CN113913710A - Be-free low-density bulk amorphous alloy and preparation method and application thereof - Google Patents

Be-free low-density bulk amorphous alloy and preparation method and application thereof Download PDF

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CN113913710A
CN113913710A CN202111196889.1A CN202111196889A CN113913710A CN 113913710 A CN113913710 A CN 113913710A CN 202111196889 A CN202111196889 A CN 202111196889A CN 113913710 A CN113913710 A CN 113913710A
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amorphous alloy
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刘思路
伍新华
彭炜
张晓平
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Panxing New Alloy Material Changzhou Co ltd
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Abstract

The invention belongs to the technical field of amorphous alloy, and particularly relates to a low-density block amorphous alloy without Be addition, a preparation method and application thereof; the low-density bulk amorphous alloy without Be addition has the atomic percentage expression as follows: al (Al)aETMbNicCudEreWherein ETM is one or more of groups IVB-VIIB; a is more than or equal to 20 and less than or equal to 22; b is more than or equal to 49 and less than or equal to 52; c is more than or equal to 7 and less than or equal to 10; d is more than or equal to 0.85a and less than or equal to 0.95 a; e is more than 0 and less than or equal to 5; a + b + c + d + e is 100. The low-density bulk amorphous alloy without the addition of Be provided by the invention does not contain a metal element Be, but contains more than 20% of Al element in the composition, so that the density is lower; each constituent element in the alloy has good biologyCompatibility, and can meet the production and use requirements of safety and environmental protection; under the condition of not adding Be element, the biocompatibility of the series of block amorphous alloys is improved by adopting the modification and enhancement effect of Er.

Description

Be-free low-density bulk amorphous alloy and preparation method and application thereof
Technical Field
The invention belongs to the technical field of amorphous alloys, and particularly relates to a low-density block amorphous alloy without Be addition, and a preparation method and application thereof.
Background
Because of the super-quenching solidification, atoms are not as easy to arrange and crystallize in order when the alloy is solidified, and the obtained solid alloy is a long-range disordered structure and has no crystal grains and crystal boundaries of crystalline alloy, so the alloy is called amorphous alloy.
The amorphous substance is a complex multi-body interaction system, and is basically characterized in that atoms and electronic structures are complex, microstructures are disordered in a long range, the system is in a metastable state in energy and has complex multiple relaxation behaviors, and the physical, chemical and mechanical properties, characteristics and structures of the system evolve with time.
Disclosure of Invention
The invention provides a low-density block amorphous alloy without Be addition, a preparation method and application thereof.
In order to solve the technical problem, the invention provides a low-density bulk amorphous alloy without Be addition, which has the atomic percentage expression as follows: al (Al)aETMbNicCudEreWherein ETM is one or more of groups IVB-VIIB; a is more than or equal to 20 and less than or equal to 22; b is more than or equal to 49 and less than or equal to 52; c is more than or equal to 7 and less than or equal to 10; d is more than or equal to 0.85a and less than or equal to 0.95 a; e is more than 0 and less than or equal to 5; a + b + c + d + e is 100.
In a second aspect, the present invention provides a method for preparing a low-density bulk amorphous alloy without Be addition, comprising: sequentially adding the raw materials into a smelting furnace according to the sequence of high and low melting points, and smelting to obtain an alloy ingot; and injecting the alloy ingot into a die, and die-casting to obtain the low-density bulk amorphous alloy without the addition of Be.
In a third aspect, the invention provides an application of a low-density bulk amorphous alloy without Be addition in implantable biomedical materials.
The invention has the beneficial effects that the low-density bulk amorphous alloy without addition of Be does not contain a metal element Be, but contains more than 20% of Al element in the composition, so the density is lower; on the other hand, each component element in the alloy has good biocompatibility, and can meet the production and use requirements of safety and environmental protection; the amorphous alloy is modified and enhanced by the Er element, so that the amorphous alloy has strong amorphous forming capability and excellent mechanical property; and finally, under the condition of not adding Be element, the biocompatibility of the series of block amorphous alloys is improved by adopting the modification and enhancement effect of Er.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and drawings.
In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an XRD pattern of an amorphous rod prepared in example 1 of the present invention;
fig. 2 is an XRD pattern of the amorphous rod prepared in example 2 of the present invention.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
At present, researchers or engineers generally improve the amorphous forming ability of the alloy by adding Be, so that a bulk amorphous alloy system with strong amorphous forming ability is obtained, meanwhile, the Be element density is extremely low, and the density of the bulk amorphous alloy system can Be effectively reduced by adding a proper amount of Be element. However, the Be element may cause toxic action to a human body, the Be element may Be precipitated into an organism environment in an ionic form when the Be-containing bulk amorphous alloy is in an organism, the Be element will continuously diffuse and permeate into the organism tissue, the Be ion will cause the toxic action of the organism tissue, may cause necrosis of surrounding organism tissue, and even induce cancer, so that there is a potential safety hazard in using the Be-containing bulk amorphous alloy in the field of implantable biomedical materials.
In order to solve the problem that the block amorphous alloy with high use safety in the field of implantable biomedical materials, the invention provides a low-density block amorphous alloy without Be addition, and the atomic percentage expression of the low-density block amorphous alloy is as follows: al (Al)aETMbNicCudEreWherein ETM is one or more of groups IVB-VIIB; a is more than or equal to 20 and less than or equal to 22; b is more than or equal to 49 and less than or equal to 52; c is more than or equal to 7 and less than or equal to 10; d is more than or equal to 0.85a and less than or equal to 0.95 a; e is more than 0 and less than or equal to 5; a + b + c + d + e is 100.
Wherein Cu has an atomic radius of
Figure BDA0003303492940000033
Atomic radius of Al is
Figure BDA0003303492940000034
The difference in the radii of Cu atoms and Al atoms is about 12%. In addition, the enthalpy of mixing Cu and Al is negative. According to the invention, the content ratio d/a of Cu to Al is set to be 0.85-0.95, so that the amorphous alloy can form a stable microstructure of a 20-face cluster, and the amorphous forming capability can be improved.
Specifically, the low-density bulk amorphous alloy without the addition of Be provided by the invention does not contain a metal element Be, but contains more than 20% of Al element in the composition, so that the density is lower; on the other hand, each component element in the alloy has good biocompatibility, and can meet the production and use requirements of safety and environmental protection; the amorphous alloy is modified and enhanced by the Er element, so that the amorphous alloy has strong amorphous forming capability and excellent mechanical property; and finally, under the condition of not adding Be element, the biocompatibility of the series of block amorphous alloys is improved by adopting the modification and enhancement effect of Er.
Preferably, the ETM may be, but is not limited to, one or more of Ti, Zr, Hf, Nb.
Optionally, the density of the low-density bulk amorphous alloy can be, but is not limited to, 6.1-6.4 g/cm3。
Specifically, the low-density bulk amorphous alloy without the Be addition contains more than 20% of Al element, so that the density is low, and the density of the low-density bulk amorphous alloy is 6.1-6.4 g/cm3。
Optionally, the critical dimension of the low-density bulk amorphous alloy is not less than 3 mm.
According to the invention, the Er element is used for modifying and enhancing the amorphous alloy, so that the amorphous alloy has strong amorphous forming capability, and a copper die casting method is adopted to prepare the bulk amorphous alloy with the critical dimension not less than 3 mm.
Optionally, the tensile yield strength of the low-density bulk amorphous alloy is not lower than 1150 MPa.
The Er element is used for modifying and reinforcing the amorphous alloy, so that the amorphous alloy has excellent mechanical properties, such as yield strength not lower than 1150MPa in stretching.
In another aspect, the present invention further provides a method for preparing a low-density bulk amorphous alloy without Be addition, comprising: sequentially adding the raw materials into a smelting furnace according to the sequence of high and low melting points, and smelting to obtain an alloy ingot; and injecting the alloy ingot into a die, and die-casting to obtain the low-density bulk amorphous alloy without the addition of Be.
Wherein, optionally, the smelting furnace can be but not limited to a vacuum arc furnace or a cold crucible suspension furnace or a vacuum induction furnace.
Alternatively, the mold may be, but is not limited to, a water-cooled copper mold.
Specifically, removing oxide skins on the surfaces of all metal raw materials, cleaning the raw materials by using industrial ethanol, and weighing according to the required mass of each raw material; sequentially stacking all metal raw materials in a vacuum arc furnace, a cold crucible suspension furnace or a vacuum induction furnace according to the sequence of melting point, and smelting after confirming no fault; after the master alloy is fully and uniformly smelted, obtaining an alloy ingot; and adding the alloy cast ingot into water-cooled copper molds with different sizes, and performing die-casting by using vacuum die-casting equipment to obtain the block amorphous alloy.
In another aspect, the low-density bulk amorphous alloy without Be addition is used for implantable biomedical materials, such as dental implants or hip implants or knee implants, because of the combined effect of not adding Be element and the modification and enhancement of amorphous alloy by element Er, the biocompatibility of the series of bulk amorphous alloys is greatly improved, and the attachment growth density on the surface of the series of bulk amorphous alloys in 30 minutes of human gingival fibroblasts is close to 1 ten thousand per cm at most2And the attachment growth density of the human gingival fibroblast cells on the surface of the commercial pure titanium within 30 minutes is only 3 thousand/cm2。
Example 1
Preparation, forming ability and performance of bulk amorphous alloy
The composition of the bulk amorphous alloy prepared in this example 1 is: al (Al)20Zr51Ni9Cu18Er2The preparation method comprises the following steps:
weighing the components in proportion, sequentially putting Al, Cu, Ni and Zr into a vacuum arc melting furnace, putting Er in the middle, vacuumizing to below 0.1Pa, and then introducing argon of 0.5Pa and striking an arc for melting; after the alloy is melted and solidified, turning over and continuing arc striking and smelting, and repeating for two to three times until the alloy is homogenized; and taking out the alloy ingot, melting the alloy ingot in a die casting machine, and pressing the melted alloy ingot into a water-cooling copper mold with the diameter of 5mm to obtain the block amorphous alloy rod.
The amorphous bar is characterized by XRD after sampling, and the characterization result is shown in figure 1; after the amorphous bar is processed into a tensile sample, a tensile test is carried out, and the test result shows that the yield strength of the amorphous bar is 1471 MPa; the amorphous bar is cultured by gingival cells after in vitro biocompatibility experiment and is subjected to fluorescence microscopyThe lens representation shows that the statistical result shows that the attachment growth density of human gingival fibroblasts on the surface of the bulk amorphous alloy within 30 minutes is 6315/cm2。
Example 2
The composition of the bulk amorphous alloy prepared in this example 2 is: al (Al)22Hf10Ti39Ni9Cu19Er, and the preparation method comprises the following steps:
weighing the components in proportion, sequentially putting Al, Cu, Ni, Ti and Hf into a vacuum arc melting furnace, putting Er in the middle, vacuumizing to below 0.1Pa, and then introducing argon of 0.5Pa and striking an arc for melting; after the alloy is melted and solidified, turning over and continuing arc striking and smelting, and repeating for two to three times until the alloy is homogenized; and taking out the alloy ingot, melting the alloy ingot in a die casting machine, and pressing the melted alloy ingot into a water-cooling copper mold with the diameter of 3mm to obtain a block amorphous alloy rod.
The amorphous bar is characterized by XRD after sampling, and the characterization result is shown in figure 2; after the amorphous bar is processed into a tensile sample, a tensile test is carried out, and the test result shows that the yield strength of the amorphous bar is 1153 MPa; after the amorphous bar is cultured by in vitro biocompatibility experiment-gingival cells, the amorphous bar is characterized by a fluorescence microscope, and statistical results show that the attachment growth density of human gingival fibroblasts on the surface of the block amorphous alloy within 30 minutes is 9967 per cm2。
Example 3
The composition of the bulk amorphous alloy prepared in this example 3 is as follows: al (Al)20Nb2Zr50Ni7Cu17Er4The preparation method comprises the following steps:
weighing the components in proportion, sequentially putting Al, Cu, Ni, Nb and Zr into a vacuum arc melting furnace, putting Er in the middle, vacuumizing to below 0.1Pa, and then introducing argon of 0.5Pa and striking an arc for melting; after the alloy is melted and solidified, turning over and continuing arc striking and smelting, and repeating for two to three times until the alloy is homogenized; and taking out the alloy ingot, melting the alloy ingot in a die casting machine, and pressing the melted alloy ingot into a water-cooling copper mold with the diameter of 5mm to obtain the block amorphous alloy rod.
After the amorphous bar is processed into a tensile sample, the tensile sample is drawnThe tensile test shows that the yield strength is 1513 MPa; after the amorphous bar is cultured by in vitro biocompatibility experiment-gingival cells, the amorphous bar is characterized by a fluorescence microscope, and statistical results show that the attachment growth density of human gingival fibroblasts on the surface of the block amorphous alloy within 30 minutes is 7092/cm2。
Comparative example 1
The composition of the bulk amorphous alloy prepared in the comparative example 1 is as follows: al (Al)17Zr53Ni9Cu18Er3The preparation method comprises the following steps:
weighing the components according to a proportion, wherein the d/a value is 1.06, sequentially putting Al, Cu, Ni and Zr into a vacuum arc melting furnace, putting Er in the middle, vacuumizing to below 0.1Pa, and then introducing argon of 0.5Pa and striking an arc for melting; after the alloy is melted and solidified, turning over and continuing arc striking and smelting, and repeating for two to three times until the alloy is homogenized; taking out the alloy cast ingot, melting in a die casting machine, pressing into a water-cooling copper mold to obtain a completely crystallized alloy bar, wherein the d/a value is not between 0.85 and 0.95, and the amorphous forming capability is sharply weakened.
After the alloy bar is processed into a tensile sample, a tensile test is carried out, and the test result shows that the yield strength of the alloy bar is 317 MPa; after the amorphous bar is cultured by in vitro biocompatibility experiment-gingival cells, the amorphous bar is characterized by a fluorescence microscope, and statistical results show that the attachment growth density of human gingival fibroblasts on the surface of the block amorphous alloy within 30 minutes is 1739/cm2。
Comparative example 2
The composition of the block alloy prepared in this comparative example 2 was: al (Al)20Hf11Ti39Ni9Cu21The preparation method comprises the following steps:
weighing the components in proportion, sequentially putting Al, Cu, Ni, Ti and Hf into a vacuum arc melting furnace, vacuumizing to below 0.1Pa, and then introducing argon of 0.5Pa and striking an arc for melting; after the alloy is melted and solidified, turning over and continuing arc striking and smelting, and repeating for two to three times until the alloy is homogenized; and taking out the alloy ingot, melting the alloy ingot in a die casting machine, and pressing the melted alloy ingot into a water-cooling copper die to obtain a bar which is fragile, so that the bar has no amorphous forming capability.
The alloy bars obtained in the examples and comparative examples were subjected to performance tests, and the data are summarized in Table 1.
TABLE 1 Property data of alloy bars obtained in examples and comparative examples
Figure BDA0003303492940000071
As can Be seen from the data in fig. 1 and 2 and table 1, the low-density bulk amorphous alloy without Be addition prepared in the embodiments of the present invention has a lower density, and when it is used in an in vitro biocompatibility experiment, the attachment growth density on the surface of the bulk amorphous alloy is significantly increased within 30 minutes; compared with the alloy bar in the comparative example 1, the d/a value is 1.06 and is not between 0.85 and 0.95, so that the amorphous forming capability of the alloy bar is sharply weakened, the mechanical property is obviously reduced, and the biocompatibility is poor; in the alloy in the comparative example 2, the d/a value is 1.05, the rare earth element Er is not modified and enhanced, the amorphous forming capability of the alloy is sharply weakened, and the obtained alloy cannot be tested for mechanical property and biocompatibility.
In conclusion, the low-density bulk amorphous alloy without the addition of Be provided by the invention does not contain the metal element Be, but contains more than 20% of Al element in the composition, so that the density is lower; on the other hand, each component element in the alloy has good biocompatibility, and can meet the production and use requirements of safety and environmental protection; the amorphous alloy is modified and enhanced by the Er element, so that the amorphous alloy has strong amorphous forming capability and excellent mechanical property; and finally, under the condition of not adding Be element, the biocompatibility of the series of block amorphous alloys is improved by adopting the modification and enhancement effect of Er.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.

Claims (9)

1. A low-density bulk amorphous alloy without Be addition is characterized in that the atomic percent expression is as follows:
AlaETMbNicCudErewherein
ETM is one or more of IVB-VIIB families;
20≤a≤22；
49≤b≤52；
7≤c≤10；
0.85a≤d≤0.95a；
0＜e≤5；
a+b+c+d+e＝100。
2. the low density bulk amorphous alloy according to claim 1,
the ETM is one or more of Ti, Zr, Hf and Nb.
3. The low density bulk amorphous alloy according to claim 1,
the density of the low-density bulk amorphous alloy is 6.1-6.4 g/cm3。
4. The low density bulk amorphous alloy according to claim 1,
the critical dimension of the low-density bulk amorphous alloy is not less than 3 mm.
5. The low density bulk amorphous alloy according to claim 1,
the tensile yield strength of the low-density bulk amorphous alloy is not lower than 1150 MPa.
6. A preparation method of a Be-free low-density bulk amorphous alloy is characterized by comprising the following steps:
sequentially adding the raw materials of each formula into a smelting furnace according to the sequence of high and low melting points, and smelting to obtain alloy ingots;
and injecting the alloy ingot into a die, and die-casting to obtain the low-density bulk amorphous alloy without the addition of Be.
7. The method according to claim 6,
the smelting furnace is a vacuum arc furnace or a cold crucible suspension furnace or a vacuum induction furnace.
8. The method according to claim 6,
the mould is a water-cooling copper mould.
9. An application of a low-density bulk amorphous alloy without Be addition in implantable biomedical materials.
CN202111196889.1A 2021-10-14 2021-10-14 Be-free low-density bulk amorphous alloy and preparation method and application thereof Pending CN113913710A (en)

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Citations (9)

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US3989517A (en) * 1974-10-30 1976-11-02 Allied Chemical Corporation Titanium-beryllium base amorphous alloys
CN1417369A (en) * 2001-11-09 2003-05-14 中国科学院物理研究所 Low-density blocky metal-glass
US20080135138A1 (en) * 2006-12-07 2008-06-12 Gang Duan Thermoplastically processable amorphous metals and methods for processing same
CN103774065A (en) * 2012-10-19 2014-05-07 华为技术有限公司 Zirconium base amorphous alloy
CN104451470A (en) * 2014-12-29 2015-03-25 东莞台一盈拓科技股份有限公司 Amorphous alloy spectacle frame and glass and production method thereof
CN104651756A (en) * 2015-02-15 2015-05-27 中国科学院金属研究所 (ZrM)-(CuN)-Ni-Al-(Re) amorphous alloy, and preparation method and application thereof
CN104745973A (en) * 2013-12-26 2015-07-01 比亚迪股份有限公司 Zr-based amorphous alloy and manufacturing method thereof
CN105714216A (en) * 2016-02-29 2016-06-29 宋佳 High-tenacity and high-plasticity amorphous alloy and preparation method and application thereof
CN108385039A (en) * 2018-02-07 2018-08-10 瑞声精密制造科技(常州)有限公司 A kind of additional high tenacity Zirconium base non-crystalline composite material and preparation method thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3989517A (en) * 1974-10-30 1976-11-02 Allied Chemical Corporation Titanium-beryllium base amorphous alloys
CN1417369A (en) * 2001-11-09 2003-05-14 中国科学院物理研究所 Low-density blocky metal-glass
US20080135138A1 (en) * 2006-12-07 2008-06-12 Gang Duan Thermoplastically processable amorphous metals and methods for processing same
CN103774065A (en) * 2012-10-19 2014-05-07 华为技术有限公司 Zirconium base amorphous alloy
CN104745973A (en) * 2013-12-26 2015-07-01 比亚迪股份有限公司 Zr-based amorphous alloy and manufacturing method thereof
CN104451470A (en) * 2014-12-29 2015-03-25 东莞台一盈拓科技股份有限公司 Amorphous alloy spectacle frame and glass and production method thereof
CN104651756A (en) * 2015-02-15 2015-05-27 中国科学院金属研究所 (ZrM)-(CuN)-Ni-Al-(Re) amorphous alloy, and preparation method and application thereof
CN105714216A (en) * 2016-02-29 2016-06-29 宋佳 High-tenacity and high-plasticity amorphous alloy and preparation method and application thereof
CN108385039A (en) * 2018-02-07 2018-08-10 瑞声精密制造科技(常州)有限公司 A kind of additional high tenacity Zirconium base non-crystalline composite material and preparation method thereof

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Application publication date: 20220111