CN111549302A - Non-biotoxicity Zr-based amorphous alloy and preparation method thereof - Google Patents
Non-biotoxicity Zr-based amorphous alloy and preparation method thereof Download PDFInfo
- Publication number
- CN111549302A CN111549302A CN202010453326.5A CN202010453326A CN111549302A CN 111549302 A CN111549302 A CN 111549302A CN 202010453326 A CN202010453326 A CN 202010453326A CN 111549302 A CN111549302 A CN 111549302A
- Authority
- CN
- China
- Prior art keywords
- smelting
- amorphous alloy
- based amorphous
- biotoxicity
- alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 52
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 51
- 239000000956 alloy Substances 0.000 claims abstract description 51
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 31
- 229910052742 iron Inorganic materials 0.000 claims abstract description 31
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 31
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 31
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 30
- 238000003723 Smelting Methods 0.000 claims description 63
- 239000010949 copper Substances 0.000 claims description 56
- 239000002994 raw material Substances 0.000 claims description 44
- 229910052751 metal Inorganic materials 0.000 claims description 38
- 239000002184 metal Substances 0.000 claims description 38
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 238000005266 casting Methods 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 6
- 238000010891 electric arc Methods 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 15
- 230000007797 corrosion Effects 0.000 abstract description 13
- 230000007547 defect Effects 0.000 abstract description 4
- 231100000701 toxic element Toxicity 0.000 abstract description 4
- 229910052796 boron Inorganic materials 0.000 abstract description 3
- 229910052745 lead Inorganic materials 0.000 abstract description 3
- 229910052758 niobium Inorganic materials 0.000 abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000006378 damage Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 210000001124 body fluid Anatomy 0.000 description 6
- 239000010839 body fluid Substances 0.000 description 6
- 244000137852 Petrea volubilis Species 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000009931 harmful effect Effects 0.000 description 4
- 231100000956 nontoxicity Toxicity 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 238000010301 surface-oxidation reaction Methods 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- 238000002513 implantation Methods 0.000 description 3
- 229910003310 Ni-Al Inorganic materials 0.000 description 2
- 229910004337 Ti-Ni Inorganic materials 0.000 description 2
- 229910011209 Ti—Ni Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 229910002059 quaternary alloy Inorganic materials 0.000 description 2
- 206010010774 Constipation Diseases 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 208000006083 Hypokinesia Diseases 0.000 description 1
- 206010041349 Somnolence Diseases 0.000 description 1
- 229910011212 Ti—Fe Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 208000007502 anemia Diseases 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000013526 supercooled liquid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/11—Making amorphous alloys
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Prostheses (AREA)
Abstract
The invention discloses a non-biotoxicity Zr-based amorphous alloy and a preparation method thereof, and relates to the technical field of amorphous alloys, wherein the non-biotoxicity Zr-based amorphous alloy consists of Zr, Cu, Al, Ti, Fe and Ni, wherein the Zr atom percentage content is 56%, the Cu atom percentage content is 24%, the Al atom percentage content is 9%, the Ni atom percentage content is 0-6%, the Ti atom percentage content is 4%, and the Fe atom percentage content is 1-7%; the invention has the beneficial effects that: the defect that common toxic elements Nb, Pb, B and V in the conventional Zr-based amorphous alloy have biological toxicity is overcome, the excellent corrosion resistance and high strength of the amorphous alloy are reserved, and the alloy is low in cost, simple to prepare and wide in adaptability.
Description
Technical Field
The invention relates to the technical field of amorphous alloys, in particular to a non-biotoxicity Zr-based amorphous alloy and a preparation method thereof.
Background
The amorphous alloy is different from a crystal material, has a long-range disordered structure, has special physicochemical properties due to the fact that molecules (or atoms and ions) forming the amorphous alloy are not in a spatially regular periodicity, and has a superplasticity phenomenon in a supercooled liquid phase region.
Most of the zirconium-based amorphous alloys contain toxic elements Nb, Pb, B and V, which causes the amorphous alloys to have a plurality of defects in biological application, firstly, because of the application of the zirconium-based amorphous alloy in the biomedical field, in particular as an organism implantation material, toxic elements in the amorphous alloy can generate a series of harmful effects on human bodies along with the prolonging of implantation time, for example, after long-term implantation, metal Pb can obstruct the synthesis of blood, so as to cause anemia of human body, headache, dizziness, hypodynamia, drowsiness, constipation, aching limbs and the like, the long-term accumulation of the metal Nb can also damage the immune system of a human body, so that the existing zirconium-based amorphous alloy has excellent performance which can be applied to biomedical materials, but is harmful to the human body, and cannot be practically applied to the field of biomedical materials at present.
Disclosure of Invention
The invention aims to solve the problems and the defects, and provides a nonbiotoxicity Zr-based amorphous alloy which overcomes the defect that common toxic elements Nb, Pb, B and V in the conventional Zr-based amorphous alloy have alloy components toxic to organisms, and retains the excellent corrosion resistance and high strength of the amorphous alloy, and a preparation method thereof.
In order to achieve the purpose, the adopted technical scheme is as follows:
a non-biotoxic Zr-based amorphous alloy, consisting of elements Zr, Cu, Al, Ti, Fe, Ni, wherein the Zr atomic percent content is 56%, and the Cu atomic percent content is 24%, the Al atomic percent content is 9%, and the Ni atomic percent content is 0-6%, the Ti atomic percent content is 4%, and the Fe atomic percent content is 1-7%, the purities of Zr, Ti, Al, Cu, Ni, Fe are industrial purities, and Zr contains Hf, the alloy chemical formula of the non-biotoxic Zr-based amorphous alloy is Zr56Cu24Al9Ni (7-x) Ti4Fex, wherein x may be 1, 3, 5 or 7.
The method for preparing the non-biotoxicity Zr-based amorphous alloy comprises the following steps:
A. preparing materials:
respectively weighing Zr, Ti, Al, Cu, Ni and Fe metal raw materials according to the composition and the atomic percentage of Zr56Cu24Al9Ni (7-x) Ti4 Fex;
B. smelting a master alloy:
smelting raw materials by adopting a vacuum arc furnace, and smelting the metal raw materials in the step A into uniform master alloy cast ingots;
C. material molding:
and D, preparing the mother alloy ingot in the step B into a rod-shaped or thin-strip-shaped zirconium-based amorphous alloy by adopting a vacuum copper mold suction casting forming rapid cooling method or a copper roll strip throwing method.
Preferably, the total mass percentage of Zr and Hf is more than 99%.
Preferably, the purities of the metal raw materials of Ti, Al, Cu, Ni and Fe are all more than 99.5%.
The preparation method of the non-biotoxicity Zr-based amorphous alloy is adopted, and the step B comprises the following steps:
b1, putting the metal raw materials into a vacuum arc melting furnace, vacuumizing to 8 x10 < -3 > Pa, and filling high-purity argon protective gas of 0.3-0.5MPa into the furnace;
b2, smelting a pure Ti ingot which is put in advance, and further reducing the oxygen content in the working cavity of the smelting furnace;
b3, uniformly smelting the metal raw materials, avoiding electric arc blowing, and obtaining uniform initial cast ingots;
and B4, repeatedly smelting the obtained cast ingot for more than 5 times to obtain a master alloy cast ingot with uniform chemical components.
Preferably, the smelting times in the step B3 and the step B4 are more than or equal to 5 times, each smelting time is 1-3min, and the smelting current is 150-220A.
The preparation method of the non-biotoxicity Zr-based amorphous alloy is adopted, and the step C comprises the following steps:
c1, vacuumizing to 5X10-1Pa in advance;
c2, smelting the small alloy to be completely molten in the step B process;
c3, opening the suction casting valve, pushing the melt metal into a copper mold by using air pressure for rapid cooling, and obtaining the alloy bar.
Preferably, the alloy rod is made to have a diameter of 2mm and a length of 40 mm.
By adopting the technical scheme, the beneficial effects are as follows:
zr element has excellent biocompatibility and is widely applied to amorphous alloy as a corrosion-resistant element, the Zr-based amorphous alloy greatly reduces the harm of the amorphous alloy to human tissues, Zr-Ni-Al alloy system with the strongest amorphous forming capability is selected under the condition of taking Zr as a base, Cu element is added to form oxide as an isolating layer and Ni element is added to promote passivation, the corrosion resistance of the material is enhanced, the amorphous forming capability of the Cu element is also improved, trace Ti, Ni and the like are added to the Zr-based amorphous alloy to help the amorphous alloy to form a compact protective film at room temperature, the Zr-based amorphous alloy has higher self-corrosion potential and smaller self-corrosion current than corresponding crystalline state in human body fluid, the corrosion resistance is obviously enhanced, trace Fe element is added to promote certain biocompatibility under the condition of ensuring no harm to human bodies, therefore, the composition of the biomedical amorphous alloy of the invention excludes the existence of harmful elements, thereby greatly reducing the harmfulness of the implant material to human tissues;
as known from relevant documents, deep eutectic valleys can be found in ternary ZrTiCu and better in quaternary alloy Zr-Cu-Ti-Ni, so that trace Fe and Al are added on the basis of the quaternary alloy Zr-Cu-Ti-Ni to further enhance the amorphous forming capability.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings of the embodiments of the present invention will be briefly described below. Wherein the drawings are only for purposes of illustrating some embodiments of the invention and are not to be construed as limiting the invention to all embodiments thereof.
FIG. 1 is an X-ray diffraction pattern of the amorphous alloy of the present invention.
Detailed Description
In order to make the objects, technical features and technical effects of the technical solutions of the present invention more clear, exemplary solutions of embodiments of the present invention will be described below clearly and completely with reference to the accompanying drawings of specific embodiments of the present invention.
Referring to fig. 1, the present application is a non-biotoxicity Zr-based amorphous alloy, which consists of Zr, Cu, Al, Ti, Fe, Ni elements, wherein the Zr atomic percent content is 56%, and the Cu atomic percent content is 24%, the Al atomic percent content is 9%, and the Ni atomic percent content is 0-6%, the Ti atomic percent content is 4%, and the Fe atomic percent content is 1-7%, the purities of Zr, Ti, Al, Cu, Ni, Fe are industrial purities, and Zr contains Hf, the alloy chemical formula of the non-biotoxicity Zr-based amorphous alloy is Zr56Cu24Al9Ni (7-x) Ti4Fex, wherein x may be 1, 3, 5, or 7, the total mass percent of Zr and Hf is greater than 99%, and the purities of the metal raw materials of Ti, Al, Cu, Ni, Fe are all greater than 99.5%;
in the first embodiment, the first step is,
the preparation method of the non-biotoxicity Zr-based amorphous alloy comprises the following steps:
A. preparing materials:
converting the raw materials into raw materials of Zr 56%, Cu 24%, Al 9%, Ni 6%, Ti 4% and Fe 1% in percentage by mass, taking chemically pure-grade particles of Zr, Cu, Al, Ni, Ti and Fe as metal raw materials according to the composition and the percentage by mass of Zr56Cu24Al9Ni (7-1) Ti4Fex, wherein the purities of the Zr, Ti, Al, Cu, Ni and Fe are industrial purities, the total mass percentage of the Zr and the Hf is more than 99%, and the purities of the Ti, Al, Cu, Ni and Fe metal raw materials are all more than 99.5%, then polishing the weighed metal raw materials of the components by using coarse sand paper to remove a surface oxidation film, then performing ultrasonic cleaning by using acetone and industrial alcohol, and drying by using a blower for standby;
B. smelting a master alloy:
b1, putting the metal raw materials into a vacuum arc melting furnace, vacuumizing to 8 x10 < -3 > Pa, and filling 0.3MPa of high-purity argon protective gas into the furnace;
b2, firstly smelting a pure Ti ingot which is put in advance, so that the oxygen content in the working cavity of the smelting furnace can be further reduced;
b3, uniformly smelting the metal raw material for 5 times to ensure the uniformity of the blank, wherein the smelting time is 1min, the smelting current is 180A, and the electric arc is prevented from blowing off to obtain a uniform initial ingot;
b4, repeatedly smelting the obtained initial ingot for 5 times, wherein the smelting time is also 1min, and the smelting current is also 180A, so as to obtain a master alloy ingot with uniform chemical components;
C. material molding:
c1, vacuumizing to 5X10-1Pa in advance;
c2, smelting the small alloy blocks in the step B process to be completely molten;
c3, placing the alloy ingot melted for many times above a copper mould, opening a suction casting valve, pushing the alloy into the copper mould by using air pressure for rapid cooling, obtaining rod-shaped amorphous alloy, namely alloy bars, with the diameter of 2mm and the length of 40mm by using vacuum suction casting and rapid cooling of the copper mould, and cleaning and drying the amorphous alloy and the copper mould by using alcohol after the melting is finished.
Thus, an amorphous alloy with uniform components can be formed, the amorphous alloy has strong corrosion resistance in human body fluid, excellent mechanical properties and no toxicity harm to human bodies, and reference can be made to the second X-ray from bottom to top in the figure 1.
In the second embodiment, the first embodiment of the method,
the preparation method of the non-biotoxicity Zr-based amorphous alloy comprises the following steps:
A. preparing materials:
converting the raw materials into raw materials of Zr 56%, Cu 24%, Al 9%, Ni 4%, Ti 4% and Fe 3% in percentage by mass, taking chemically pure-grade particles of Zr, Cu, Al, Ni, Ti and Fe as metal raw materials according to the composition and the percentage by mass of Zr56Cu24Al9Ni (7-3) Ti4Fex, wherein the metal raw materials of Zr, Ti, Al, Cu, Ni and Fe have industrial purity, the total percentage by mass of Zr and Hf is more than 99%, and the purity of the metal raw materials of Ti, Al, Cu, Ni and Fe is more than 99.5%, then polishing the weighed metal raw materials of the components by using coarse sand paper to remove a surface oxidation film, then performing ultrasonic cleaning by using acetone and industrial alcohol, and drying by using a blower for standby;
smelting a master alloy:
b1, putting the metal raw materials into a vacuum arc melting furnace, vacuumizing to 8 x10 < -3 > Pa, and filling 0.5MPa of high-purity argon protective gas into the furnace;
b2, firstly smelting a pure Ti ingot which is put in advance, so that the oxygen content in the working cavity of the smelting furnace can be further reduced;
b3, uniformly smelting the metal raw material for more than 5 times to ensure the uniformity of the blank, wherein the smelting time is 3min, the smelting current is 220A, and the electric arc is prevented from blowing off to obtain a uniform initial ingot;
b4, repeatedly smelting the obtained initial ingot for more than 5 times, wherein the smelting time is also 3min, and the smelting current is also 220A, so as to obtain a master alloy ingot with uniform chemical components;
C. material molding:
c1, vacuumizing to 5X10-1Pa in advance;
c2, smelting the small alloy blocks in the step B process to be completely molten;
c3, placing the alloy ingot melted for many times above a copper mould, opening a suction casting valve, pushing the alloy into the copper mould by using air pressure for rapid cooling, obtaining rod-shaped amorphous alloy, namely alloy bars, with the diameter of 2mm and the length of 40mm by using vacuum suction casting and rapid cooling of the copper mould, and cleaning and drying the amorphous alloy and the copper mould by using alcohol after the melting is finished.
Therefore, the amorphous alloy with very uniform components can be formed, the corrosion resistance of the amorphous alloy in human body fluid can be obviously enhanced, the mechanical property is excellent, the amorphous alloy has no toxicity and harm to the human body, and the third X-ray counted from bottom to top in the figure 1 can be referred.
In the third embodiment, the first step is that,
the preparation method of the non-biotoxicity Zr-based amorphous alloy comprises the following steps:
A. preparing materials:
converting the raw materials into raw materials of Zr 56%, Cu 24%, Al 9%, Ni 4%, Ti 4% and Fe 3% in percentage by mass, taking chemically pure-grade particles of Zr, Cu, Al, Ni, Ti and Fe as metal raw materials according to the composition and the percentage by mass of Zr56Cu24Al9Ni (7-5) Ti4Fex, wherein the metal raw materials of Zr, Ti, Al, Cu, Ni and Fe have industrial purity, the total percentage by mass of Zr and Hf is more than 99%, and the purity of the metal raw materials of Ti, Al, Cu, Ni and Fe is more than 99.5%, then polishing the weighed metal raw materials of the components by using coarse sand paper to remove a surface oxidation film, then performing ultrasonic cleaning by using acetone and industrial alcohol, and drying by using a blower for standby;
smelting a master alloy:
b1, putting the metal raw materials into a vacuum arc melting furnace, vacuumizing to 8 x10 < -3 > Pa, and filling 0.2MPa of high-purity argon protective gas into the furnace;
b2, firstly smelting a pure Ti ingot which is put in advance, so that the oxygen content in the working cavity of the smelting furnace can be further reduced;
b3, uniformly smelting the metal raw material for more than 5 times to ensure the uniformity of the blank, wherein the smelting time is 3min, the smelting current is 220A, and the electric arc is prevented from blowing off to obtain a uniform initial ingot;
b4, repeatedly smelting the obtained initial ingot for more than 5 times, wherein the smelting time is also 2min, and the smelting current is also 200A, so as to obtain a master alloy ingot with uniform chemical components;
C. material molding:
c1, vacuumizing to 5X10-1Pa in advance;
c2, smelting the small alloy blocks in the step B process to be completely molten;
c3, placing the alloy ingot melted for many times above a copper mould, opening a suction casting valve, pushing the alloy into the copper mould by using air pressure for rapid cooling, obtaining rod-shaped amorphous alloy, namely alloy bars, with the diameter of 2mm and the length of 40mm by using vacuum suction casting and rapid cooling of the copper mould, and cleaning and drying the amorphous alloy and the copper mould by using alcohol after the melting is finished.
Therefore, the amorphous alloy with very uniform components can be formed, the corrosion resistance of the amorphous alloy in human body fluid can be obviously enhanced, the mechanical property is excellent, the amorphous alloy has no toxicity and harm to the human body, and the fourth X-ray counted from bottom to top in the figure 1 can be referred.
In the fourth embodiment, the first step is that,
the preparation method of the non-biotoxicity Zr-based amorphous alloy comprises the following steps:
A. preparing materials:
converting the raw materials into raw materials of Zr 56%, Cu 24%, Al 9%, Ni 4%, Ti 4% and Fe 3% in percentage by mass, taking chemically pure-grade particles of Zr, Cu, Al, Ni, Ti and Fe as metal raw materials according to the composition and the percentage by mass of Zr56Cu24Al9Ni (7-7) Ti4Fex, wherein the metal raw materials of Zr, Ti, Al, Cu, Ni and Fe have industrial purity, the total percentage by mass of Zr and Hf is more than 99%, and the purity of the metal raw materials of Ti, Al, Cu, Ni and Fe is more than 99.5%, then polishing the weighed metal raw materials of the components by using coarse sand paper to remove a surface oxidation film, then performing ultrasonic cleaning by using acetone and industrial alcohol, and drying by using a blower for standby;
smelting a master alloy:
b1, putting the metal raw materials into a vacuum arc melting furnace, vacuumizing to 8 x10 < -3 > Pa, and filling 0.5MPa of high-purity argon protective gas into the furnace;
b2, firstly smelting a pure Ti ingot which is put in advance, so that the oxygen content in the working cavity of the smelting furnace can be further reduced;
b3, uniformly smelting the metal raw material for more than 5 times to ensure the uniformity of the blank, wherein the smelting time is 3min, the smelting current is 220A, and the electric arc is prevented from blowing off to obtain a uniform initial ingot;
b4, repeatedly smelting the obtained initial ingot for more than 5 times, wherein the smelting time is also 3min, and the smelting current is also 200A, so as to obtain a master alloy ingot with uniform chemical components;
C. material molding:
c1, vacuumizing to 5X10-1Pa in advance;
c2, smelting the small alloy blocks in the step B process to be completely molten;
c3, placing the alloy ingot melted for many times above a copper mould, opening a suction casting valve, pushing the alloy into the copper mould by using air pressure for rapid cooling, obtaining rod-shaped amorphous alloy, namely alloy bars, with the diameter of 2mm and the length of 40mm by using vacuum suction casting and rapid cooling of the copper mould, and cleaning and drying the amorphous alloy and the copper mould by using alcohol after the melting is finished.
Therefore, the amorphous alloy with very uniform components can be formed, the corrosion resistance of the amorphous alloy in human body fluid can be obviously enhanced, the mechanical property is excellent, the amorphous alloy has no toxicity and harm to the human body, and the fifth X-ray counted from bottom to top in the figure 1 can be referred.
Aiming at improving the biocompatibility and corrosion resistance of the amorphous alloy, the Zr-Cu-Al-Ni-Ti-Fe hexahydric component is selected aiming at the biomedical field, so that harmful elements do not exist in the alloy component and the alloy has good electrochemical corrosion performance in human body fluid, in the well-known field, Zr element has excellent biocompatibility and is widely used as a corrosion resistant element in amorphous alloy, in the case of taking Zr as a base, a Zr-Ni-Al alloy system having the strongest amorphous forming ability is selected, adding Cu element to form oxide as isolating layer and Ni element to promote passivation and raise the corrosion resistance of the material, the Cu element also improves the amorphous forming capability, and a trace amount of Fe element is added finally, so that certain biocompatibility is improved under the condition of ensuring no harm to a human body;
in conclusion, the amorphous alloy is prepared by adopting vacuum arc furnace smelting and suction casting methods, the proportion is wide, the preparation process is simple, the production cost is low, and the obtained amorphous alloy has uniform components, excellent mechanical property, strong corrosion resistance and good biocompatibility.
Claims (8)
1. The non-biotoxicity Zr-based amorphous alloy is characterized in that the non-biotoxicity Zr-based amorphous alloy consists of Zr, Cu, Al, Ti, Fe and Ni, wherein the Zr atom percent content is 56%, the Cu atom percent content is 24%, the Al atom percent content is 9%, the Ni atom percent content is 0-6%, the Ti atom percent content is 4%, the Fe atom percent content is 1-7%, the purities of the Zr, Ti, Al, Cu, Ni and Fe are industrial purities, the Zr contains Hf, and the alloy chemical formula of the non-biotoxicity Zr-based amorphous alloy is Zr56Cu24Al9Ni (7-x) Ti4Fex, wherein x can be 1, 3, 5 or 7.
2. A method for preparing the non-biotoxicity Zr-based amorphous alloy according to claim 1, characterized by comprising the following steps:
A. preparing materials:
respectively weighing Zr, Ti, Al, Cu, Ni and Fe metal raw materials according to the composition and the atomic percentage of Zr56Cu24Al9Ni (7-x) Ti4 Fex;
B. smelting a master alloy:
smelting raw materials by adopting a vacuum arc furnace, and smelting the metal raw materials in the step A into uniform master alloy cast ingots;
C. material molding:
and D, preparing the mother alloy ingot in the step B into a rod-shaped or thin-strip-shaped zirconium-based amorphous alloy by adopting a vacuum copper mold suction casting forming rapid cooling method or a copper roll strip throwing method.
3. The non-biotoxicity Zr-based amorphous alloy according to claim 1, characterized in that: the total mass percent of Zr and Hf is more than 99%.
4. The non-biotoxicity Zr-based amorphous alloy according to claim 1, characterized in that: the purities of the Ti, Al, Cu, Ni and Fe metal raw materials are all more than 99.5%.
5. The method for preparing the non-biotoxicity Zr-based amorphous alloy according to claim 2, wherein the step B comprises the following steps:
b1, putting the metal raw materials into a vacuum arc melting furnace, vacuumizing to 8 x10 < -3 > Pa, and filling high-purity argon protective gas of 0.3-0.5MPa into the furnace;
b2, smelting a pure Ti ingot which is put in advance, and further reducing the oxygen content in the working cavity of the smelting furnace;
b3, uniformly smelting the metal raw materials, avoiding electric arc blowing, and obtaining uniform initial cast ingots;
and B4, repeatedly smelting the obtained cast ingot for more than 5 times to obtain a master alloy cast ingot with uniform chemical components.
6. The method for preparing the non-biotoxicity Zr-based amorphous alloy according to claim 5, wherein the method comprises the following steps: the smelting times in the step B3 and the step B4 are more than or equal to 5 times, each smelting time is 1-3min, and the smelting current is 150-220A.
7. The method for preparing the non-biotoxicity Zr-based amorphous alloy according to claim 2, wherein the step C comprises the following steps:
c1, vacuumizing to 5X10-1Pa in advance;
c2, smelting the small alloy to be completely molten in the step B process;
c3, opening the suction casting valve, pushing the melt metal into a copper mold by using air pressure for rapid cooling, and obtaining the alloy bar.
8. The method for preparing the non-biotoxicity Zr-based amorphous alloy according to claim 7, characterized in that: the diameter of the alloy bar is 2mm, and the length is 40 mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010453326.5A CN111549302A (en) | 2020-05-26 | 2020-05-26 | Non-biotoxicity Zr-based amorphous alloy and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010453326.5A CN111549302A (en) | 2020-05-26 | 2020-05-26 | Non-biotoxicity Zr-based amorphous alloy and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111549302A true CN111549302A (en) | 2020-08-18 |
Family
ID=72008499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010453326.5A Pending CN111549302A (en) | 2020-05-26 | 2020-05-26 | Non-biotoxicity Zr-based amorphous alloy and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111549302A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113981335A (en) * | 2021-10-29 | 2022-01-28 | 盘星新型合金材料(常州)有限公司 | Trace element modified Be-free block amorphous alloy and preparation method and application thereof |
| CN114032478A (en) * | 2021-11-11 | 2022-02-11 | 盘星新型合金材料(常州)有限公司 | Zr-based amorphous alloy with plasticity and preparation method thereof |
| CN115961220A (en) * | 2022-11-04 | 2023-04-14 | 江苏科技大学 | Method for improving pitting corrosion resistance of Zr-based amorphous alloy through Ti element microalloying composite electrochemical cathode hydrogen charging treatment |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101225501A (en) * | 2007-01-16 | 2008-07-23 | 中国科学院物理研究所 | Zirconium-based block metal glass and preparation method thereof |
| CN102071370A (en) * | 2011-01-11 | 2011-05-25 | 大连理工大学 | High-anticorrosion Zr-Al-Ni-Nb block amorphous alloy |
| CN104762497A (en) * | 2015-05-05 | 2015-07-08 | 湖南理工学院 | Zr-Al-Ni-Cu bulk amorphous alloy series with indoor temperature compressive plasticity and high strength |
| CN105603336A (en) * | 2016-01-13 | 2016-05-25 | 东莞劲胜精密组件股份有限公司 | Zirconium-based amorphous alloy and preparation method thereof |
| US10494698B1 (en) * | 2014-10-01 | 2019-12-03 | Materion Corporation | Methods for making zirconium based alloys and bulk metallic glasses |
-
2020
- 2020-05-26 CN CN202010453326.5A patent/CN111549302A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101225501A (en) * | 2007-01-16 | 2008-07-23 | 中国科学院物理研究所 | Zirconium-based block metal glass and preparation method thereof |
| CN102071370A (en) * | 2011-01-11 | 2011-05-25 | 大连理工大学 | High-anticorrosion Zr-Al-Ni-Nb block amorphous alloy |
| US10494698B1 (en) * | 2014-10-01 | 2019-12-03 | Materion Corporation | Methods for making zirconium based alloys and bulk metallic glasses |
| CN104762497A (en) * | 2015-05-05 | 2015-07-08 | 湖南理工学院 | Zr-Al-Ni-Cu bulk amorphous alloy series with indoor temperature compressive plasticity and high strength |
| CN105603336A (en) * | 2016-01-13 | 2016-05-25 | 东莞劲胜精密组件股份有限公司 | Zirconium-based amorphous alloy and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 王明海: "《冶金生产概论》", 31 August 2008 * |
| 罗绍华等: "《功能材料》", 31 December 2012 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113981335A (en) * | 2021-10-29 | 2022-01-28 | 盘星新型合金材料(常州)有限公司 | Trace element modified Be-free block amorphous alloy and preparation method and application thereof |
| CN113981335B (en) * | 2021-10-29 | 2022-09-23 | 盘星新型合金材料(常州)有限公司 | Microelement modified Be-free block amorphous alloy and preparation method and application thereof |
| CN114032478A (en) * | 2021-11-11 | 2022-02-11 | 盘星新型合金材料(常州)有限公司 | Zr-based amorphous alloy with plasticity and preparation method thereof |
| CN115961220A (en) * | 2022-11-04 | 2023-04-14 | 江苏科技大学 | Method for improving pitting corrosion resistance of Zr-based amorphous alloy through Ti element microalloying composite electrochemical cathode hydrogen charging treatment |
| CN115961220B (en) * | 2022-11-04 | 2023-10-27 | 江苏科技大学 | Method for improving pitting corrosion resistance of Zr-based amorphous alloy by Ti element microalloying composite electrochemical cathode hydrogen charging treatment |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111549302A (en) | Non-biotoxicity Zr-based amorphous alloy and preparation method thereof | |
| KR100749658B1 (en) | Sputtering target and method for production thereof | |
| WO2018107830A1 (en) | Highly plastic zirconium-based bulk amorphous alloy with no beryllium or nickel, and method for preparing same | |
| CN105886966B (en) | A kind of zirconium base multicomponent non-crystaline amorphous metal with high thermal stability and preparation method thereof | |
| CN109207872B (en) | Nickel-free beryllium-free copper-free zirconium-based block amorphous alloy with high amorphous forming capability and preparation method thereof | |
| CN109252112B (en) | Ti-based amorphous alloy with super-large amorphous forming capability and preparation method thereof | |
| CN101128609A (en) | Method for casting titanium alloy | |
| JP2004353053A (en) | Titanium based amorphous alloy | |
| CN108796305B (en) | Ti-based Ti-Fe-Zr-Sn-Y biomedical alloy and preparation method thereof | |
| AU751819B2 (en) | Two phase titanium aluminide alloy | |
| CN109355602B (en) | Nickel-free beryllium-free zirconium-based amorphous alloy with high glass forming capability and preparation and application thereof | |
| CN114045446A (en) | Zr-based amorphous alloy with nanoscale thermoplastic forming capability and preparation method and application thereof | |
| JP2801370B2 (en) | Method for producing molded metal article with low oxygen content | |
| CN112063937B (en) | Nickel-free beryllium-free zirconium-based amorphous alloy and preparation method and application thereof | |
| CN111636026B (en) | High-niobium low-density refractory multi-principal-element alloy and vacuum drop casting method thereof | |
| CN115354246B (en) | Rare earth modified light block amorphous alloy and preparation method and application thereof | |
| CN116791014A (en) | Biocompatible TiZrNbAl refractory high-entropy alloy with improved corrosion resistance in simulated body fluid by nanosecond laser shock peening | |
| CN109504925B (en) | zirconium-based bulk amorphous alloy and preparation method and application thereof | |
| CN107779790B (en) | Germanic no without phosphorus large scale palladium base amorphous alloy of nickel of one kind and preparation method thereof | |
| CN111996471B (en) | Zirconium-based amorphous alloy and preparation method and application thereof | |
| JPH0331777B2 (en) | ||
| CN104164578A (en) | Low-modulus high-corrosion-resistance ternary Ni-Ti-Cu alloy and preparation method thereof | |
| CN1847424A (en) | Copper-base lump non-crystalline alloy | |
| CN108913945B (en) | A kind of high-strength titanium alloy and preparation method thereof | |
| CN106735171A (en) | A kind of titanium aluminium pre-alloyed powder puts hydrogen and two step dehydrogenation high temperature insostatic pressing (HIP) manufacturing process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200818 |
|
| RJ01 | Rejection of invention patent application after publication |