CN112831703A - Niobium-copper alloy material and preparation method thereof - Google Patents
Niobium-copper alloy material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a niobium-copper alloy material and a preparation method thereof, wherein the niobium-copper alloy material comprises the following components in percentage by mass: 97-99.5% of niobium and 0.5-3% of copper, and is prepared by the following preparation method: (1) mixing the raw materials according to a formula, and carrying out high-energy ball milling to obtain an intermediate material; (2) performing discharge plasma sintering on the obtained intermediate material, and cooling to obtain the niobium-copper alloy material; the spark plasma sintering comprises first temperature rise, first heat preservation, second temperature rise, second heat preservation, third temperature rise, third heat preservation and temperature reduction which are sequentially carried out under constant pressure. The nano-crystalline niobium-copper two-phase alloy is formed by using niobium as a main component and copper as an auxiliary component, so that the niobium-copper alloy has the advantages of excellent biocompatibility, strong antibacterial property, good osteogenesis promoting effect, corrosion resistance, metallic luster and the like, shows good corrosion resistance in a physiological environment, and can be used as an orthopedic medical material.
Description
Technical Field
The invention relates to the field of alloy preparation, in particular to a niobium-copper alloy material and a preparation method thereof, and particularly relates to a niobium-copper alloy material for an antibacterial orthopedic screw and a preparation method thereof.
Background
At present, the metal-based biomaterial is widely applied to the clinical medical field of orthopedics, dentistry and the like, and is vital to the reconstruction and repair of the hard tissues of the human body and the improvement of the life quality of patients. Wherein, the fixing device made of metal material is widely applied to the traditional fracture treatment. The medical biological metal fixing device clinically used at present mainly comprises stainless steel, cobalt-based alloy, titanium and alloy thereof, magnesium, tantalum and other metals and alloys thereof.
For example, CN111388762A discloses a nano-doped skeleton alloy material, which comprises an alloy base material and a thermal coating, the alloy material of the present invention is compounded by aluminum, copper, manganese, nano-silica and magnesium, so as to effectively improve the mechanical strength of the finished product, wherein an adhesive is added to further improve the bonding strength between metal materials and improve the overall strength of the finished product, and the thermal coating uses tetrabutyl titanate as a precursor, and prepares the alloy coating through hydrolysis deposition, thereby improving the corrosion resistance of the finished product.
CN103421990A discloses an alloy material for a bone-strengthening steel nail, which comprises, by mass, 10-15% of titanium, 5-7% of zirconium, 2-5% of palladium, 1-3% of platinum, 0.3-0.7% of ruthenium, 0.02-0.5% of boron and the balance of aluminum. The alloy material is implanted into bones by utilizing the interaction between metals, can reach the elastic range suitable for human mechanics, has strong instant bearing capacity, and can effectively prolong the service life of the alloy material.
Stainless steel materials are used in the biomedical field for the first time and are also most widely used. SUS316L is an austenitic stainless steel, and is the only material used for bone fixation, spinal fixation, and cardiovascular and urinary catheters, and may cause strong biotoxicity problems due to the large amount of nickel element contained therein. Stainless steel has poor wear resistance, which is one of the main reasons why cobalt-based alloys have been introduced (ASTM F75, Vitallium) for the manufacture of hip joint prostheses. Cobalt-based alloys generally refer to Co — Cr-based alloys, which exhibit excellent corrosion resistance even in a chloride environment and have good wear resistance. They also have good mechanical properties, have a high modulus of elasticity (220-230GPa) similar to that of stainless steel (about 200GPa), and are an order of magnitude higher than cortical bone (20-30 GPa). However, upon contact with bones, due to their high modulus, a stress shielding effect is produced to adjacent bones, and the lack of mechanical stimulation to bones may induce resorption thereof, resulting in eventual failure and loosening of the implant. In addition, Co and Ni elements in the alloy have serious sensitization, so that the application of the Co and Ni elements is limited to a certain extent.
Although a number of alloy-based screws have been successfully used in the clinic, these metal screws have several drawbacks. Firstly, the metal implant material is corroded or abraded in a physiological environment, so that metal ions are dissolved out, and symptoms such as allergy and the like are caused; secondly, the stress shielding is mentioned above, the metal material is difficult to have Young modulus matching with human bone, so that the load can not be transferred to adjacent bone tissue by the metal material, the healing of the bone is not facilitated, and secondary fracture can be caused by serious people; meanwhile, because the operation is complicated, the metal screw cannot be degraded in vivo and needs to be taken out through a secondary operation, and various complications caused by postoperative bacterial infection still remain one of the challenges in medicine. Namely, the hot research on medical metal materials mainly aims at improving biocompatibility, increasing bone-promoting effect, bone conductivity, mechanical properties and corrosion resistance, and obtaining medical metal with biological functionality to solve complications such as bacterial infection in the operation.
Disclosure of Invention
In view of the problems in the prior art, the present invention aims to provide a niobium-copper alloy material and a preparation method thereof, wherein the prepared niobium-copper alloy material has the advantages of excellent biocompatibility, strong antibacterial property, bone promotion effect, osteoconductivity, corrosion resistance, metallic luster, etc., shows good corrosion resistance in physiological environment, and has excellent antibacterial property, and can be used as a metal material for orthopedic medical use.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a niobium-copper alloy material, which comprises the following components by mass: 97 to 99.5 percent of niobium and 0.5 to 3 percent of copper.
The niobium-copper alloy material provided by the invention adopts niobium as a main component and copper as an auxiliary component to form the nanocrystalline niobium-copper two-phase alloy through the design of the components, so that the niobium-copper alloy has the advantages of excellent biocompatibility, good bone formation promoting effect, corrosion resistance, metallic luster and the like, shows good corrosion resistance in a physiological environment, and can be used as an orthopedic medical material.
In the present invention, the niobium-copper alloy material may contain, in terms of mass%, 97 to 99.5% of niobium, for example, 97%, 97.5%, 98%, 98.5%, 99% or 99.5%, but the present invention is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
In the present invention, the content of copper in the niobium-copper alloy material is 0.5 to 3% by mass, and may be, for example, 0.5%, 1%, 1.5%, 2%, 2.5%, or 3%, but not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
In the invention, the sum of the mass percentages of niobium and copper in the niobium-copper alloy is 100%.
As a preferable technical scheme of the invention, the niobium-copper alloy material has the grain size of 30-400nm, the compressive strength of 1-1.9GPa and the Vickers hardness of 300-400 Hv.
In the present invention, the niobium-copper alloy material may have a crystal grain size of 30 to 400nm, for example, 30mm, 40mm, 50mm, 60mm, 70mm, 80mm, 90mm, 100mm, 150mm, 200mm, 250mm, 300mm, 350mm, or 400nm, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
In the present invention, the niobium-copper alloy material may have a compressive strength of 1 to 1.9GPa, for example, 1GPa, 1.1GPa, 1.2GPa, 1.3GPa, 1.4GPa, 1.5GPa, 1.6GPa, 1.7GPa, 1.8GPa or 1.9GPa, etc., but is not limited to the recited values, and other values not recited in this range are also applicable.
In the present invention, the Vickers hardness of the niobium-copper alloy material is 300-400Hv, and may be, for example, 300Hv, 310Hv, 320Hv, 330Hv, 340Hv, 350Hv, 360Hv, 370Hv, 380Hv, 390Hv, or 400Hv, but is not limited to the values listed, and other values not listed in the range are also applicable.
In a second aspect, the present invention provides a method for preparing the niobium-copper alloy according to the first aspect, the method comprising the steps of:
(1) mixing the raw materials according to a formula, and carrying out high-energy ball milling to obtain an intermediate material;
(2) performing discharge plasma sintering on the intermediate material obtained in the step (1), and cooling to obtain the niobium-copper alloy material;
the spark plasma sintering comprises first temperature rise, first heat preservation, second temperature rise, second heat preservation, third temperature rise, third heat preservation and temperature reduction which are sequentially carried out under constant pressure.
The niobium-copper alloy material provided by the invention overcomes the defect of large difference of niobium-copper melting points by adopting a specific sintering process and a multi-section sintering mode, so that the prepared niobium-copper alloy material has a nanocrystalline niobium-copper two-phase alloy, and the niobium-copper alloy material has good biocompatibility, strong antibacterial property and certain bone-promoting effect.
The high-energy ball milling is a conventional technical means in the field, such as controlling the rotating speed in the high-energy ball milling to be 1500-.
As a preferred technical scheme of the invention, the high-energy ball milling in the step (1) is carried out under a protective atmosphere.
Preferably, the high energy ball milling time in step (1) is 6-24h, such as 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h or 24h, but not limited to the recited values, and other values not recited in the range are also applicable.
As a preferable technical scheme of the invention, the intermediate material in the step (2) is subjected to discharge plasma sintering, namely the intermediate material is placed in a mould for sintering.
Preferably, before the spark plasma sintering in step (2), the vacuum is applied until the absolute vacuum degree is less than or equal to 6Pa, such as 6Pa, 5Pa, 4Pa, 3Pa, 2Pa or 1Pa, but not limited to the values listed, and other values not listed in the range are also applicable. The vacuum pumping in the invention is to place the mould of the intermediate material in a sintering furnace and then carry out vacuum pumping.
In a preferred embodiment of the present invention, the constant pressure is 30 to 80MPa, and may be, for example, 30MPa, 35MPa, 40MPa, 45MPa, 50MPa, 55MPa, 60MPa, 65MPa, 70MPa, 75MPa or 80MPa, but is not limited to the values listed above, and other values not listed above in this range are also applicable. In the present invention, the pressurization in the spark plasma sintering is realized by mechanical pressurization.
Preferably, the first temperature rise rate is 50 to 150 ℃/min, for example, 50 ℃/min, 60 ℃/min, 70 ℃/min, 80 ℃/min, 90 ℃/min, 100 ℃/min, 110 ℃/min, 120 ℃/min, 130 ℃/min, 140 ℃/min, 150 ℃/min, 160 ℃/min, 170 ℃/min, 180 ℃/min, 190 ℃/min or 200 ℃/min, etc., but is not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the end point temperature of the first temperature rise is 400-.
Preferably, the holding temperature of the first holding temperature is the same as the end temperature of the first temperature rise.
Preferably, the first incubation time is 1-5min, for example, 1min, 1.5min, 2min, 2.5min, 3min, 3.5min, 4min, 4.5min, or 5min, but not limited to the recited values, and other values not recited in this range are also applicable.
In a preferred embodiment of the present invention, the second temperature rise rate is 50 to 150 ℃/min, for example, 50 ℃/min, 60 ℃/min, 70 ℃/min, 80 ℃/min, 90 ℃/min, 100 ℃/min, 110 ℃/min, 120 ℃/min, 130 ℃/min, 140 ℃/min, 150 ℃/min, 160 ℃/min, 170 ℃/min, 180 ℃/min, 190 ℃/min, or 200 ℃/min, and the like, but the present invention is not limited to the above-mentioned values, and other values not listed in the above range are also applicable.
Preferably, the end point temperature of the second temperature rise is 700-850 ℃, and may be, for example, 700 ℃, 710 ℃, 720 ℃, 730 ℃, 740 ℃, 750 ℃, 760 ℃, 770 ℃, 780 ℃, 790 ℃, 800 ℃, 810 ℃, 820 ℃, 830 ℃, 840 ℃ or 850 ℃, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the second maintained temperature is the same as the second elevated temperature end point temperature.
Preferably, the time of the second heat preservation is 1-5min, for example, 1min, 1.5min, 2min, 2.5min, 3min, 3.5min, 4min, 4.5min or 5min, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
As a preferable embodiment of the present invention, the rate of the third temperature rise is 10 to 90 ℃/min, and for example, 10 ℃/min, 20 ℃/min, 30 ℃/min, 40 ℃/min, 50 ℃/min, 60 ℃/min, 70 ℃/min, 80 ℃/min or 90 ℃/min, etc., but is not limited to the above-mentioned values, and other values not listed in the above range are also applicable.
Preferably, the end point temperature of the third temperature rise is 900-.
Preferably, the third holding temperature is the same as the third elevated temperature end point temperature.
Preferably, the third incubation time is 1-10min, such as 1min, 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min or 10min, but not limited to the recited values, and other values not recited in this range are also applicable.
In a preferred embodiment of the present invention, the cooling rate of the cooling is 50 to 200 ℃/min, for example, 50 ℃/min, 100 ℃/min, 150 ℃/min, or 200 ℃/min, but the present invention is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the end point temperature of the temperature reduction is 300-350 ℃, and can be, for example, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃ or 350 ℃, etc., but is not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the furnace cooling is carried out after the temperature reduction reaches the end temperature.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) mixing the raw materials according to a formula, and carrying out high-energy ball milling to obtain an intermediate material;
(2) performing discharge plasma sintering on the intermediate material obtained in the step (1), and cooling to obtain the niobium-copper alloy material;
the discharge plasma sintering comprises first temperature rise, first heat preservation, second temperature rise, second heat preservation, third temperature rise, third heat preservation and temperature reduction which are sequentially carried out under the constant pressure of 30-80 MPa;
the temperature rise rate of the first temperature rise is 100-;
the temperature rise rate of the second temperature rise is 100-;
the temperature rise rate of the third temperature rise is 10-90 ℃/min, the end point temperature is 900-;
the cooling rate of the cooling is 50-200 ℃/min, the end temperature of the cooling is 300-350 ℃, and furnace cooling is carried out after the end temperature.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the niobium-copper alloy material provided by the invention has the advantages that through the improvement of the components and the preparation process, the grain size of the prepared niobium-copper alloy material is 30-400nm, the compressive strength is 1-1.9GPa, and the Vickers hardness is 300-400 Hv.
(2) The niobium-copper alloy material provided by the invention has a nanocrystalline niobium-copper biphasic structure, has the advantages of excellent biocompatibility, strong antibacterial property, good osteogenesis promoting effect, corrosion resistance, metallic luster and the like through the design of a specific preparation method, shows good corrosion resistance in a physiological environment, and can be used as an orthopedic medical material.
Drawings
FIG. 1 is a photograph of a niobium-copper alloy material provided in example 1 of the present invention;
FIG. 2 is an SEM photograph of a niobium-copper alloy material provided in example 1 of the present invention;
FIG. 3 is an SEM photograph of the niobium-copper alloy material provided in example 2 of the present invention.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
The embodiment provides a niobium-copper alloy material, which comprises the following components in percentage by mass: 98% of niobium and 2% of copper.
The preparation method comprises the following steps:
(1) mixing the raw materials according to a formula, and carrying out high-energy ball milling to obtain an intermediate material;
(2) performing discharge plasma sintering on the intermediate material obtained in the step (1), and cooling to obtain the niobium-copper alloy material;
the high-energy ball milling in the step (1) is carried out in a protective atmosphere, and the high-energy ball milling time is 12 hours;
the step (2) of performing discharge plasma sintering on the intermediate material is to place the intermediate material in a mold, before the discharge plasma sintering, vacuumizing is performed until the absolute vacuum degree is 6Pa, and the discharge plasma sintering comprises first temperature rise, first heat preservation, second temperature rise, second heat preservation, third temperature rise, third heat preservation and temperature reduction which are sequentially performed under the constant pressure of 50 MPa;
the temperature rise rate of the first temperature rise is 150 ℃/min, the end point temperature is 450 ℃, the heat preservation temperature of the first heat preservation is the same as the end point temperature of the first temperature rise, and the first heat preservation time is 3 min;
the temperature rising rate of the second temperature rise is 150 ℃/min, the end point temperature is 775 ℃, the heat preservation temperature of the second heat preservation is the same as the end point temperature of the second temperature rise, and the second heat preservation time is 1 min;
the temperature rise rate of the third temperature rise is 50 ℃/min, the end point temperature is 1000 ℃, the heat preservation temperature of the third heat preservation is the same as the end point temperature of the third temperature rise, and the third heat preservation time is 5 min;
the cooling rate of the cooling is 120 ℃/min, the end point temperature of the cooling is 325 ℃, and furnace cooling is carried out after the end point temperature.
The photograph of the obtained niobium-copper alloy material is shown in FIG. 1, the SEM photograph of the niobium-copper alloy material is shown in FIG. 2, and the properties of the obtained niobium-copper alloy material are detailed in Table 1.
Example 2
The embodiment provides a niobium-copper alloy material, which comprises the following components in percentage by mass: 97% of niobium and 3% of copper.
The preparation method comprises the following steps:
(1) mixing the raw materials according to a formula, and carrying out high-energy ball milling to obtain an intermediate material;
(2) performing discharge plasma sintering on the intermediate material obtained in the step (1), and cooling to obtain the niobium-copper alloy material;
the high-energy ball milling in the step (1) is carried out in a protective atmosphere, and the high-energy ball milling time is 24 hours;
the step (2) of performing discharge plasma sintering on the intermediate material is to place the intermediate material in a mold, before the discharge plasma sintering, vacuumizing is performed until the absolute vacuum degree is 3Pa, and the discharge plasma sintering comprises first temperature rise, first heat preservation, second temperature rise, second heat preservation, third temperature rise, third heat preservation and temperature reduction which are sequentially performed under the constant pressure of 30 MPa;
the temperature rise rate of the first temperature rise is 150 ℃/min, the end point temperature is 600 ℃, the heat preservation temperature of the first heat preservation is the same as the end point temperature of the first temperature rise, and the first heat preservation time is 1 min;
the temperature rise rate of the second temperature rise is 100 ℃/min, the end point temperature is 700 ℃, the heat preservation temperature of the second heat preservation is the same as the end point temperature of the second temperature rise, and the second heat preservation time is 5 min;
the temperature rise rate of the third temperature rise is 10 ℃/min, the end point temperature is 1100 ℃, the heat preservation temperature of the third heat preservation is the same as the end point temperature of the third temperature rise, and the third heat preservation time is 10 min;
the cooling rate of the cooling is 50 ℃/min, the end point temperature of the cooling is 350 ℃, and furnace cooling is carried out after the end point temperature.
The SEM photograph of the obtained niobium-copper alloy material is shown in FIG. 3, and the properties of the obtained niobium-copper alloy material are detailed in Table 1.
Example 3
The embodiment provides a niobium-copper alloy material, which comprises the following components in percentage by mass: 99.5 percent of niobium and 0.5 percent of copper.
The preparation method comprises the following steps:
(1) mixing the raw materials according to a formula, and carrying out high-energy ball milling to obtain an intermediate material;
(2) performing discharge plasma sintering on the intermediate material obtained in the step (1), and cooling to obtain the niobium-copper alloy material;
the high-energy ball milling in the step (1) is carried out in a protective atmosphere, and the high-energy ball milling time is 6 hours;
the step (2) of performing discharge plasma sintering on the intermediate material is to place the intermediate material in a mold, before the discharge plasma sintering, vacuumizing is performed until the absolute vacuum degree is 1Pa, and the discharge plasma sintering comprises first temperature rise, first heat preservation, second temperature rise, second heat preservation, third temperature rise, third heat preservation and temperature reduction which are sequentially performed under the constant pressure of 80 MPa;
the temperature rise rate of the first temperature rise is 100 ℃/min, the end point temperature is 400 ℃, the heat preservation temperature of the first heat preservation is the same as the end point temperature of the first temperature rise, and the first heat preservation time is 5 min;
the temperature rise rate of the second temperature rise is 150 ℃/min, the end point temperature is 850 ℃, the heat preservation temperature of the second heat preservation is the same as the end point temperature of the second temperature rise, and the second heat preservation time is 3 min;
the temperature rise rate of the third temperature rise is 90 ℃/min, the end point temperature is 900 ℃, the heat preservation temperature of the third heat preservation is the same as the end point temperature of the third temperature rise, and the third heat preservation time is 1 min;
the cooling rate of the cooling is 200 ℃/min, the end point temperature of the cooling is 300 ℃, and furnace cooling is carried out after the end point temperature.
The properties of the obtained niobium-copper alloy material are detailed in table 1.
Comparative example 1
The only difference from example 1 is that the first temperature holding was not performed, and the properties of the obtained niobium-copper alloy material are detailed in table 1.
Comparative example 2
The only difference from example 1 is that the second soaking was not performed, and the properties of the obtained niobium-copper alloy material are detailed in table 1.
Comparative example 3
The only difference from example 1 is that the third temperature keeping was not performed, and the properties of the obtained niobium-copper alloy material are detailed in table 1.
Comparative example 4
The difference from example 1 is only that the holding time of the first heat preservation is 10min, and the properties of the obtained niobium-copper alloy material are detailed in table 1.
Comparative example 5
The difference from example 1 is only that the second heat preservation time is 10min, and the properties of the obtained niobium-copper alloy material are detailed in table 1.
Comparative example 6
The difference from the example 1 is only that the holding time of the third heat preservation is 20min, and the properties of the obtained niobium-copper alloy material are detailed in table 1.
Comparative example 7
The only difference from example 1 is that the third temperature rise rate is 150 ℃/min, and the properties of the obtained niobium-copper alloy material are detailed in Table 1.
The compressive strength of the niobium-copper alloy material in the above examples and comparative examples was measured by a universal compression testing machine, and the vickers hardness was measured by a vickers hardness measuring instrument; corrosion performance an open circuit potential was tested for 2 hours and an open circuit potential-time curve was recorded using an electrochemical workstation with Hanks balanced salt solution as electrolyte at 37 c according to ISO10271:2011 standard. Potentiodynamic scanning was performed 5 minutes after completion of the Open Circuit Potential (OCP) test, at a scanning rate of 10mV/min, over a scanning range of-0.5V-1.0V vs. OCP, and potentiodynamic polarization curves were recorded. After obtaining the polarization curve, the corrosion potential Ecorr and the corrosion current density Icorr of the niobium-copper alloy are extracted from the polarization curve by a tafel slope extrapolation method. The antibacterial activity of Nb-Cu alloys against escherichia coli (e.coli, ATCC25922) and staphylococcus aureus (s.aureus, ATCC25923) was evaluated according to ISO22196:2007, comparing pure niobium and pure copper materials. Comparing a pure niobium material with a pure copper material, the in-vitro osteogenesis promoting capacity of the niobium-copper alloy is verified in mouse osteogenesis precursor cells MC3T 3-E1. And verified by ALP testing and alizarin red staining.
TABLE 1 Properties of niobium-copper alloy materials
The results of the above examples and comparative examples show that the niobium-copper alloy material provided by the present invention has a nanocrystalline niobium-copper biphasic structure, has excellent biocompatibility and good osteogenesis promoting effect, is corrosion resistant, has metallic luster, and the like, shows good corrosion resistance in physiological environment, and can be used as an orthopedic medical material by the design of the specific preparation method.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. The niobium-copper alloy material is characterized by comprising the following components in percentage by mass: 97 to 99.5 percent of niobium and 0.5 to 3 percent of copper.
2. The niobium-copper alloy material as claimed in claim 1, wherein the niobium-copper alloy material has a grain size of 30 to 400nm, a compressive strength of 1 to 1.9GPa, and a Vickers hardness of 300-400 Hv.
3. The method for producing a niobium-copper alloy material according to claim 1 or 2, wherein the production method comprises the steps of:
(1) mixing the raw materials according to a formula, and carrying out high-energy ball milling to obtain an intermediate material;
(2) performing discharge plasma sintering on the intermediate material obtained in the step (1), and cooling to obtain the niobium-copper alloy material;
the spark plasma sintering comprises first temperature rise, first heat preservation, second temperature rise, second heat preservation, third temperature rise, third heat preservation and temperature reduction which are sequentially carried out under constant pressure.
4. The method of claim 3, wherein the high energy ball milling of step (1) is performed under a protective atmosphere;
preferably, the time of the high-energy ball milling in the step (1) is 6 to 24 hours.
5. The production method according to claim 3 or 4, wherein the step (2) of subjecting the intermediate material to discharge plasma sintering is carried out by placing the intermediate material in a mold;
preferably, before the spark plasma sintering in the step (2), vacuumizing is carried out until the absolute vacuum degree is less than or equal to 6 Pa.
6. The production method according to any one of claims 3 to 5, wherein the constant pressure is 30 to 80 MPa;
preferably, the temperature rise rate of the first temperature rise is 50-150 ℃/min;
preferably, the end temperature of the first temperature rise is 400-600 ℃;
preferably, the holding temperature of the first holding temperature is the same as the end temperature of the first temperature rise;
preferably, the time of the first heat preservation is 1-5 min.
7. The production method according to any one of claims 3 to 6, wherein the second temperature rise is performed at a temperature rise rate of 50 to 150 ℃/min;
preferably, the end temperature of the second temperature rise is 700-850 ℃;
preferably, the second holding temperature is the same as the second temperature-rise end temperature;
preferably, the time of the second heat preservation is 1-5 min.
8. The production method according to any one of claims 3 to 7, wherein the rate of temperature rise of the third temperature rise is 10 to 90 ℃/min;
preferably, the end temperature of the third temperature rise is 900-;
preferably, the heat preservation temperature of the third heat preservation is the same as the terminal temperature of the third temperature rise;
preferably, the time of the third heat preservation is 1-10 min.
9. The method according to any one of claims 3 to 8, wherein the cooling rate of the cooling is 50 to 200 ℃/min;
preferably, the end temperature of the temperature reduction is 300-350 ℃;
preferably, the furnace cooling is carried out after the temperature reduction reaches the end temperature.
10. The method of manufacturing of claims 3-9, comprising the steps of:
(1) mixing the raw materials according to a formula, and carrying out high-energy ball milling to obtain an intermediate material;
(2) performing discharge plasma sintering on the intermediate material obtained in the step (1), and cooling to obtain the niobium-copper alloy material;
the discharge plasma sintering comprises first temperature rise, first heat preservation, second temperature rise, second heat preservation, third temperature rise, third heat preservation and temperature reduction which are sequentially carried out under the constant pressure of 30-80 MPa;
the temperature rise rate of the first temperature rise is 100-;
the temperature rise rate of the second temperature rise is 100-;
the temperature rise rate of the third temperature rise is 10-90 ℃/min, the end point temperature is 900-;
the cooling rate of the cooling is 50-200 ℃/min, the end temperature of the cooling is 300-350 ℃, and furnace cooling is carried out after the end temperature.
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