isostatic pressing temperature is 1180°C. Eight parallel samples were prepared using the same method as Example 1. The macroscopic composition of the added key elements P, As, Se, Ag, Cd, and Te was compared and analyzed using inductively coupled isotropic mass spectrometry. The RSD distribution range of the samples was determined to be 0.83% to 1.95%, a slightly larger range than in Example 1.

[0129] Comparative Example 1

[0130] In this comparative example, eight parallel samples were prepared using the method disclosed in Example 1 of the patent CN 116809915 A-Powder High-Trace Alloy Micro-area Uniform Standard Material of the same applicant. The macroscopic composition of some key elements added, P, As, Se, Ag, Cd, and Te, was compared and analyzed by inductively coupled isotropic mass spectrometry, as shown in Table 2:

[0131] Table 2 Comparative analysis of the uniformity of key elements added to GH4169 in the preparation of comparative example 1 (μg / g)

[0132]

[0133] The RSD distribution range of the samples was determined to be 7.61% to 50.01% using the same method as in Example 1, and the macroscopic uniformity was far inferior to that of Examples 1 and 2.

[0134] It should be noted that the trace elements in the powder high-temperature alloy trace element micro-area uniform standard material (FGH96 powder high-temperature alloy) originally recorded in CN 116809915 A do not contain Cd. When the method is used to prepare the trace element Cd-containing standard material GH4169 alloy of the present invention, the deviation of the trace element Cd is large.

[0135] Compared with the prior art, the present invention can prepare a standard alloy material containing the trace element Cd by adding a trace element solution with a target composition ratio to a GH4169 alloy matrix powder preheated at more than 100°C, ball milling the powder in a sealed environment under an inert gas at 200°C to 300°C, controlling the hot isostatic pressing temperature and isothermal forging. The trace element Cd in the standard alloy material can be uniformly distributed at a microscopic scale (10μm).

[0136] Comparative Example 2

[0137] This comparative example discloses a method for preparing a GH4169 trace element ultrafine region uniform standard material using a solution addition method. This method differs from Example 1 in that the hot isostatic pressing temperature is 1200°C. Eight parallel samples were prepared using the same method as Example 1. The macroscopic composition of the added key elements P, As, Se, Ag, Cd, and Te was compared and analyzed using inductively coupled isotropic mass spectrometry. The RSD distribution range of the samples was determined to be 7.45% to 16.68%, significantly larger than that of Example 1.

[0138] in conclusion:

[0139] By comparing Example 1 and Comparative Example 1, it can be seen that P, As, Se, Ag, Cd, and Te in the GH4169 trace element ultrafine region uniform standard material prepared by the present invention can obtain good dispersion uniformity, can avoid the occurrence of segregation at the microscale (10 μm) in the subsequent heat treatment forming process, and ensure the uniformity of trace elements at the microscale (10 μm), and the RSD distribution range is 0.73% to 1.82%.

[0140] By comparing Example 1, Example 6 and Comparative Example 2, it can be seen that the optimal range of hot isostatic pressing temperature is 1100°C to 1180°C.

[0141] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by any technician familiar with this technical field within the technical scope disclosed by the present invention should be covered by the scope of protection of the present invention.

Claims

1. A method for preparing GH4169 trace element ultrafine region uniform standard material by solution addition method, characterized in that: include: A trace element solution with a target composition ratio is added to a GH4169 alloy matrix powder preheated at a temperature greater than 100° C. to obtain a high-temperature alloy trace element micro-area uniform standard material powder containing the trace elements.

2. The method for preparing GH4169 trace element ultrafine region uniform standard substance by solution addition method according to claim 1, characterized in that: The heating temperature of the GH4169 alloy matrix powder is 110°C to 150°C.

3. The method for preparing GH4169 trace element ultrafine region uniform standard substance by solution addition method according to claim 2, characterized in that: The mass volume ratio of the GH4169 alloy matrix powder to the trace element solution is 10-30:1-10 g / ml.

4. The method for preparing GH4169 trace element ultrafine region uniform standard substance by solution addition method according to claim 3, characterized in that: The high-temperature alloy trace element micro-area uniform standard material powder containing trace elements needs to be ball-milled to improve the uniformity of the trace elements.

5. The method for preparing GH4169 trace element ultrafine region uniform standard substance by solution addition method according to claim 4, characterized in that: The ball milling mixing is carried out at 200° C. to 300° C. in a sealed environment under inert gas.

6. The method for preparing GH4169 trace element ultrafine region uniform standard substance by solution addition method according to claim 5, characterized in that: The mixing speed of the ball milling is 350 r / min to 500 r / min, and the mixing time is 1 h to 2 h.

7. The method for preparing GH4169 trace element ultrafine region uniform standard substance by solution addition method according to claim 6, characterized in that: The method for preparing GH4169 trace element ultrafine region uniform standard material by solution addition method comprises: S1: Select GH4169 superalloy powder with target particle size as the matrix powder; S2: adding a trace element solution with a target composition ratio to a GH4169 alloy matrix powder preheated at greater than 100° C. to obtain a high-temperature alloy trace element micro-area uniform standard material powder preform containing the trace elements; S3: vacuum degassing the standard substance powder preform; S4: hot isostatic pressing the standard substance powder preform that has undergone vacuum degassing; S5: Isothermal forging is performed on the standard material powder preform that has completed the hot isostatic pressing treatment to cause plastic deformation, thereby obtaining a finished forging of the GH4169 high-temperature alloy trace element micro-area uniform standard material.

8. The method for preparing GH4169 trace element ultrafine region uniform standard substance by solution addition method according to claim 7, characterized in that: The particle size of the matrix powder in step S1 ranges from 15 μm to 25 μm.

9. The method for preparing GH4169 trace element ultrafine region uniform standard substance by solution addition method according to claim 8, characterized in that: The hot isostatic pressing temperature in step S4 is 1100°C to 1180°C.

10. A GH4169 high temperature alloy trace element micro-area uniform standard material, characterized in that: The preparation method of GH4169 trace element ultrafine region uniform standard substance using solution addition method according to any one of claims 1-9 can achieve microscopic scale (10 μm) uniformity with a uniformity distribution range of 0.73% to 1.82%.

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