NICKEL-BASED SUPERALLOY FOR 3D PRINTING AND POWDER PREPARATION METHOD THEREOF

Abstract

A nickel-based superalloy for three-dimension (3D) printing and a powder preparation method thereof are provided. The method of preparing the nickel-based superalloy and its powder includes: RE microalloying combined with vacuum melting, degassing, refining, atomization with reasonable parameters, and a sieving process. The new method significantly reduces the cracking sensitivity of the “non-weldable” PM nickel-based superalloys, and broadens the 3D printing process window. The as-printed part has no cracks, and good mechanical properties. In addition, the powder prepared by the new method has higher sphericity and better flowability, and less irregular powders. The yield of fine powders with a particle size of 15-53 μm and medium-sized powders with a particle size of 53-106 μm that are required for 3D printing is greatly improved, which meet the requirements for 3D printing of high-quality, low-cost nickel-based superalloy powder.

Claims

1. A nickel-based superalloy for three-dimension (3D) printing, comprising the following components in percentage by mass: Co: 14-23 wt %; Cr: 11-15 wt %; Al: 2-5 wt %; Ti: 3-6 wt %; Mo: 2.7-5 wt %; W: 0.5-3 wt %; Ta: 0.5-4 wt %; Nb: 0.25-3 wt %; Zr: 0.02-0.06 wt %; B: 0.01-0.05 wt %; C: 0.0015-0.1 wt %; RE: 0.05-0.18 wt %; and Ni: the balance; or another non-weldable nickel-based superalloy is used as a matrix, and 0.05-0.18 wt % of RE is added to the matrix, wherein the another non-weldable nickel-based superalloy is one selected from the group consisting of IN738LC, CM247LC, CMSX-4, René 142, and Hastelloy X; or one selected from the group consisting of nickel-based superalloys IN718 and IN625 is used as the matrix, and 0.05-0.18 wt % of RE is added to the matrix.

2. The nickel-based superalloy according to claim 1, comprising the following components in percentage by mass: Co: 20.6 wt %; Cr: 13 wt %; Al: 3.4 wt %; Ti: 3.9 wt %; Mo: 3.8 wt %; W: 2.1 wt %; Ta: 2.4 wt %; Nb: 0.9 wt %; Zr: 0.05 wt %; B: 0.03 wt %; C: 0.04 wt %; RE: 0.06-0.18 wt %; and Ni: the balance.

3. The nickel-based superalloy according to claim 1, wherein RE is at least one selected from the group consisting of Sc, Y, La, Ce, and Er.

4. The nickel-based superalloy according to claim 3, wherein RE is Sc, or RE is a mixture of Sc and at least one selected from the group consisting of Y, La, Ce, and Er.

5. A method for preparing powder of the nickel-based superalloy according to claim 1, comprising the following steps: step 1: vacuum melting: formulating raw materials according to designed components, putting the raw materials into a melting crucible of a powder atomization furnace, then vacuum melting the raw materials by induction heating under a vacuum degree of higher than 0.1 Pa; step 2: degassing: after the raw materials are melted and completely alloyed to obtain a molten master alloy melt, vacuum degassing the molten master alloy melt for 10 min-20 min; step 3: refining: introducing high-purity inert gas into the powder atomization furnace to 0.1-0.11 MPa, and holding the molten master alloy melt at a temperature range of 1600° C.-1650° C. for 10 min-15 min; step 4: atomization: flowing the molten master alloy melt down a draft tube at a flow rate of 3.5 kg/min-5 kg/min, atomizing the molten master alloy melt into fine droplets with 3 MPa-5 MPa high-pressure and the high-purity inert gas, cooling and solidifying the fine droplets to form spherical powders, and collecting the spherical powders using a tank; and step 5: sieving: sieving the spherical powders by airflow classification and ultrasonic vibration under an inert gas atmosphere after the spherical powders are fully cooled, to obtain spherical nickel-based superalloy powders with a particle size of 53-106 μm and a particle size of 15-53 μm, and then vacuum packaging the spherical nickel-based superalloy powders to obtain the powder of the nickel-based superalloy; wherein the high-purity inert gas is helium, argon, or a mixture gas of argon and helium, with a purity of 99.99 wt %, and an oxygen content less than 0.0001 wt %.

6. The method according to claim 5, wherein the raw materials contain Al-RE intermediate alloy.

7. The method according to claim 5, wherein a total yield of medium-sized powders with the particle size of 53-106 μm and fine powders with the particle size of 15-53 μm is 88.5%-91.5%.

8. The method according to claim 5, wherein the powder of the nickel-based superalloy for 3D printing has an oxygen content less than or equal to 0.0126 wt %, and a sulfur content less than or equal to 0.0056 wt %.

9. The method according to claim 8, wherein the powder of the nickel-based superalloy for 3D printing has an oxygen content less than or equal to 0.01 wt %, and a sulfur content less than or equal to 0.004 wt %.

10. The method according to claim 5, wherein the powder of the nickel-based superalloy for 3D printing has a flowability of 15-25 s/50 g, preferably 15.5-16 s/50 g, through an aperture of 2.5 mm.

11. The method according to claim 5, the nickel-based superalloy comprises the following components in percentage by mass: Co: 20.6 wt %; Cr: 13 wt %; Al: 3.4 wt %; Ti: 3.9 wt %; Mo: 3.8 wt %; W: 2.1 wt %; Ta: 2.4 wt %; Nb: 0.9 wt %; Zr: 0.05 wt %; B: 0.03 wt %; C: 0.04 wt %; RE: 0.06-0.18 wt %; and Ni: the balance.

12. The method according to claim 5, wherein RE is at least one selected from the group consisting of Sc, Y, La, Ce, and Er.

13. The method according to claim 12, wherein RE is Sc, or RE is a mixture of Sc and at least one selected from the group consisting of Y, La, Ce, and Er.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0058] FIG. 1 presents a scanning electron microscope (SEM) image showing the morphology of the René 104 alloy powder with minor RE elements in Example 1;

[0059] FIG. 2 presents a high-magnification SEM image showing the morphology of the René 104 alloy powder with minor RE elements in Example 1;

[0060] FIG. 3 presents a particle size distribution curve of the René 104 alloy powder with minor RE elements in Example 1;

[0061] FIG. 4 presents an SEM image showing the microstructure of the René 104 alloy part prepared in Example 4;

[0062] FIG. 5 presents an SEM image showing the morphology of the René 104 alloy powder without minor RE elements in Comparative Example 1;

[0063] FIG. 6 presents a high-magnification SEM image showing the morphology of the René 104 alloy powder without minor RE elements in Comparative Example 1; and

[0064] FIG. 7 presents a particle size distribution curve of the René 104 alloy powder without minor RE elements in Comparative Example 1.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0065] The present disclosure will be further described below with reference to the accompanying drawings and specific examples.

Example 1

[0066] The method provided in the present disclosure was applied to the René 104 nickel-based superalloy below. The RE element Sc was added in a mass fraction of 0.08%. The alloy includes in percentage by weight: 20.6Co-13Cr-3.4Al-3.9Ti-3.8Mo-2.1W-2.4Ta-0.9Nb-0.05Zr-0.03B-0.04C-0.08Sc-the balance of Ni. The steps of preparing nickel-based superalloy powder for 3D printing using the technical solutions provided in the present disclosure were as follows:

[0067] (1) vacuum melting: putting René 104 nickel-based superalloy raw materials with RE Sc element added in a mass fraction of 0.08% into the melting crucible of a powder atomization furnace, and then heating and melting the raw materials in a vacuum atmosphere of 0.05 Pa by using an intermediate frequency (IF) induction power supply;

[0068] (2) degassing: vacuum degassing for 15 min after the raw materials are melted and completely alloyed;

[0069] (3) refining: introducing high-purity argon into the furnace to 0.1 MPa, a purity of the argon being 99.99 wt %, and an oxygen content of the argon being 0.00006 wt %, and holding the metal melt at 1650° C. for 15 min;

[0070] (4) atomization: flowing the melt down a draft tube at a weight flow rate of 3.8 kg/min, atomizing the metal melt into fine droplets with 4 MPa high-pressure and high-purity argon, the droplets being cooled and solidified to form spherical powders, and collecting the powders using a tank; and

[0071] (5) sieving: sieving the powders by airflow classification and ultrasonic vibration under an inert gas atmosphere after the powders are fully cooled, to obtain spherical nickel-based superalloy powders with a particle size of 15-53 μm and 53-106 μm, and then vacuum packaging.

[0072] FIG. 1 presents an SEM image showing the René 104 nickel-based superalloy powder particles with 0.08% of RE elements that are prepared by gas atomization in Example 1 of the present disclosure. There are relatively few irregular powders or satellite powders, and the sphericity is high.

[0073] FIG. 2 presents a high-magnification SEM image showing the René 104 nickel-based superalloy powder particles with 0.08% of RE Sc elements that are prepared by gas atomization in Example 1 of the present disclosure. The sphericity is high, and the powder surface is smooth. The powders are mainly dendrites and a small number of cellular structures with fine grain sizes.

[0074] FIG. 3 presents a particle size distribution curve of René 104 nickel-based superalloy powders with 0.08% of RE elements that are prepared by gas atomization in Example 1 of the present disclosure. The particle size distribution is narrow, and the total yield of fine powders with a particle size of 15-53 μm and medium-sized powders with a particle size of 53-106 μm is up to 91.5%.

[0075] After analysis, the prepared René 104 nickel-based superalloy powder with 0.08% of RE elements has an oxygen content of 0.0093%, a sulfur content of 0.0021%, and a flowability of 15.8 s/50 g through a 2.5 mm aperture. The prepared powder has excellent performance, and can satisfy the requirements for 3D printing.

Example 2

[0076] The method provided in the present disclosure was applied to the René 104 nickel-based superalloy below. The RE element Y was added in a mass fraction of 0.08%. The alloy includes in percentage by weight: 20.6Co-13Cr-3.4Al-3.9Ti-3.8Mo-2.1W-2.4Ta-0.9Nb-0.05Zr-0.03B-0.04C-0.08Y-the balance of Ni. The steps of preparing nickel-based superalloy powder for 3D printing using the technical solutions provided in the present disclosure were as follows:

[0077] (1) vacuum melting: putting René 104 nickel-based superalloy raw materials with RE element Y added in a mass fraction of 0.08% into the melting crucible of a powder atomization furnace, and heating and melting the raw materials in a vacuum atmosphere of 0.05 Pa by using an IF induction power supply;

[0078] (2) degassing: vacuum degassing for 15 min after the raw materials are melted and completely alloyed;

[0079] (3) refining: introducing high-purity argon into the furnace to 0.1 MPa, a purity of the argon being 99.99 wt %, and an oxygen content of the argon being 0.00006 wt %, and holding the metal melt at 1650° C. for 15 min;

[0080] (4) atomization: flowing the melt down a draft tube at a weight flow rate of 3.8 kg/min, atomizing the metal melt into fine droplets with 4 MPa high-pressure and high-purity argon, the droplets being cooled and solidified to form spherical powders, and collecting the powders using a tank; and

[0081] (5) sieving: sieving the powders by airflow classification and ultrasonic vibration under an inert gas atmosphere after the powders are fully cooled, to obtain spherical nickel-based superalloy powders with a particle size of 15-53 μm and 53-106 μm, and then vacuum packaging. The total yield of fine powders with a particle size of 15-53 μm and medium-sized powders with a particle size of 53-106 μm is 88.7%.

[0082] After analysis, the prepared René 104 nickel-based superalloy powder with 0.08% of RE Y element has an oxygen content of 0.0126%, a sulfur content of 0.0056%, and a flowability of 24.3 s/50 g through a 2.5 mm aperture.

Example 3

[0083] The method provided in the present disclosure was applied to the René 104 nickel-based superalloy below. The RE elements Sc and Y were added in a mass fraction of 0.08%. The alloy includes in percentage by weight: 20.6Co-13Cr-3.4A1-3.9Ti-3.8Mo-2.1W-2.4Ta-0.9Nb-0.05Zr-0.03B-0.04C-0.04Sc-0.04Y-the balance of Ni. The steps of preparing nickel-based superalloy powder for 3D printing using the technical solutions provided in the present disclosure were as follows:

[0084] (1) vacuum melting: putting René 104 nickel-based superalloy raw materials with Sc element added in a mass fraction of 0.04% and Y element added in a mass fraction of 0.04% into the melting crucible of a powder atomization furnace, and heating and melting the raw materials in a vacuum atmosphere of 0.05 Pa by using an IF induction power supply;

[0085] (2) degassing: vacuum degassing for 15 min after the raw materials are melted and completely alloyed;

[0086] (3) refining: introducing high-purity argon into the furnace to 0.1 MPa, a purity of the argon being 99.99 wt %, and an oxygen content of the argon being 0.00006 wt %, and holding the metal melt at 1650° C. for 15 min;

[0087] (4) atomization: flowing the melt down a draft tube at a weight flow rate of 3.8 kg/min, atomizing the metal melt into fine droplets with 4 MPa high-pressure and high-purity argon, the droplets being cooled and solidified to form spherical powders, and collecting the powders using a tank; and

[0088] (5) sieving: sieving the powders by airflow classification and ultrasonic vibration under an inert gas atmosphere after the powders are fully cooled, to obtain spherical nickel-based superalloy powders with a particle size of 15-53 μm and 53-106 μm, and then vacuum packaging. The total yield of fine powders with a particle size of 15-53 μm and medium-sized powders with a particle size of 53-106 μm is 90.2%.

[0089] After analysis, the prepared René 104 nickel-based superalloy powder with 0.04% of RE Sc element and 0.04% of RE Y element has an oxygen content of 0.0114%, a sulfur content of 0.0048%, and a flowability of 21.2 s/50 g through a 2.5 mm aperture.

Example 4

[0090] A René 104 alloy block was prepared with the alloy powder prepared in Example 1 as raw materials based on the 3D printing process parameters in Comparative Example 1 of Chinese Patent No. CN108941560B. Specific parameters of the SLM process are as follows:

[0091] the laser power is 225 W, the spot diameter is 0.12 mm, the scanning speed is 600 mm/s, the scanning space is 0.11 mm, and the powder layer thickness is 0.03 mm. (Partition strategy is not used.)

[0092] FIG. 4 is an SEM image showing the microstructure of the René 104 alloy prepared in Example 4. The as-built part has a dense structure, in which no cracks are observed.

[0093] After testing, the prepared René 104 alloy has a density of 99.2%, the yield strength of 913 MPa, tensile strength of 1247 MPa, and elongation of 13.3% at room temperature. Compared with the as-fabricated part after crack elimination by SPS in Example 1 of Chinese Patent No. CN108941560B, the yield strength and the tensile strength are increased by 21.6% and 38.4% respectively.

[0094] Using the alloy and its powder provided by the present disclosure, the as-built part with no cracks and excellent mechanical properties was prepared by the building process parameters corresponding to the most severe cracking and the worst performance in Chinese Patent No. CN108941560B. This indicates that the alloy and its powder provided by the present disclosure can broaden the 3D printing process window.

Comparative Example 1

[0095] The method provided in the present disclosure was applied to the René 104 nickel-based superalloy below. The alloy includes in percentage by weight: 20.6Co-13Cr-3.4Al-3.9Ti-3.8Mo-2.1W-2.4Ta-0.9Nb-0.05Zr-0.03B-0.04C-the balance of Ni. The steps of preparing nickel-based superalloy powder for 3D printing using the technical solutions provided in the present disclosure were as follows:

[0096] (1) vacuum melting: putting René 104 nickel-based superalloy raw materials into the melting crucible of a powder atomization furnace, and heating and melting the raw materials in a vacuum atmosphere of 0.05 Pa by using an IF induction power supply;

[0097] (2) degassing: vacuum degassing for 15 min after the raw materials are melted and completely alloyed;

[0098] (3) refining: introducing high-purity argon into the furnace to 0.1 MPa, a purity of the argon being 99.99 wt %, and an oxygen content of the argon being 0.00006 wt %, and holding the metal melt at 1650° C. for 15 min;

[0099] (4) atomization: flowing the melt down a draft tube at a weight flow rate of 3.8 kg/min, atomizing the metal melt into fine droplets with 4 MPa high-pressure and high-purity argon, the droplets being cooled and solidified to form spherical powders, and collecting the powders using a tank; and

[0100] (5) sieving: sieving the powders by airflow classification and ultrasonic vibration under an inert gas atmosphere after the powders are fully cooled, to obtain spherical nickel-based superalloy powders with a particle size of 53-106 μm and 15-53 μm, and then vacuum packaging.

[0101] FIG. 5 presents an SEM image showing the René 104 nickel-based superalloy powder without minor RE elements that is prepared by gas atomization in Comparative Example 1 of the present disclosure. It can be observed that there are relatively many irregular powders or satellite powders.

[0102] FIG. 6 presents a high-magnification SEM image showing the René 104 nickel-based superalloy powder without minor RE elements that is prepared by gas atomization in Comparative Example 1 of the present disclosure. There are satellite powders adhering to the powder surface.

[0103] FIG. 7 presents a particle size distribution curve of René 104 nickel-based superalloy powder without minor RE elements that is prepared by gas atomization in Comparative Example 1 of the present disclosure. The particle size distribution is wider than that in Example 1, and the total yield of fine powders with a particle size of 15-53 μm and medium-sized powders with a particle size of 53-106 μm is only 74.1%.

[0104] After analysis, the prepared René 104 nickel-based superalloy powder has an oxygen content of 0.017%, a sulfur content of 0.0067%, and no flowability through a 2.5 mm aperture. The prepared powder has poor performance, and cannot satisfy the requirements for 3D printing.

Comparative Example 2

[0105] The method provided in the present disclosure was applied to the René 104 nickel-based superalloy below. The alloy includes in percentage by weight: 20.6Co-13Cr-3.4Al-3.9Ti-3.8Mo-2.1W-2.4Ta-0.9Nb-0.05Zr-0.03B-0.04C-0.04Sc-the balance of Ni. The steps of preparing nickel-based superalloy powder for 3D printing using the technical solutions provided in the present disclosure were as follows:

[0106] (1) vacuum melting: putting René 104 nickel-based superalloy raw materials with RE element Sc added in a mass fraction of 0.04% into the melting crucible of a powder atomization furnace, and heating and melting the raw materials in a vacuum atmosphere of 0.05 Pa by using an IF induction power supply;

[0107] (2) degassing: vacuum degassing for 15 min after the raw materials are melted and completely alloyed;

[0108] (3) refining: introducing high-purity argon into the furnace to 0.1 MPa, a purity of the argon being 99.99 wt %, and an oxygen content of the argon being 0.00006 wt %, and holding the metal melt at 1650° C. for 15 min;

[0109] (4) atomization: flowing the melt down a draft tube at a weight flow rate of 3.8 kg/min, atomizing the metal melt into fine droplets with 4 MPa high-pressure and high-purity argon, the droplets being cooled and solidified to form spherical powders, and collecting the powders using a tank; and

[0110] (5) sieving: sieving the powders by airflow classification and ultrasonic vibration under an inert gas atmosphere after the powders are fully cooled, to obtain spherical nickel-based superalloy powders with a particle size of 15-53 μm and 53-106 μm, and then vacuum packaging. The total yield of fine powders with a particle size of 15-53 μm and medium-sized powders with a particle size of 53-106 μm is only 80.6%.

[0111] After analysis, the prepared René 104 nickel-based superalloy powder with 0.04% of RE Sc element has an oxygen content of 0.0144%, a sulfur content of 0.0073%, and a flowability of 40.5 s/50 g through a 2.5 mm aperture. When the added RE elements content is too low, the flowability of the powder is poor, which is not conducive to 3D printing.

Comparative Example 3

[0112] The method provided in the present disclosure was applied to the René 104 nickel-based superalloy below. The alloy includes in percentage by weight: 20.6Co-13Cr-3.4Al-3.9Ti-3.8Mo-2.1W-2.4Ta-0.9Nb-0.05Zr-0.03B-0.04C-0.20Sc-the balance of Ni. The steps of preparing nickel-based superalloy powder for 3D printing using the technical solutions provided in the present disclosure were as follows:

[0113] (1) vacuum melting: putting René 104 nickel-based superalloy raw materials with RE element Sc added in a mass fraction of 0.20% into the melting crucible of a powder atomization furnace, and heating and melting the raw materials in a vacuum atmosphere of 0.05 Pa by using an IF induction power supply;

[0114] (2) degassing: vacuum degassing for 15 min after the raw materials are melted and completely alloyed;

[0115] (3) refining: introducing high-purity argon into the furnace to 0.1 MPa, a purity of the argon being 99.99 wt %, and an oxygen content of the argon being 0.00006 wt %, and holding the metal melt at 1650° C. for 15 min;

[0116] (4) atomization: flowing the melt down a draft tube at a weight flow rate of 3.8 kg/min, atomizing the metal melt into fine droplets with 4 MPa high-pressure and high-purity argon, the droplets being cooled and solidified to form spherical powders, and collecting the powders using a tank; and

[0117] (5) sieving: sieving the powders by airflow classification and ultrasonic vibration under an inert gas atmosphere after the powders are fully cooled, to obtain spherical nickel-based superalloy powders with a particle size of 15-53 μm and 53-106 μm, and then vacuum packaging. The total yield of fine powders with a particle size of 15-53 μm and medium-sized powders with a particle size of 53-106 μm is only 82%.

[0118] After analysis, the prepared René 104 nickel-based superalloy powder with 0.20% of RE Sc element has an oxygen content of 0.0087%, a sulfur content of 0.0018%, and a flowability of 17.4 s/50 g through a 2.5 mm aperture. In the process of melting and gas-atomizing, adding excessive RE elements would not further improve the powder performance, but increase the cost and the percentage of powders with a particle size of below 15 μm, and reduce the yield of powders that meet the required particle size for 3D printing.