CN113981291B - High-entropy alloy gradient material and preparation method thereof - Google Patents

High-entropy alloy gradient material and preparation method thereof Download PDF

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CN113981291B
CN113981291B CN202111207466.5A CN202111207466A CN113981291B CN 113981291 B CN113981291 B CN 113981291B CN 202111207466 A CN202111207466 A CN 202111207466A CN 113981291 B CN113981291 B CN 113981291B
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陈冰清
闫泰起
熊华平
黄帅
赵梓钧
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AECC Beijing Institute of Aeronautical Materials
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Abstract

The invention belongs to the technical field of high-entropy alloy, and relates to a high-entropy alloy gradient material and a preparation method thereof. One side of the gradient material is NbTiMoVX high-entropy alloy, and X is Hf or Zr; the other side is NbTiMoVXSi alloy which takes NbTiMoVX multi-component high-entropy solid solution as a matrix and Nb 5 Si 3 The intermetallic compound is an alloy structure of a reinforcing phase; nb 5 Si 3 The content of the reinforcing phase gradually increases from one layer of the high-entropy alloy to the other side. The high-entropy alloy gradient material gold is prepared by adopting an additive manufacturing technology and a two-channel coaxial powder feeding mode. Nb can be realized in this way 5 Si 3 The gradient transition of the content of the reinforcing phase realizes the smooth transition forming of the gradient material from high toughness to high strength.

Description

High-entropy alloy gradient material and preparation method thereof
Technical Field
The invention belongs to the technical field of high-entropy alloy, and relates to a high-entropy alloy gradient material and a preparation method thereof.
Background
The material science is long troubled by the trade-off between strength and toughness in metal materials. The mass production and scientific research practice show that: the traditional metal material presents an inverted relation of strength improvement and plasticity reduction on the strength and toughness performance. This variation of "trade-off" greatly limits the range of applications for certain high-strength metal materials.
The research of the gradient metal material provides new revelation for the development of material science. The gradient structure with the characteristic of non-uniform distribution is introduced into the material organization structure, so that the limitation of 'this trade-off' between the strength and the toughness of the metal material can be effectively broken, the material can have higher toughness while the strength of the material is improved, and further research shows that the gradient structure can improve various properties of the material.
With the continuous improvement of the working temperature and the thrust-weight ratio of the advanced aeroengine, extremely high requirements are provided for the working temperature and the comprehensive mechanical property of hot end parts such as turbine blades, combustion chambers and the like, the parts often need higher high-temperature strength and room-temperature toughness at the same time, and the traditional materials and most ultrahigh-temperature structural materials cannot meet the design requirements.
In response to the above application requirements, a new heat-resistant structure with complex functions must be developed, for example, one side of the structure must have an ultra-high-temperature strength to withstand the high temperature of the surface and the thermal shock, and the other side of the structure is provided with high toughness by another metal to improve the deformation resistance of the material.
Disclosure of Invention
The purpose of the invention is: the high-entropy alloy gradient material and the preparation method thereof are provided to solve the problem that the traditional metal material cannot have high strength and high toughness, and provide a material technical basis for the development of hot-end components of aero-engines.
In order to solve the technical problem, the technical scheme of the invention is as follows:
on one hand, a high-entropy alloy gradient material is provided, and one side of the gradient material is NbTiMoVX high-entropy alloy; the other side is NbTiMoVXSi alloy which takes NbTiMoVX high-entropy alloy as a matrix and Nb 5 Si 3 The intermetallic compound is an alloy structure of a reinforcing phase;
from the high-entropy alloy side, the proportion of the NbTiMoVX high-entropy alloy is decreased gradually, and Nb is 5 Si 3 The duty ratio is increased.
X in the NbTiMoVX high-entropy alloy is Hf or Zr.
Nb in the NbTiMoVXSi alloy 5 Si 3 The volume content of the reinforcing phase is 10-50%.
Starting from the high-entropy alloy side, in a specific embodiment, five layers of Nb in the NbTiMoVXSi alloy follow 5 Si 3 The volume contents of the reinforcing phase are as follows in sequence: 8-12%, 18-22%, 28-32%, 38-42% and 48-50%. Preferably, five layers of Nb in NbTiMoVXSi alloy follow 5 Si 3 The volume contents of the reinforcing phase are as follows in sequence: 10%, 20%, 30%, 40%, 50%.
The total thickness of the high-entropy alloy gradient material is 3-12 mm; the thickness of each layer is 0.5-2 mm.
On the other hand, the preparation method of the high-entropy alloy gradient material is provided, and the high-entropy alloy gradient material is prepared by adopting an additive manufacturing technology and a double-channel coaxial powder feeding mode.
One channel is used for conveying NbTiMoVX high-entropy alloy powder; the other channel carries mixed Nb + Si powder. The Si element can be made to react with the Nb element preferentially, and the reaction between other metal elements can be avoided.
The particle size of the NbTiMoVX high-entropy alloy powder is 53-106 mu m; the particle size of the Nb + Si mixed powder is 45-75 mu m.
In the technical scheme of the invention, the gradient transition material is divided into six layers, the first layer is NbTiMoVX high-entropy alloy, and the next five layers are respectively Nb in the NbTiMoVXSi alloy 5 Si 3 The volume contents of the reinforcing phase are as follows in sequence: 8-12%, 18-22%, 28-32%, 38-42% and 48-50%. By adopting the design, the components between the layers cannot be mutated, a good metallurgical bonding interface can be formed between the layers, and cracks cannot be generated due to the sudden increase of the proportion of the enhanced phase; meanwhile, the difference of the physical and chemical properties such as the thermal expansion coefficient and the like of the adjacent alloy layers is not large, and the residual thermal stress in the gradient material can be reduced; correspondingly, the mechanical properties of the material can also form a gradient transition in the gradient material.
The invention has the beneficial effects that:
(1) the designed one-side NbTiMoVX high-entropy alloy consists of five high-melting-point metal elements, can form a high-entropy stable solid solution structure, and has high room-temperature fracture toughness and better strength as a toughness end of a gradient material. In the designed alloy, the enthalpy of mixing among several elements is very small, and chemical reaction is not easy to occur, so that a multi-element super solid solution phase is formed; meanwhile, elements with too high melting points such as Ta and W are not added into the alloy, so that the risk of segregation of alloy components is reduced. Wherein, Ti, V and Zr can be dissolved with Nb infinitely and can play a toughening role in the alloy; mo and Hf elements have larger lattice distortion and solid solution strengthening effect, can obviously refine alloy structure and improve high-temperature strength, hardness and plasticity.
(2) The other side of the gradient material is a multi-component high-entropy solid solution matrix + Nb 5 Si 3 The intermetallic compound reinforcing phase can fully exert the performance advantages of the material, realize the good matching of high-temperature strength and room-temperature toughness and ensure that the strong end of the gradient material has high strength. In-situ generated Nb in high entropy matrices 5 Si 3 The intermetallic compound reinforcing phase has thermodynamic stability at high temperature and extremely high strength, can obviously improve the strength of the material when uniformly distributed in the high-entropy alloy matrix, can keep the reinforcing effect on the high-entropy matrix at high temperature, and is suitable for serving as a hot-end part material of an aeroengine.
(3) By using a forming mode of additive manufacturing layer by layer, Nb can be realized 5 Si 3 The gradient transition of the content of the reinforcing phase realizes the smooth transition forming of the gradient material from high toughness to high strength.
(4) The total thickness of the high-entropy alloy gradient material is 3-12 mm, and the thickness of each layer is 0.5-2 mm. Within this range, the thickness of each layer and the total thickness of the material can be adjusted as desired. The layer thickness is less than 0.5mm, the element diffusion between layers and the influence of the interface between layers are increased, and the mechanical property is reduced; the layer thickness is more than 2mm, and the thickness of each layer and the total thickness of the material are large, so that residual thermal stress generated by laser additive manufacturing is too large, and deformation and even fracture are easy to occur.
Detailed Description
In the following description, well-known structures and techniques are not shown to avoid unnecessarily obscuring the present invention.
The NbTiMoVX high-entropy alloy comprises the following components in atomic percentage: 21 to 33.5 atomic percent of Nb element, 14.5 to 25 atomic percent of Ti element, 15.5 to 23.5 atomic percent of Mo element, 9.5 to 22 atomic percent of V element, 8.5 to 18 atomic percent of X element, and X is Hf or Zr.
Example 1:
(1) one side of the designed gradient material is NbTiMoVHf high-entropy alloy;
the NbTiMoVHf high-entropy alloy comprises the following components in atomic percentage: the atomic percent of Nb element is 33.5%, the atomic percent of Ti element is 19.5%, the atomic percent of Mo element is 17.5%, the atomic percent of V element is 12%, and the atomic percent of Hf element is 17.5%.
Then five layers of Nb in NbTiMoVHfSi alloy 5 Si 3 The volume contents of the reinforcing phase are as follows in sequence: 10%, 20%, 30%, 40%, 50%.
(2) Respectively and uniformly mixing Nb + Ti + Mo + V + Hf powder and Nb + Si powder according to the designed components, and respectively placing the Nb + Ti + Mo + V + Hf powder and the Nb + Si powder into two synchronous powder feeders of laser additive manufacturing equipment; ti-6Al-4V alloy is adopted as a substrate material for laser additive manufacturing.
(3) Firstly, preparing a NbTiMoVHf high-entropy alloy layer with the thickness of 0.5mm on a substrate by adopting single-channel powder feeding of Nb + Ti + Mo + V + Hf;
(4) and then preparing the next five layers, and adopting a double-channel coaxial powder feeding mode, wherein one channel is used for conveying Nb + Ti + Mo + V + Hf mixed powder, and the other channel is used for conveying Nb + Si mixed powder. Adjusting laser additive manufacturing parameters according to specific chemical components of each layer of the required prepared alloy, so that Nb + Ti + Mo + V + Hf powder and Nb + Si powder react in situ on the substrate to form Nb-Ti-Mo-Hf high-entropy alloy with NbTiMoVHf as a matrix 5 Si 3 The intermetallic compound is an alloy structure of a reinforcing phase, and the thickness of each layer is 0.5 mm.
Laser additive manufacturing parameters: the laser power is 2500W, the scanning speed is 700mm/min, the diameter of a light spot is 1.5mm, and the flow of protective gas is 20L/min; the powder feeding amount of Nb + Ti + Mo + V + Hf powder is 2000rpm, and the flow rate of a powder carrier is 8L/min; nb + Si powder: the first layer, the powder feeding amount is 400rpm, and the powder carrier flow is 6L/min; the second layer, the powder feeding amount is 800rpm, and the flow rate of the powder carrier is 7L/min; the third layer, the powder feeding amount is 1200rpm, and the flow rate of the powder carrier is 7L/min; the fourth layer, the powder feeding amount is 1600rpm, and the flow rate of the powder carrier is 8L/min; and the fifth layer, the powder feeding amount is 2000rpm, and the flow rate of the powder carrier is 8L/min.
(5) The method can prepare the Nb alloy gradually transited from the NbTiMoVHf high-entropy alloy to 50 percent of volume fraction Nb 5 Si 3 The total thickness of the gradient material for reinforcing the high-entropy alloy matrix is 3 mm.
The mechanical property test results of each layer of alloy in example 1 are shown in table 1:
TABLE 1
Figure BDA0003306417030000051
Example 2:
different from the embodiment 1, one side of the designed gradient material is NbTiMoVHf high-entropy alloy;
the NbTiMoVHf high-entropy alloy comprises the following components in atomic percentage: the atomic percent of Nb element is 26%, the atomic percent of Ti element is 21%, the atomic percent of Mo element is 20%, the atomic percent of V element is 19.5%, and the atomic percent of Hf element is 13.5%.
Then five layers of Nb in NbTiMoVHfSi alloy 5 Si 3 The volume contents of the reinforcing phase are as follows in sequence: 8%, 18%, 28%, 38%, 48%. The thickness of each layer is 1mm, and the total thickness of the gradient material is 6 mm.
Laser additive manufacturing parameters: the laser power is 2800W, the scanning speed is 850mm/min, the diameter of a light spot is 1.5mm, and the flow of protective gas is 30L/min; the powder feeding amount of Nb + Ti + Mo + V + Hf powder is 2500rpm, and the flow rate of a powder carrier is 9L/min; nb + Si powder: the first layer, the powder feeding amount is 500rpm, and the powder carrier flow is 6L/min; the second layer, the powder feeding amount is 1000rpm, and the flow rate of the powder carrier is 7L/min; the third layer, the powder feeding amount is 1500rpm, and the flow rate of the powder carrier is 8L/min; the fourth layer, the powder feeding amount is 2000rpm, and the flow rate of the powder carrier is 8L/min; and the fifth layer, the powder feeding amount is 2500rpm, and the flow rate of the powder carrier is 9L/min.
The mechanical property test results of each layer of alloy in example 2 are shown in table 2:
TABLE 2
Figure BDA0003306417030000061
Example 3:
different from the embodiment 1, one side of the designed gradient material is NbTiMoVZr high-entropy alloy,
the NbTiMoVZr high-entropy alloy comprises the following components in percentage by atom: the atomic percent of Nb element is 23.5%, the atomic percent of Ti element is 21.5%, the atomic percent of Mo element is 22%, the atomic percent of V element is 15%, and the atomic percent of Zr element is 18%.
Then Nb in five-layer NbTiMoVZrSi alloy 5 Si 3 The volume contents of the reinforcing phase are as follows in sequence: 10%, 20%, 30%, 40%, 50%. The thickness of each layer is 1.5mm, and the total thickness of the gradient material is 9 mm.
Laser additive manufacturing parameters: laser power is 3000W, scanning speed is 900mm/min, the diameter of a light spot is 2.0mm, and the flow of protective gas is 30L/min; the powder feeding amount of Nb + Ti + Mo + V + Hf powder is 3000rpm, and the flow rate of a powder carrier is 10L/min; nb + Si powder: the first layer, the powder feeding amount is 600rpm, and the powder carrier flow is 6L/min; the second layer, the powder feeding amount is 1200rpm, and the flow rate of the powder carrier is 7L/min; the third layer, the powder feeding amount is 1800rpm, and the flow rate of the powder carrier is 8L/min; the fourth layer, the powder feeding amount is 2400rpm, and the powder carrier flow is 9L/min; and the fifth layer, the powder feeding amount is 3000rpm, and the flow rate of the powder carrier is 10L/min.
The mechanical property test results of each layer of alloy in example 3 are shown in table 3:
TABLE 3
Figure BDA0003306417030000071
Example 4:
different from the embodiment 1, one side of the designed gradient material is NbTiMoVZr high-entropy alloy;
the NbTiMoVZr high-entropy alloy comprises the following components in percentage by atom: the atomic percent of Nb element is 29.5%, the atomic percent of Ti element is 22.5%, the atomic percent of Mo element is 23.5%, the atomic percent of V element is 15%, and the atomic percent of Zr element is 9.5%.
Then Nb in five-layer NbTiMoVZrSi alloy 5 Si 3 The volume contents of the reinforcing phase are as follows in sequence: 12%, 22%, 32%, 42% and 50%. Each layer is 2mm thick and the total thickness of the gradient material is 12 mm.
Laser additive manufacturing parameters: the laser power is 3200W, the scanning speed is 950mm/min, the diameter of a light spot is 2.5mm, and the flow of protective gas is 40L/min; the powder feeding amount of Nb + Ti + Mo + V + Hf powder is 3500rpm, and the flow rate of a powder carrier is 10L/min; nb + Si powder: the first layer, the powder feeding amount is 700rpm, and the flow rate of the powder carrier is 7L/min; the second layer, the powder feeding amount is 1400rpm, and the flow rate of the powder carrier is 8L/min; the third layer, the powder feeding amount is 2100rpm, and the flow rate of the powder carrier is 9L/min; the fourth layer, the powder feeding amount is 2800rpm, and the powder carrier flow is 10L/min; and the fifth layer, the powder feeding amount is 3500rpm, and the flow rate of the powder carrier is 10L/min.
The mechanical property test results of each layer of alloy in example 4 are shown in table 4:
TABLE 4
Figure BDA0003306417030000072
Figure BDA0003306417030000081
As can be seen from the data in tables 1 to 4, with Nb in the high entropy alloy matrix 5 Si 3 The volume content of the reinforcing phase is gradually increased, the strength of the material is increased, and the toughness is reduced. Therefore, the prepared gradient material can gradually transit from high toughness at one side to high strength at the other side, and the gradient transition of the structure and the performance is realized.

Claims (5)

1. A high-entropy alloy gradient material is characterized in that: one side of the gradient material is NbTiMoVHf high-entropy alloy; the other side is NbTiMoVHfSi alloy, the structure of the NbTiMoVHfSi alloy takes NbTiMoVHf high-entropy alloy as a matrix and Nb 5 Si 3 The intermetallic compound is a reinforcing phase;
from the NbTiMoVHf high-entropy alloy side, the NbTiMoVHf high-entropy alloy proportion is decreased gradually, and Nb 5 Si 3 The proportion is increased progressively; nb in the NbTiMoVHfSi alloy 5 Si 3 The volume content of the reinforcing phase is 10-50%;
starting from the NbTiMoVHf high-entropy alloy side, and then five layers of Nb in the NbTiMoVHfSi alloy 5 Si 3 The volume contents of the reinforcing phase are as follows in sequence: 8-12%, 18-22%, 28-32%, 38-42% and 48-50%.
2. A high entropy alloy gradient material as defined in claim 1, wherein: starting from the NbTiMoVHf high-entropy alloy side, and then five layers of Nb in the NbTiMoVHfSi alloy 5 Si 3 The volume contents of the reinforcing phase are as follows in sequence: 10%, 20%, 30%, 40%, 50%.
3. A high entropy alloy gradient material as defined in claim 1, wherein: the total thickness of the high-entropy alloy gradient material is 3-12 mm; the thickness of each layer is 0.5-2 mm.
4. A method of producing the high-entropy alloy gradient material of claim 1, characterized in that: the high-entropy alloy gradient material is prepared by adopting an additive manufacturing technology and a double-channel coaxial powder feeding mode;
one channel is used for conveying NbTiMoVHf high-entropy alloy powder, and the other channel is used for conveying Nb + Si mixed powder; the Si element can be made to react with the Nb element preferentially, and the reaction between other metal elements can be avoided.
5. The method of claim 4, wherein: the particle size of the NbTiMoVHf high-entropy alloy powder is 53-106 mu m; the particle size of the Nb + Si mixed powder is 45-75 mu m.
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Citations (7)

* Cited by examiner, † Cited by third party
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