CN111647772A

CN111647772A - Medical zirconium-based composite material with low elastic modulus and high strength and preparation method thereof

Info

Publication number: CN111647772A
Application number: CN202010493485.8A
Authority: CN
Inventors: 湛永钟; 罗礼营; 汤宏群; 卢海滨; 张嘉凯; 舒适
Original assignee: Guangxi University
Current assignee: Guangxi University
Priority date: 2020-06-02
Filing date: 2020-06-02
Publication date: 2020-09-11
Anticipated expiration: 2040-06-02
Also published as: CN111647772B

Abstract

The invention discloses a medical zirconium-based composite material with low elastic modulus and high strength and a preparation method thereof, belonging to the field of medical biomaterials, wherein the composite material comprises the following raw materials in percentage: titanium diboride 1.0-3.0 wt.%, titanium 6.67 &7.86 wt.%, niobium 20.36-21.10 wt.%, and zirconium for the balance. The invention is realized by utilizing TiB₂In-situ self-generation reaction mechanism in the titanium-containing zirconium-based alloy, the generated TiB is used as a reinforcing phase to reinforce the performance of the alloy, so that the zirconium-based biomedical alloy with the volume fraction of the TiB reinforcing phase of 2.54-7.70 vol.% is obtained, and the alloy has the characteristics of low elastic modulus, high strength and good comprehensive performance after phase analysis, microscopic structure observation and analysis, mechanical property, corrosion performance and other tests, and meets the requirements of clinical medicine on implanted materials.

Description

Medical zirconium-based composite material with low elastic modulus and high strength and preparation method thereof

Technical Field

The invention belongs to the field of biomedical materials, and particularly relates to a medical zirconium-based composite material with low elastic modulus and high strength and a preparation method thereof.

Background

Numerous studies have shown that if the material of the implant has a modulus of elasticity that is higher than that of the human body

High, it will make the mechanical properties of the human hard tissue substitute material and natural bone not match, resulting in severe stress shielding effect. When external force acts on a human body, the stress borne by the implant material cannot be effectively transferred, so that bone absorption and loosening after the implant is implanted are caused, human bones are weakened and withered, the implant can be failed, and the human body can be injured.

Recently, stress shielding effect caused by mismatch of elastic deformation of the interface of the implant and the human tissue due to the difference of elastic modulus has attracted extensive attention of researchers and medical staff in the related field. The case of implant operation failure due to large difference of elastic modulus occurs frequently. At present, the elastic modulus of most metal medical biomaterials, such as titanium and alloy thereof, zirconium and alloy thereof is 55 GPa-125 GPa, which is far higher than that of natural bones of human bodies, and does not meet the applicable mechanical standard of human body implants. The elastic modulus of the traditional biomedical alloy Ti-6Al-4V reaches 110GPa, is much higher than that of human bones (10-30 GPa), contains V and Al elements, both have certain cytotoxicity, and if the alloy is enriched in a human body, a series of complications of the nervous system and the visceral system of the human body can be caused. Research shows that the enrichment of Al element easily causes Alzheimer disease (senile dementia), and the enrichment of V element easily causes kidney damage. The developed zirconium-based metal glass still has a much higher elastic modulus (80-119 GPa) than that of human bones, and has poor mechanical properties, thus not meeting the requirements of clinical medical application.

At present, the elastic modulus of single-phase beta titanium and zirconium alloys developed by a large number of researchers is extremely close to the natural skeleton of a human body and has good clinical applicability, so that the single-phase beta titanium and zirconium alloys become a novel biomedical material with a great application prospect. However, because of the metastable body-centered cubic structure of the single-phase beta-type titanium and zirconium alloy, the mechanical properties such as ultimate compressive strength, yield strength, hardness and the like are greatly reduced compared with the alpha-type titanium and zirconium alloy. In addition, the magnetic susceptibility of zirconium is much lower than that of titanium, so that image distortion caused by magnetization during nuclear magnetic resonance detection can be avoided, and the reliability of diagnosis is facilitated.

Therefore, there is a need for development of a novel medical biomaterial having both low elastic modulus and high strength and excellent overall performance.

Disclosure of Invention

In order to solve the technical problems, the invention provides a medical zirconium-based composite material with low elastic modulus and high strength and a preparation method thereof.

In order to achieve the purpose, the invention provides the following technical scheme:

a medical zirconium-based composite material with low elastic modulus and high strength is prepared from titanium diboride, titanium, niobium and zirconium, and is a zirconium-based biomedical alloy with 2.54-7.70 vol.% of TiB reinforcing phase.

Further, the composite material comprises the following raw materials in percentage by weight: 1.0-3.0 wt.% of titanium diboride, 6.67-7.86 wt.% of titanium, 20.36-21.10 wt.% of niobium and the balance of zirconium.

Further, the composite material comprises the following raw materials in percentage by weight: titanium diboride 1.0 wt.%, titanium 6.67 wt.%, niobium 21.10 wt.%, and the balance zirconium.

Furthermore, the elastic modulus of the composite material is 29.93-32.81 GPa, and the elastic energy is 18.04-24.50 MJ/m³The maximum compression strength is 1204-1397 MPa, and the extensibility is 33.01-39.04%.

The invention provides a preparation method of a medical zirconium-based composite material with low elastic modulus and high strength, which comprises the following steps:

(1) weighing raw materials: respectively removing oxide skins on the surfaces of titanium diboride, titanium, niobium and zirconium, and weighing the raw materials according to the mass percentage of each component for later use;

(2) preparation before smelting: removing impurities in the vacuum furnace, sequentially stacking the weighed raw materials of titanium, zirconium, niobium and titanium diboride into the vacuum furnace from low melting point to high melting point, vacuumizing, and introducing argon;

(3) smelting a sample: and arc striking and smelting in an argon atmosphere, wherein the smelting temperature range is 3000-3500 ℃, and the composite material is obtained after the crucible copper and the sample are cooled to room temperature.

Further, in the step (2), the steps of vacuumizing and introducing argon for washing are repeated for 2-3 times, and residual air in the furnace is removed as much as possible.

Further, in the step (2), the degree of vacuum in the vacuum furnace was 3.5 × 10^-3～6.5×10^-3Pa。

Further, in the step (3), the number of times of arc melting is 4-6.

Further, in the step (3), the smelting voltage is 220V, and the smelting current is controlled to be 100-200A.

The reaction principle of the invention is as follows: TiB₂Reacts with Ti in the material:

Ti+B→TiB (1)

Ti+2B→TiB₂(2)

TiB₂+Ti→2 TiB (3)

according to the thermodynamic theory of the reaction system, the reaction energy is carried out with the proviso that the Gibbs free energy change (. DELTA.G) < 0. After approximate processing is adopted, the delta G expression of the reaction formula is obtained as follows:

(1) formula (II): Δ G ═ 163176+5.86T

(2) Formula (II): Δ G ═ 142256+10.25T

(3) Formula (II): Δ G ═ 41840-8.79T

According to the thermodynamic criterion of the in-situ spontaneous reaction, the fact that the 3 reactions can be carried out within the temperature range of 500-3000K can be obtained. According to the thermodynamic theory, the larger the absolute value of Δ G < 0, the easier the reaction proceeds under the same conditions, and the arrangement of Δ G is from small to large: (1) < 2 > < 3 >, the available reaction (1) proceeds first in thermodynamic terms.

However, since △ G is also negative in reaction (3), Ti in the material causes the reaction to proceed toward the generation of TiB, and thus both thermodynamic calculations and chemical equilibrium analysis indicate that TiB is generated₂And finally forms a TiB strengthening phase with more stable thermodynamic property in the matrix with Ti. The TiB reinforcing phase is used as the in-situ reinforcing ceramic phase of the composite material and has good affinity.

The invention has the following beneficial effects:

1. the material is prepared from titanium diboride, titanium, niobium and zirconium, the zirconium-based composite material is generated by using a method for generating the reinforcing phase TiB by in-situ self-generation of the titanium diboride and the titanium, the reinforcing phase TiB is in-situ nucleated and grown from a metal aggregate, the thermodynamic property of the reinforcing phase is stable, the surface of the reinforcing body is free from pollution, a series of problems of surface (interface) wetting, interface reaction and the like of the reinforcing body and a base body in the conventional preparation process are avoided, and the processes of independent synthesis, addition, treatment and the like of the reinforcing body are omitted, so that the process difficulty and the cost are reduced; the reinforcement has good compatibility with the matrix, stable interface and high interface bonding strength.

2. The invention adopts an in-situ autogenous strengthening process to combine TiB fibers or particles as ceramic reinforcing phase with beta-type zirconium and niobium alloy phase to obtain the metal-based medical composite material with a single-phase beta-type alloy matrix, and optimizes the comprehensive mechanical property and corrosion resistance of the alloy while keeping the advantage of low elastic modulus of metastable beta phase. The reinforcing phase TiB has good chemical stability, excellent specific strength and rigidity, excellent impact conductivity and corrosion resistance, and does not contain cytotoxic elements; the composite material has 2.54-7.70 vol.% of TiB reinforcing phase obtained by calculation, the TiB reinforcing phase has good reactivity in the novel zirconium-based alloy, the reaction condition is simple and easy to achieve, the TiB reinforcing phase is well combined with a metal matrix, the inherent brittleness of the TiB reinforcing phase can be effectively eliminated, the fatigue damage of the TiB reinforcing phase under the physiological condition can be effectively eliminated, and the respective advantages of the two materials of transition metal and active ceramic can be exerted.

3. The biomedical composite material designed by the invention has the elastic modulus of 29.93-32.81 GPa and the elastic energy of 18.04-24.50 MJ/m³The maximum compression strength is 1204-1397 MPa, and the extensibility is 33.01-39.04%. Therefore, the processing property is good, and the requirements of clinical medicine on implantation materials are met. The excellent comprehensive performance also makes the material become a potential biomedical material with wide application prospect.

4. When the material is manufactured, the vacuum melting furnace with the copper crucible water cooling structure is used for melting, raw materials are sequentially placed in the vacuum melting furnace from low melting point to high melting point during melting, the placed raw materials are firstly contacted with electric arc, the temperature is high, the raw materials at the bottom are contacted with the water-cooled copper crucible, the temperature is low, and therefore alloy can be uniformly mixed and fully reacted while the melting loss rate is effectively reduced. The preparation method is simple and easy to operate, high in efficiency and low in cost.

Drawings

FIG. 1 is a stress-strain plot for various embodiments of the present invention. (in the figure: curve A-example 1, curve B-example 2, and curve C-example 3).

FIG. 2 is an XRD pattern for each example of the present invention (a for example 1, b for example 2, and c for example 3).

FIG. 3 is a SEM photograph of example 1 of the present invention.

FIG. 4 is a Tafel polarization plot of example 1 of the present invention.

FIG. 5 is a SEM photograph of example 2 of the present invention.

FIG. 6 is a Tafel polarization plot of example 2 of the present invention.

FIG. 7 is a SEM photograph of example 3 of the present invention.

FIG. 8 is a Tafel polarization plot of example 3 of the present invention.

Detailed Description

The present invention is described in detail below with reference to specific embodiments, which are provided for illustration only and are not intended to limit the invention.

Example 1

A preparation method of a medical zirconium-based composite material with low elastic modulus and high strength comprises the following steps:

(1) weighing raw materials: respectively removing oxide skins on the surfaces of titanium diboride, titanium, niobium and zirconium, clamping the metal block into small blocks by using a hydraulic clamp, and weighing 10g of raw materials according to the mass percentage in the table 1 for later use; the purity of the raw materials is more than or equal to 99.9 percent;

TABLE 1 ingredient ratio

Alloy composition	Zr/wt.％	Nb/wt.％	Ti/wt.％	TiB₂/wt.％
					Content (wt.)	71.23	21.1	6.67	1.0

(2) Preparation before smelting: the impurities in the vacuum furnace are removed,cleaning the vacuum furnace by absolute ethyl alcohol, then placing the weighed raw materials of titanium, zirconium, niobium and titanium diboride into a non-consumable vacuum arc furnace in sequence from low melting point to high melting point, vacuumizing, and controlling the vacuum degree to be 3.5 × 10^-3～6.5×10^-3Pa, introducing argon gas for gas washing to remove residual air, repeatedly performing the steps of vacuumizing and gas washing for 3 times, and finally introducing argon gas until a pressure gauge displays positive pressure;

(3) smelting a sample: and (3) arc striking smelting in an argon atmosphere, wherein oxygen-absorbing titanium ingots are smelted for 60 seconds to consume oxygen possibly existing in the furnace. And then gradually adding current to 150A to ensure that the smelting temperature range is 3000-3500 ℃, and smelting the samples one by one for 120 s. After the sample is completely cooled, the sample is turned over by using a turning rod, and the melting is continued for 6 times. After 6 times of melting, two samples with a mass of 10g were turned over and melted into a 20g sample. Repeatedly smelting the mixed sample for 6 times according to the conditions to ensure that the raw materials can be uniformly mixed and fully reacted in the smelting process;

and cooling the crucible copper and the sample to room temperature to obtain the zirconium-based composite material.

(4) And detecting the mechanical property and the corrosion property of the prepared zirconium-based composite material.

1) The above prepared samples were cut into standards by wire: 5X 10mm, the surface of the standard sample is cleaned and then subjected to a compression test on a material testing system Instron8801 at a speed of 1mm/min, the resulting experimental data being processed to produce a stress-strain curve, as shown in Curve A of figure 1. The obtained sample was processed and then subjected to XRD detection and analysis and SEM (scanning electron microscope) observation and analysis, as shown in fig. 2(a) and 3.

2) Before an electrochemical corrosion test, the prepared sample is cut into a cylindrical sample with the diameter of 14mm multiplied by 4mm, then 320#, 600#, 1000#, 1500# and 2000# silicon carbide abrasive paper is adopted to polish the sample to be smooth, the surface is mechanically polished by diamond paste, and the circular surface with the diameter of 14mm is used as a test surface. All samples are kept in a HH-1 model constant temperature water bath box at 37 ℃ and artificial saliva is used as corrosive liquid, the specific components of the artificial saliva are shown in a table 2, and the preparation of the artificial saliva is in accordance with ISO/TR10271 standard.

TABLE 2 Artificial saliva ingredient Table

The electrochemical corrosion experiment adopts a three-electrode system, a composite material is used as a working electrode, a platinum electrode is used as an auxiliary electrode, a saturated calomel electrode is used as a reference electrode, and after the three-electrode system is installed, a CS310 electrochemical workstation is used for collecting electrochemical corrosion experiment data of the composite material.

Before the Tafel diagram data in the electrochemical corrosion test is tested, an open-circuit potential test is firstly carried out to ensure that the composite material tends to have stable potential in the artificial saliva electrolyte, the open-circuit time of the test is 900S, the sampling interval is 0.1A/S, the potential is limited to-1V, after a stable and straight open-circuit potential curve is obtained, the Tafel electrochemical corrosion test is carried out, and the experimental parameters adopted by the Tafel test are that the scanning surface potential range is-1.5V-3V, the scanning speed (R) is 0.002V/S, the scanning frequency is 4.00Hz, the standing time (Q) is 2S, and the sensitivity (S) is 1.0 × 10^-4A/V。

The experimental results are shown in FIGS. 1 to 4. Fig. 2(a) is an XRD spectrum of a sample in example 1 of the present invention, and fig. 3 is an SEM picture thereof. From the figure, we can conclude that the reinforcing phase TiB is generated in the composite material at this time and only consists of the reinforcing phase TiB and the matrix phase beta-Zr (Nb is dissolved in the matrix), and the reinforcing phase is distributed in a network shape in the matrix.

FIG. 1 is a stress-strain plot for each example of the present invention, wherein curve A represents the sample of this example. Analysis of the curve A in FIG. 1 and the curve A in FIG. 4 shows that the composite material of the present embodiment has an elastic modulus of 31.97GPa, which is more suitable for the natural bone tissue of human body, and an elastic performance of 19.72MJ/m³The compressive strength is 1289Mpa, the elongation is 36.25 percent, and the corrosion rate is 1.105 × 10^-6The m/year has very good comprehensive performance and meets the requirements of clinical medicine on implantation materials. This is due to the reinforcing phase TiB being distributed in a network in the matrix of the materialThe properties are more stable and balanced, so that the composite material has the best overall properties, particularly the corrosion resistance, and therefore the corrosion rate is the lowest.

In the present invention, we use TiB₂The mechanism of in situ self-generation in the excess titanium acts as a mechanism for the generation of the TiB reinforcing phase. According to the reaction thermodynamic conditions and the product ratio of the reaction in the high-temperature environment of vacuum non-consumable arc melting, a relational expression of the ratio of the enhanced phase volume to the sample volume fraction can be obtained:

in the formula, ρ_sAs the overall density of the sample, M_sFor sample weighing, Mo_(TiB)Is the relative molecular weight of TiB in the sample, Mo_(TiB2)As a reactant TiB₂Relative molecular weight.

In accordance with again that,

the reactant TiB can be deduced₂The relational expression of the addition amount and the generated volume fraction of the reinforcing phase is as follows:

in the formula (I), the compound is shown in the specification,

as a reactant TiB₂And (4) mass fraction.

The volume fraction of TiB in the reinforcing phase in this example was calculated to be 2.54 vol.% according to the above formula.

Example 2

(1) weighing raw materials: respectively removing oxide skins on the surfaces of titanium diboride, titanium, niobium and zirconium, clamping the metal block into small blocks by using a hydraulic clamp, and weighing 10g of raw materials according to the mass percentage in the table 3 for later use; the purity of the raw materials is more than or equal to 99.9 percent;

TABLE 3 ingredient ratio

Alloy composition	Zr/wt.％	Nb/wt.％	Ti/wt.％	TiB₂/wt.％
					Content (wt.)	70.0	20.74	7.26	2.0

(2) Preparation before smelting, namely removing impurities in a vacuum furnace, cleaning the vacuum furnace by absolute ethyl alcohol, sequentially putting weighed raw materials of titanium, zirconium, niobium and titanium diboride into a non-consumable vacuum arc furnace according to the sequence of low melting point to high melting point, vacuumizing, and controlling the vacuum degree to be 3.5 × 10^-3～6.5×10^-3Pa, introducing argon gas for gas washing to remove residual air, repeatedly performing the steps of vacuumizing and gas washing for 3 times, and finally introducing argon gas until a pressure gauge displays positive pressure;

and cooling the crucible copper and the sample to room temperature to obtain the composite material.

(4) The composite material obtained in this example 2 was tested for mechanical properties and corrosion performance according to the method of example 1.

The results of the experiments are shown in FIGS. 1, 2, 5 and 6. Fig. 2(b) is an XRD spectrum of a sample in example 2 of the present invention, and fig. 5 is an SEM picture thereof. From the figure, we can conclude that the reinforcing phase TiB is generated in the composite material at this time and only consists of the reinforcing phase TiB and the matrix phase beta-Zr (Nb is dissolved in the matrix), and the reinforcing phase is uniformly distributed in a network shape and a granular shape in the matrix.

FIG. 1 is a stress-strain plot for each example of the present invention, wherein curve B represents the sample of this example. Analysis of the curves B and 6 in FIG. 1 shows that the composite material of the present embodiment has an elastic modulus of 32.81GPa, and an elastic performance of 18.04MJ/m³The compressive strength is 1204Mpa, the elongation is 39.04%, and the corrosion rate is 4.952 × 10^-6m/year, has better comprehensive performance and meets the requirements of clinical medicine on implantation materials.

In the case of the formulation of this example, the reinforcing phase TiB presents a reticular and granular distribution, with the granules nested within the reticular structure, which is also of good performance since it is not as dense and uniform as example 1, but slightly less corrosion-resistant than example 1, but rather exhibits superior ductility.

The volume fraction of reinforcing phase TiB in this example was 5.11 vol.% obtained by calculating the volume of reinforcing phase as in example 1.

Example 3

(1) weighing raw materials: respectively removing oxide skins on the surfaces of titanium diboride, titanium, niobium and zirconium, clamping the metal block into small blocks by using a hydraulic clamp, and weighing 10g of raw materials according to the mass percentage in the table 4 for later use; the purity of the raw materials is more than or equal to 99.9 percent; (ii) a

TABLE 4 ingredient ratio

Alloy composition	Zr/wt.％	Nb/wt.％	Ti/wt.％	TiB₂/wt.％
					Content (wt.)	68.78	20.36	7.86	3.0

(3) smelting a sample: in the arc striking smelting in the argon atmosphere, firstly, oxygen-absorbing titanium ingots are smelted for 60s to consume oxygen possibly existing in the furnace. And then gradually adding current to 150A to ensure that the smelting temperature range is 3000-3500 ℃, and smelting the samples one by one for 120 s. After the sample is completely cooled, the sample is turned over by using a turning rod, and the melting is continued for 6 times. After 6 times of melting, two samples with a mass of 10g were turned over and melted into a 20g sample. Repeatedly smelting the mixed sample for 6 times according to the conditions to ensure that the raw materials can be uniformly mixed and fully reacted in the smelting process;

(4) The composite material obtained in this example 3 was tested for mechanical properties and corrosion performance according to the method of example 1.

The experimental results are shown in FIGS. 1, 2, 7 and 8, FIG. 2(C) is an XRD pattern and FIG. 7 is an SEM picture of the sample of example 3 of the present invention, it can be seen from the XRD pattern that the reinforcing phase TiB is generated in the composite material at this time and is composed of the reinforcing phase TiB and the matrix phase β -Zr (Nb is dissolved therein), the reinforcing phase presents needle-like fiber morphology in the matrix and is uniformly distributed, FIG. 1 is a stress-strain diagram of various examples of the present invention, wherein curve C represents the stress-strain curve of the sample of this example, and analysis of the curves C and 8 in FIG. 1 shows that the composite material of this example has an elastic modulus of 29.93Gpa which is more suitable for the natural bone tissue of human body and an elastic energy of 24.50MJ/m³The compressive strength is 1397Mpa, the extensibility is 33.01%, and the corrosion rate is 3.048 × 10^-6m/year, has better comprehensive performance and meets the requirements of clinical medicine on implantation materials.

In the case of the formulation of the present experimental example, the reinforcing phase TiB presents a uniform distribution of acicular fibers, is less uniform and dense than the network structure of example 1, and has good overall properties, but a slightly inferior corrosion resistance compared to example 1.

The volume fraction of the reinforcing phase TiB in this example was 7.70 vol.% obtained by the same method as in example 1 for calculating the volume of the reinforcing phase.

As can be seen from the above examples 1-3 and FIGS. 1-8, the amount of the TiB reinforcing phase is not in direct proportion to the performance of the composite material, and the morphology and distribution of the reinforcing phase are different depending on the amount of the reinforcing phase. Therefore, the addition amount of TiB is controlled, and the proper amount of the reinforcing phase can form a form and distribution which are favorable for the performance. As in the present invention, the volume fraction of reinforcing phase in example 1 was 2.54 vol%, which formed a favorable network distribution morphology for corrosion performance, while as the reinforcing phase increased to 5.11 vol% and 7.70 vol%, the reinforcing phase exhibited non-continuous network, granular and needle-like morphologies, which did not contribute to the improvement of the corrosion performance of the composite material, although other properties were improved, and thus the corrosion performance was inferior to that of example 1, with the best overall performance of example 1 being the best of the three examples.

The above description is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.

Claims

1. The medical zirconium-based composite material with low elastic modulus and high strength is characterized by comprising the following raw materials in percentage by weight: 1.0-3.0 wt.% of titanium diboride, 6.67-7.86 wt.% of titanium, 20.36-21.10 wt.% of niobium and the balance of zirconium.

2. The low elastic modulus high strength medical zirconium based composite material according to claim 1, wherein the composite material comprises the following raw materials in percentage by weight: titanium diboride 1.0 wt.%, titanium 6.67 wt.%, niobium 21.10 wt.%, and the balance zirconium.

3. The medical zirconium based composite material with low elastic modulus and high strength according to claim 1, wherein the medical zirconium based composite material has 2.54 to 7.70 vol.% of TiB reinforcing phase.

4. The medical zirconium-based composite material with low elastic modulus and high strength as claimed in any one of claims 1 to 3, wherein the medical zirconium-based composite material has an elastic modulus of 29.93 to 32.81GPa and an elastic energy of 18.04 to 24.50MJ/m³The compressive strength is 1204-1397 MPa, and the extensibility is 33.01-39.04%.

5. A method for preparing a low modulus of elasticity high strength medical zirconium based composite material according to any of claims 1 to 4, comprising the steps of:

(2) preparation before smelting: removing impurities in the vacuum furnace, stacking the weighed raw materials of titanium, zirconium, niobium and titanium diboride into the vacuum furnace in sequence according to the sequence of melting points from low to high, vacuumizing, and introducing argon;

(3) smelting a sample: and arc striking and smelting in an argon atmosphere, wherein the smelting temperature range is 3000-3500 ℃, and the zirconium-based composite material is obtained after the crucible copper and the sample are cooled to room temperature.

6. The method for preparing a low elastic modulus high strength medical zirconium based composite material according to claim 5, wherein in the step (2), the degree of vacuum in the vacuum furnace is 3.5 × 10^-3～6.5×10^-3Pa。

7. The method for preparing the medical zirconium-based composite material with low elastic modulus and high strength as claimed in claim 5, wherein in the step (3), the number of arc melting is 4-6.

8. The method for preparing the medical zirconium-based composite material with low elastic modulus and high strength as claimed in claim 5, wherein in the step (3), the melting voltage is 220V, and the melting current is controlled to be 100-200A.