CN115301940A - Ti-Zr-Cu titanium alloy powder for laser additive manufacturing and preparation method and application thereof - Google Patents
Ti-Zr-Cu titanium alloy powder for laser additive manufacturing and preparation method and application thereof Download PDFInfo
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- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- B33—ADDITIVE MANUFACTURING TECHNOLOGY
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Abstract
Ti-Zr-Cu titanium alloy powder for laser additive manufacturing and a preparation method and application thereof. The invention belongs to the field of alloy powder for laser additive manufacturing. The invention aims to solve the technical problems of poor plasticity and toughness and low strength of a titanium alloy member caused by the defects that the titanium alloy powder for additive manufacturing and the titanium alloy part formed by SLM (melt extrusion molding) of the existing titanium alloy powder are easy to generate cracks, air holes, inclusions, poor interlayer bonding and the like. The invention relates to Ti-Zr-Cu series titanium alloy powder for laser additive manufacturing, which comprises the following components in percentage by mass: 35% -37%, nickel powder: 9% -11%, copper powder: 9% -11%, zirconium powder: 35% -37% of iron powder: 5 to 7 percent. The method comprises the following steps: and drying the raw material powder at low temperature under the protection of inert gas, screening and uniformly mixing to obtain Ti-Zr-Cu series titanium alloy powder. The Ti-Zr-Cu titanium alloy powder for laser additive manufacturing is used for selective laser melting of 3D printing titanium alloy components.
Description
Technical Field
The invention belongs to the field of alloy powder for laser additive manufacturing, and particularly relates to Ti-Zr-Cu titanium alloy powder for laser additive manufacturing and a preparation method and application thereof.
Background
Compared with material reduction manufacturing and equal material manufacturing technologies, the additive manufacturing technology has unique advantages and brings great changes to manufacturing industries. Due to the rapid development of laser manufacturing technology, selective Laser Melting (SLM) molding technology is gradually mature and becomes one of the most potential technologies in the field of additive manufacturing. The SLM forming technology is a novel manufacturing technology for printing and forming parts layer by layer from bottom to top on a two-dimensional section of a three-dimensional model after being sliced, wherein alloy powder is melted after absorbing high-density energy of a laser beam, and then is rapidly cooled and solidified. The SLM forming technology is suitable for wide range of materials, auxiliary work such as a die, a cutter and the like is not needed in the forming process, materials are saved, the development cycle is short, and parts with complex shapes and excellent comprehensive mechanical properties can be formed at one time. In addition, the SLM forming technology can also produce small-batch customized products at relatively low cost, so that customized quantitative production is realized. Therefore, the SLM molding technology has been applied to the fields of automobile manufacturing, aerospace, biomedical and defense industries, and the like.
The titanium alloy has the characteristics of low density, high specific strength, good corrosion resistance and the like, and is widely applied to the fields of aerospace, ocean, chemical engineering and the like. Therefore, the SLM forming technology is applied to the field of titanium alloy, and has important significance for improving the comprehensive performance of parts. The titanium alloy part manufactured by adopting the SLM forming technology has the following advantages: (1) The heat input is small, the cooling rate is high in the molding process, the prepared titanium alloy part has a fine structure and low microsegregation degree, and the low-melting-point eutectic phase and the formation of liquefied cracks are favorably inhibited; (2) The geometric shape of the titanium alloy micro-melting tank in the SLM forming process is deep and narrow, the change of the local heat flow direction is large, and the formation of isometric crystal structure is facilitated; (3) The SLM forming method has the advantages that the SLM forming method is used for forming parts with complex shapes, forming accuracy is higher, and the surface quality of formed parts is better. Therefore, the SLM forming method is hopeful to prepare high-quality titanium alloy parts with equiaxed or near equiaxed structures and easily controlled metallurgical defects.
However, when the SLM forms the titanium alloy parts, under the scanning of the laser beam with high energy density, the titanium alloy is melted and then rapidly solidified, the process of melting the titanium alloy from solid to liquid and solidifying from liquid to solid is extremely fast and is not easy to control, especially the cooling rate of the titanium alloy molten pool can reach 100k/s. Meanwhile, the influence of the structure components of the metal powder for SLM forming on the performance of the titanium alloy part is complex, if the components of the metal powder are not proper, the defects of cracks, air holes, inclusions, poor interlayer bonding and the like in the titanium alloy formed part are easily caused, and even the performance defects of poor ductility and toughness, low strength and the like are caused, so that the function of the metal powder for SLM forming of the titanium alloy is very important.
Disclosure of Invention
The invention aims to solve the technical problems that the titanium alloy member has poor plasticity and toughness and low strength caused by the defects that the titanium alloy powder for additive manufacturing and the titanium alloy part formed by SLM (melt spinning) of the existing titanium alloy powder are lack at present and the defects of cracks, pores, inclusion, poor interlayer bonding and the like are easy to generate, and provides Ti-Zr-Cu titanium alloy powder for laser additive manufacturing and a preparation method and application thereof.
The invention relates to Ti-Zr-Cu series titanium alloy powder for laser additive manufacturing, which comprises the following components in percentage by mass: 35% -37%, nickel powder: 9% -11%, copper powder: 9% -11%, zirconium powder: 35% -37% of iron powder: 5 to 7 percent.
Further limited, the titanium alloy powder is prepared from the following titanium powder in percentage by mass: 35%, nickel powder: 11% of copper powder: 12% and zirconium powder: 35% and iron powder: 7 percent of the composition.
Further limited, the titanium alloy powder is prepared from the following titanium powder in percentage by mass: 37% nickel powder: 11% of copper powder: 10% and zirconium powder: 37% and iron powder: 5 percent of the components.
Further, the particle size of each powder in the titanium alloy powder is less than 80 meshes.
The preparation method of the Ti-Zr-Cu titanium alloy powder for laser additive manufacturing comprises the following steps:
and drying the raw material powder at low temperature under the protection of inert gas, screening and uniformly mixing to obtain Ti-Zr-Cu series titanium alloy powder.
Further limiting, the temperature of low-temperature drying is 100-200 ℃, and the time is 1-2h.
Further limited, the inert gas is Ar, and the gas purity is more than 99.999%.
Further defined, the sieved pore size is 50 μm to 100 μm.
The Ti-Zr-Cu titanium alloy powder for laser additive manufacturing is used for selective laser melting of 3D printing titanium alloy components.
Further limiting, the deposited metal of the selected laser melting 3D printing titanium alloy component comprises the following chemical components in percentage by mass: c:0.02% -0.04%, H:0.001% -0.002%, O:0.001% -0.002%, ni:10.5% -12.5%, cu: 10.0-12.5%, S is less than or equal to 0.001%, P is less than or equal to 0.001%, zr:33.5% -37.5%, ti:32.5% -36.0%, fe:4.5 to 5.5 percent.
Compared with the prior art, the invention has the following remarkable effects:
1) The invention achieves the effects of refining crystal grains and increasing the alloy strength by adding Zr, simultaneously, utilizes the characteristic that Zr and Ti can be infinitely dissolved in solution, so that intermetallic compounds are not formed in the alloy to reduce the alloy performance, and in addition, because the enthalpy of mixing between Ti and Zr is 0, the acting force between Ti atoms and Zr atoms can not be influenced by adding Zr.
2) In the present alloy system, if the Zr content is less than 6%, the influence of the atomic distance on the elastic modulus is dominant, so that the increase in the Zr content results in a decrease in the elastic modulus. When the Zr content exceeds 6%, the atom bonding force is increased to account for the dominant factor, and the elastic modulus of the material is gradually increased along with the increase of the Zr content; the invention adjusts the lattice constant of the alloy in a quenching state by adjusting the content of Zr so as to adjust the generation mechanism of alpha' martensite, controls the content of Zr to be 33.5-37.5%, achieves the best balance between grain refinement, strengthening effect on Ti-Zr-Cu alloy and alloy cost, improves the grain refinement effect and the strength increase effect of Zr with excessive content no longer obviously, and greatly increases the alloy cost.
3) According to the invention, the transformation temperature of alpha' martensite in the titanium alloy is greatly reduced by adding Fe, the eutectoid decomposition reaction of Ti-Fe is beta → alpha + TiFe, only when the alloy components are close to the eutectoid point and annealing is carried out for a long time at the temperature slightly lower than the critical point, the annealed structure can be obtained, the titanium alloy containing more than 4% of iron can obtain the beta structure by quenching. About 5 percent of Fe is added into the Ti-Zr alloy, so that the width of the alpha' martensite can be obviously refined, the bending strength and the hardness are improved, and the abrasion performance of the alloy is improved; fe also has the effect of inhibiting the formation of omega phase, which can greatly reduce the plasticity of the alloy.
4) Ni and Cu are beta-phase stable elements, can form eutectic with titanium and zirconium, and obviously reduce the melting point of the alloy, thereby reducing the power of laser and heat input and being very beneficial to controlling the microstructure size of the alloy; however, too high Cu may form intermetallic brittle phases with titanium; ni can improve the high temperature and corrosion resistance properties of the alloy, but too much Ni content can significantly reduce the flow spreading properties of the liquid molten metal.
Drawings
FIG. 1 is a macro morphology photograph of Ti-Zr-Cu based titanium alloy powder for additive manufacturing of example 1;
FIG. 2 is a spectrum diagram of the additive manufacturing Ti-Zr-Cu based titanium alloy powder of example 1;
FIG. 3 is a micrograph of a selected area laser melted 3D printed titanium alloy component of example 1;
FIG. 4 is a macro morphology photograph of the Ti-Zr-Cu based titanium alloy powder for additive manufacturing of example 2;
FIG. 5 is a power spectrum of Ti-Zr-Cu-based titanium alloy powder for additive manufacturing according to example 2;
FIG. 6 is a microstructure photograph of a selected area laser melted 3D printed titanium alloy component of example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The experimental procedures used in the following examples are conventional unless otherwise specified. The materials, reagents, methods and apparatus used, unless otherwise specified, are conventional and commercially available to those skilled in the art.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains" or any other variation thereof, as used in the following embodiments, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates the singular.
Example 1: the Ti-Zr-Cu titanium alloy powder for laser additive manufacturing in this embodiment is prepared from, by mass: 35%, nickel powder: 11% of copper powder: 12% and zirconium powder: 35% of iron powder: 7 percent of the titanium alloy powder, and the granularity of all metal powder in the titanium alloy powder is less than 80 meshes.
The method for preparing the Ti-Zr-Cu titanium alloy powder for laser additive manufacturing comprises the following steps:
under the protection of Ar gas with the purity of more than 99.999 percent, drying titanium powder, nickel powder, copper powder, zirconium powder and iron powder for 1 hour at the low temperature of 100 ℃, sieving by a pore diameter of 100 mu m, and uniformly mixing to obtain the Ti-Zr-Cu series titanium alloy powder.
Applying the Ti-Zr-Cu titanium alloy powder for laser additive manufacturing to selective laser melting 3D printing of titanium alloy components;
the parameters of the selective laser melting 3D printing process are shown in table 1:
TABLE 1 Selective laser melting 3D printing Process parameters
The deposited metal of the selective laser melting 3D printing titanium alloy component comprises the following chemical components in percentage by mass: c:0.02%, H:0.002%, O:0.002%, ni:11.5%, cu:11.5%, S is less than or equal to 0.001%, P is less than or equal to 0.001%, zr:35.5%, ti:35.5%, fe:5.0 percent, and the balance of other inevitable impurities.
From FIG. 3, it can be seen that the sample has no weld defects such as air holes and cracks.
Example 2: the Ti-Zr-Cu titanium alloy powder for laser additive manufacturing in the embodiment is prepared from the following titanium powder in percentage by mass: 37% nickel powder: 11% of copper powder: 10% of zirconium powder: 37% and iron powder: 5 percent of the titanium alloy powder, and the granularity of all metal powder in the titanium alloy powder is less than 80 meshes.
The method for preparing the Ti-Zr-Cu titanium alloy powder for laser additive manufacturing comprises the following steps:
under the protection of Ar gas with the purity of more than 99.999 percent, drying titanium powder, nickel powder, copper powder, zirconium powder and iron powder at the low temperature of 200 ℃ for 1.5h, sieving by a pore diameter of 100 mu m, and uniformly mixing to obtain Ti-Zr-Cu series titanium alloy powder.
Applying the Ti-Zr-Cu titanium alloy powder for laser additive manufacturing to selective laser melting 3D printing of titanium alloy components;
the parameters of the selective laser melting 3D printing process are shown in the table 2:
TABLE 2 Selective laser melting 3D printing Process parameters
The deposited metal of the selective laser melting 3D printing titanium alloy component comprises the following chemical components in percentage by mass: c:0.02%, H:0.002%, O:0.002%, ni:12.0%, cu:12.0%, S is less than or equal to 0.001%, P is less than or equal to 0.001%, zr:34.0%, ti:36.0%, fe:5.0 percent, and the balance of other inevitable impurities.
As can be seen from FIG. 6, the sample has no welding defects such as air holes and cracks.
The above description is only a preferred embodiment of the present invention, and these embodiments are based on different implementations of the present invention, and the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The Ti-Zr-Cu titanium alloy powder for laser additive manufacturing is characterized by comprising the following components in percentage by mass: 35% -37%, nickel powder: 9% -11%, copper powder: 9% -11%, zirconium powder: 35% -37% of iron powder: 5 to 7 percent.
2. The Ti-Zr-Cu titanium alloy powder for laser additive manufacturing according to claim 1, wherein the titanium alloy powder is prepared from, by mass: 35%, nickel powder: 11% of copper powder: 12% and zirconium powder: 35% and iron powder: 7 percent of the composition.
3. The Ti-Zr-Cu titanium alloy powder for laser additive manufacturing according to claim 1, wherein the titanium alloy powder comprises, in mass percent, titanium powder: 37%, nickel powder: 11% of copper powder: 10% of zirconium powder: 37% and iron powder: 5 percent of the components.
4. The Ti-Zr-Cu-based titanium alloy powder for laser additive manufacturing according to claim 1, wherein the particle size of each powder in the titanium alloy powder is 80 mesh or smaller.
5. The method for preparing the Ti-Zr-Cu titanium alloy powder for laser additive manufacturing according to any one of claims 1 to 4, wherein the method comprises the following steps:
and drying the raw material powder at low temperature under the protection of inert gas, screening and uniformly mixing to obtain Ti-Zr-Cu series titanium alloy powder.
6. The method of claim 5, wherein the low temperature drying is performed at a temperature of 100-200 ℃ for 1-2 hours.
7. The method of claim 5, wherein the inert gas is Ar and the gas purity is greater than 99.999%.
8. The method of claim 5, wherein the size of the sieved pores is 50 μm to 100 μm.
9. The use of the Ti-Zr-Cu based titanium alloy powder for laser additive manufacturing of any one of claims 1 to 4 for selective laser melting of 3D printed titanium alloy components.
10. The application of claim 9, wherein the deposited metal of the 3D printed titanium alloy component by selective laser melting comprises the following chemical components in percentage by mass: c:0.02% -0.04%, H:0.001% -0.002%, O:0.001% -0.002%, ni:10.5% -12.5%, cu: 10.0-12.5%, S is less than or equal to 0.001%, P is less than or equal to 0.001%, zr:33.5% -37.5%, ti:32.5% -36.0%, fe:4.5 to 5.5 percent.
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