CN102703842A - Zirconium base blocky amorphous/nanocrystalline alloy with antibacterial action and preparation method thereof - Google Patents

Zirconium base blocky amorphous/nanocrystalline alloy with antibacterial action and preparation method thereof Download PDF

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CN102703842A
CN102703842A CN2012102027071A CN201210202707A CN102703842A CN 102703842 A CN102703842 A CN 102703842A CN 2012102027071 A CN2012102027071 A CN 2012102027071A CN 201210202707 A CN201210202707 A CN 201210202707A CN 102703842 A CN102703842 A CN 102703842A
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alloy
amorphous
zirconium
nanometer crystal
blocky
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CN102703842B (en
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张涛
花能斌
黄璐
逄淑杰
李然
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Beihang University
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Beihang University
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Abstract

The invention discloses a zirconium base blocky amorphous/nanocrystalline alloy with an antibacterial action and a preparation method thereof. The components of the alloy in atomic percentage are ZraAlbCocAgd, wherein a is 50%-55%, b is 15%-17.5%, c is 22.5%-30%, and d is 3%-10%. According to the blocky amorphous alloy provided by the invention, (1), the blocky amorphous alloy has an efficient antibacterial element Ag and has a favorable antibacterial or bacteriostatic function; (2), through carrying out a heat treatment on the blocky amorphous alloy at a certain temperature, the nm-grade Ag is separated out from an amorphous alloy matrix, and such an alloy with an amorphous/nanocrystalline structure has a more favorable antibacterial performance; (3), the zirconium base blocky amorphous/nanocrystalline alloy has strong amorphous formation capability, and the zirconium base amorphous alloy with a critical diameter which is not less than 8 mm can be prepared by adopting a copper die casting method; and (4), compared with a conventional biological medical alloy, the zirconium base blocky amorphous/nanocrystalline alloy has a higher yield strength, a lower modulus of elasticity and better mechanical biocompatibility. Therefore, the series of the amorphous alloys have a wide application prospect in the fields of structural materials, biological materials, medical instruments and the like.

Description

A kind of zirconium-based bulk amorphous/nanometer crystal alloy and preparation method thereof with anti-microbial effect
Technical field
The present invention relates to a kind of bulk amorphous alloy/nanometer crystal alloy material, more particularly, be a kind of contain silver element have zirconium-based bulk amorphous/nanometer crystal alloy of anti-microbial effect and preparation method thereof.
Background technology
The bio-medical metallic substance is the metal or alloy that is used for biomedical sector, has high mechanical strength and anti-fatigue performance, is clinical application load embedded material the most widely.The application of this type of material is very extensive, relates to all respects such as sclerous tissues, soft tissue, artificial organs and surgery auxiliary appliance.Be used for clinical medical metal material and mainly contained stainless steel, cobalt base alloy and titanium base alloy etc.In addition, also have shape memory alloy, precious metal and pure metal tantalum, niobium, zirconium etc.Subject matter during medical metal material is used is: because the corrosion of physiological environment can cause metals ion to organize diffusion to cause the transformation of toxic side effect, embedded material self property and the infectation of bacteria after the implant surgery towards periphery.Bacterium can form biofilm load in the implants material surface of implant into body and adjacent tissue, thereby local organization produced to destroy causes infection.Even give the antibiotic prophylaxis treatment of system before the art; The infection rate of artificial coxa and total knee arthroplasty still reaches 0.5% and 4% respectively; And need carry out antibiotic therapy in hospital, take out the incidence average out to 5.8% of the serious pin track infection of screw or dismounting exterior fixing rack.It is thus clear that the infections relating of joint prosthesis and implants postoperative remains a great problem that the bio-medical metal is used, the bio-medical metallic substance that exploitation has an antibacterial is significant to the infection rate that reduces after the implant surgery.In order to make medical metal material obtain antibacterial; Normally obtain to contain the film of high-efficiency antimicrobial elemental copper or silver through the means of ion implantation or magnetron sputtering, thereby make medical metal material have antibacterial on medical metal material (like titanium alloy, medical stainless steel or vitallium) surface.But because film is with basal body binding force is relatively poor and embedded material in use can wear and tear, the antibacterial of said material can be lost after using certain hour gradually.Other class methods in medical metal, add copper exactly or the silver element alloying makes it to have antibacterial; As in stainless steel, adding a certain amount of copper; Make alloy separate out tiny ε-Cu phase through antibiotic thermal treatment again; Thereby the acquisition antibacterial is same, in stainless steel, adds the stainless steel that a certain amount of silver also can obtain to have antibacterial.
Zirconium-base amorphous alloy has HS, high firmness, high-fracture toughness and excellent corrosion resistance nature, thereby receives people and pay close attention to widely and study, especially in the application of structured material and technical field of biological material.Zirconium-base amorphous alloy has very high erosion resistance and excellent biological compatibility in anthropomorphic dummy's liquid solution.In addition, zirconium-base amorphous alloy also has high elastic limit and lower Young's modulus, is about 2% (medical stainless steel is merely 0.3%) like the elastic deformation amount; Young's modulus is that (titanium or titanium alloy is 110～125GPa to 70～100GPa; Medical 316L stainless steel is 200GPa), more (elastic limit of natural bone is about 1%, and Young's modulus is 20～40GPa) near natural bone than medical metal material commonly used at present; Simultaneously; Zirconium-base amorphous alloy also has excellent biological compatibility, and this makes zirconium-base amorphous alloy at joint prosthesis, and bio-medical aspects such as femoral head supporter and dentistry implant have broad application prospects.Thereby exploitation contains the zirconium-base amorphous alloy of high-efficiency antimicrobial silver element; Make it have antibacterial and have good mechanics of non-crystaline amorphous metal and chemical property simultaneously, the zirconium-base amorphous alloy of this structure-function integration has application promise in clinical practice in the bio-medical field.
In addition, because germ is ubiquitous, unwanted bacteria is threatening people's Health and Living constantly.For fear of the cross infection of bacterium, the research of anti-biotic material and application more and more receive people's attention.
Summary of the invention
Technology of the present invention is dealt with problems: be directed against particularly higher this problem of embedded material postoperative infectation of bacteria probability of present medical metal material; In order to reduce its infectation of bacteria probability; A kind of ZrAl-Co-Ag block amorphous alloy is provided; Contain 3%～10% high-efficiency antimicrobial Ag element in the alloy, can suppress the growth of streptococcus aureus effectively.
Of the present invention another dealt with problems: pass through in addition this Zr-Al-CoAg block amorphous alloy thermal treatment under 803～853K; Acquisition contains the amorphous/nanocrystalline composite diphase material of F.C.C. (fcc)-Ag of 5～50nm in noncrystal substrate; Can further improve its anti-microbial property, the zirconium-base amorphous/nanometer crystal alloy of this structure-function integration has a good application prospect in the bio-medical field.
The present invention's advantage compared with prior art is:
(1) the present invention contains antiseptic elements Ag efficiently, has good antibiotic or bacteria resistance function, and the zirconium-base amorphous/nanometer crystal alloy with antibacterial of the present invention is a block amorphous alloy field reported first;
(2) the present invention through thermal treatment after, separate out other F.C.C. of nm level (fcc)-Ag in the non-crystaline amorphous metal matrix, the alloy of this amorphous/nanocrystalline structure has better anti-microbial property;
(3) the present invention has strong amorphous formation ability, adopts copper mold casting method can prepare the zirconium-base amorphous alloy that critical diameter is not less than 8mm;
(4) the present invention and traditional bio-medical alloy phase ratio, (1990MPa～2000MPa), (93GPa～94GPa), the mechanics biocompatibility is better for lower Young's modulus to have higher ys.
Description of drawings
The Zr that Fig. 1 makes for the present invention 53Al 16Co 27.9Ag 3.1Block amorphous alloy, Zr 53Al 16Co 24.8Ag 6.2Block amorphous alloy, Zr 53Al 16Co 23.25Ag 7.75The XRD figure spectrum of block amorphous alloy;
The Zr that Fig. 2 makes for the present invention 53Al 16Co 27.9Ag 3.1Block amorphous alloy, Zr 53Al 16Co 24.8Ag 6.2Block amorphous alloy, Zr 53Al 16Co 23.25Ag 7.75The DSC curve of block amorphous alloy;
The Zr that Fig. 3 makes for the present invention 53Al 16Co 27.9Ag 3.1Block amorphous alloy, Zr 53Al 16Co 24.8Ag 6.2Block amorphous alloy, Zr 53Al 16Co 23.25Ag 7.75The room temperature stress under compression strain curve of block amorphous alloy;
The Zr that Fig. 4 makes for the present invention 53Al 16Co 23.25Ag 7.75The transmission electron microscope photo of block amorphous alloy after thermal treatment under 813K and the 843K.
Embodiment
Introduce the present invention in detail below in conjunction with accompanying drawing and specific embodiment.But following embodiment only limits to explain the present invention, and protection scope of the present invention should comprise the full content of claim, is not limited only to present embodiment.The present invention is a kind of zirconium-based bulk amorphous/nanometer crystal alloy with anti-microbial effect and preparation method thereof, wherein/represent to refer to non-crystaline amorphous metal or amorphous and nanocrystalline simultaneous alloy.
Said alloy composition composition is atomic percent: Zr aAl bCo cAg d, wherein a:50%～55%, b:15%～17.5%, c:22.5%～30%, d:3%～10%, its antibiotic rate to streptococcus aureus reaches 74-99%.
Said alloy Zr aAl bCo cAg dThe atomic percent of moity is: a:53%, b:16%, c:27.9%, d:3.1%, and it has high amorphous formation ability, and the critical formation size that can prepare non-crystaline amorphous metal is greater than 8mm, and its antibiotic rate to streptococcus aureus reaches more than 74%.
Said alloy Zr aAl bCo cAg dThe atomic percent of moity is: a:53%, b:16%, c:24.8%, d:6.2%, and it has high amorphous formation ability, and the critical formation size that can prepare non-crystaline amorphous metal is greater than 16mm, and its antibiotic rate to streptococcus aureus reaches more than 83%.
Said alloy Zr aAl bCo cAg dThe atomic percent of moity is: a:53%, b:16%, c:23.25%, d:7.75%, and it has high amorphous formation ability, and the critical formation size that can prepare non-crystaline amorphous metal is greater than 20mm, and its antibiotic rate to streptococcus aureus reaches more than 90%.
Said alloy can obtain to contain the fcc-Ag amorphous/nanocrystalline alloy of 5～50nm through thermal treatment under 803～853K, and this amorphous/nanocrystalline alloy reaches more than 99% the antibiotic rate of streptococcus aureus.
The mass percent purity of said zirconium (Zr) is 99.8%; The mass percent purity of cobalt (Co) is 99.98%; The mass percent purity of aluminium (Al) is 99.9%; The mass percent purity of silver (Ag) is 99.9%.
It is following to prepare a kind of zirconium-based bulk amorphous/nanometer crystal alloy step with anti-microbial effect:
Step 1: according to the said batching of claim 1
Press Zr aAl bCo cAg dNominal composition take by weighing each element;
Step 2: melting system Zr aAl bCo cAg dMother alloy
With step 1 claim desired raw material put into vacuum arc fumace;
Regulate the vacuum tightness 2 * 10 of the Vakuumkammer of vacuum arc fumace -3Pa～5 * 10 -3Pa fills vacuum tightness to 0.1 * 10 that high-purity (99.999%) argon gas makes Vakuumkammer then 5Pa～0.8 * 10 5Pa;
Behind arc melting 120～300s, current interruption forms first alloy pig;
First alloy pig that overturns, behind arc melting 120～300s, current interruption forms second alloy pig;
Second alloy pig that overturns, behind arc melting 120～300s, current interruption, furnace cooling takes out, and makes mother alloy;
Step 3: copper mold casting method prepares the block amorphous alloy sample
The mother alloy that step 2 prepares is put into high frequency furnace;
Regulate the vacuum tightness 2 * 10 of the Vakuumkammer of high frequency furnace -3Pa～5 * 10 -3Pa fills vacuum tightness to 0.1 * 10 that high-purity (99.999%) argon gas makes Vakuumkammer then 5Pa～0.8 * 10 5Pa; Under temperature sensor 1200～1500K, be poured in the copper mold behind smelting time 1～3min, and promptly make the block amorphous alloy bar with the copper mold cooling;
Step 4: crystallization and thermal treatment prepares bulk amorphous alloy/nanometer crystal alloy sample
The non-crystaline amorphous metal that step 3 prepares is put into vacuum heat treatment furnace;
With non-crystaline amorphous metal thermal treatment 5～10min under 803～853K, furnace cooling promptly makes bulk amorphous alloy/nanometer crystal alloy sample then.
With its xsect of block amorphous alloy bar intercepting that the copper mold casting makes, carry out X-ray diffraction test and transmission electron microscope test; From as cast condition pole longitudinal section intercepting small amount of sample, utilize DSC (DSC) to carry out heat analysis; The intercepting specification is the non-crystaline amorphous metal bar of 2mm (diameter) * 4mm (highly) from the pole, utilizes its room temperature Static Compression mechanics performance of universal testing machine test; The intercepting specification is the sheet alloy sample of 10mm (length) * 10mm (width) * 2mm (highly), carries out the anti-microbial property evaluation by QB/T2591-2003 " antibiotic plastic---anti-microbial property TP and antibacterial effect " standard.Main experimental arrangement is following:
(1) detects with bacterium and add bacterium and measure: streptococcus aureus bacterium ATCC6538, concentration 6.0 * 10 5Cfu/ml.
(2) detection method: sample to be detected is handled with 75% ethanol disinfection and dried, bacterial classification is subsequent use with the bacteria suspension that saline water is diluted to proper concn.The bacteria suspension of getting 8 microlitres drops in sample surfaces, and (8mm * 8mm) cover on it makes bacteria suspension between sample and film, form uniform liquid film with the thick polyvinylidene film of 0.1mm.Keep relative humidity 90% to cultivate 18-24 hour at 37 ℃.With saline water bacterium liquid is washed, be diluted to suitable concentration gradient, get 0.1ml and be uniformly coated on the aseptic nutrient agar that has prepared.Cultivated observations 18-24 hour in 37 ℃.Negative control replaces with aseptic plate, and other operation is identical.
(3) the antibiotic rate calculation formula is: R (%)=(A-B)/A * 100
In the formula:
R-antibiotic rate (%)
A-negative control sample average reclaims colony count (cfu/ sheet)
B-antibiotic sample average reclaims colony count (cfu/ sheet).
Below in conjunction with following each embodiment the present invention is elaborated.
Embodiment 1:
Adopt copper mold casting method to prepare the Zr that diameter is 8mm 53Al 16Co 27.9Ag 3.1Block amorphous alloy
Step 1: batching
Press Zr 53Al 16Co 27.9Ag 3.1Nominal composition take by weighing raw material;
Wherein, the mass percent purity of zirconium (Zr) is 99.8%; The mass percent purity of cobalt (Co) is 99.98%; The mass percent purity of aluminium (Al) is 99.9%; The mass percent purity of silver (Ag) is 99.9%.
Step 2: melting system Zr 53Al 16Co 27.9Ag 3.1Mother alloy
With step 1 claim raw material put into vacuum arc fumace;
Regulate the vacuum tightness 5 * 10 of the Vakuumkammer of vacuum arc fumace -3Pa fills vacuum tightness to 0.5 * 10 that high-purity (99.999%) argon gas makes Vakuumkammer then 5Pa;
Behind arc melting 240s, current interruption forms first alloy pig;
First alloy pig that overturns, behind arc melting 180s, current interruption forms second alloy pig;
Second alloy pig that overturns, behind arc melting 180s, current interruption forms the 3rd alloy pig;
The 3rd alloy pig that overturns, behind arc melting 180s, current interruption, furnace cooling takes out, and makes mother alloy;
Step 3: the preparation diameter is the Zr of 8mm 53Al 16Co 27.9Ag 3.1Block amorphous alloy
The mother alloy that step 2 makes is put into high frequency furnace;
Regulate the vacuum tightness 5 * 10 of the Vakuumkammer of high frequency furnace -3Pa fills vacuum tightness to 0.5 * 10 that high-purity (99.999%) argon gas makes Vakuumkammer then 5Pa;
Under temperature sensor 1500K, be molded in the copper mold behind the smelting time 2min, and promptly make the Zr of diameter 8mm with the copper mold cooling 53Al 16Co 27.9Ag 3.1The block amorphous alloy bar.
Step 4: the structure that characterizes bulk amorphous alloy with X-ray diffraction method
The Zr that embodiment 1 is made 53Al 16Co 27.9Ag 3.1The X-ray diffraction test is carried out in its longitudinal section of block amorphous alloy bar intercepting, and its X ray diffracting spectrum is seen Fig. 1.X-coordinate is 2 θ angles among the figure, and ordinate zou is diffraction intensity (intensity); Can find out that from diffracting spectrum this sample is a non-crystal structure.
Step 5: utilize DSC (DSC) to carry out heat analysis
The Zr that embodiment 1 is made 53Al 16Co 27.9Ag 3.1Its heart portion pocket of block amorphous alloy bar intercepting carries out hot analytical test to it, obtains thermodynamical coordinate.Its DSC curve is seen Fig. 2, and X-coordinate is temperature (unit K) among the figure; Ordinate zou is heat (heat flow), and downward direction is heat release (Exothermic), its glass transition temp (T g) be 753K, crystallization temperature (T x) be 808K, supercooling liquid phase region (T x-T g) 55K, liquidus temperature (T 1) 1235K, reduction glass transformation temperature (T Rg) 0.609.
Step 6: adopt testing machine for mechanical properties test Zr 53Al 16Co 27.9Ag 3.1The room temperature compression mechanical property of block amorphous alloy, the stress-strain(ed) curve of its compression process is as shown in Figure 3.Can find out that this alloy ys is 1990MPa, Young's modulus is 93GPa, amount of plastic deformation 1.7%.
Step 7: to Zr 53Al 16Co 27.9Ag 3.1The tabular sample of non-crystaline amorphous metal has carried out the anti-microbial property test, and its antibiotic rate to streptococcus aureus is 74%.
Embodiment 2:
Adopt copper mold casting method to prepare the Zr that diameter is 16mm 53Al 16Co 24.8Ag 6.2Block amorphous alloy
Step 1: batching
Press Zr 53Al 16Co 24.8Ag 6.2Nominal composition take by weighing raw material;
Wherein, the mass percent purity of zirconium (Zr) is 99.8%; The mass percent purity of cobalt (Co) is 99.98%; The mass percent purity of aluminium (Al) is 99.9%; The mass percent purity of silver (Ag) is 99.9%.
Step 2: melting system Zr 53Al 16Co 24.8Ag 6.2Mother alloy
With step 1 claim raw material put into vacuum arc fumace;
Regulate the vacuum tightness 3 * 10 of the Vakuumkammer of vacuum arc fumace -3Pa fills vacuum tightness to 0.8 * 10 that high-purity (99.999%) argon gas makes Vakuumkammer then 5Pa;
Behind arc melting 300s, current interruption forms first alloy pig;
First alloy pig that overturns, behind arc melting 120s, current interruption forms second alloy pig;
Second alloy pig that overturns, behind arc melting 240s, current interruption forms the 3rd alloy pig;
The 3rd alloy pig that overturns, behind arc melting 180s, current interruption, furnace cooling takes out, and makes mother alloy;
Step 3: the preparation diameter is the Zr of 16mm 53Al 16Co 24.8Ag 6.2Block amorphous alloy
The mother alloy that step 2 makes is put into high frequency furnace;
Regulate the vacuum tightness 5 * 10 of the Vakuumkammer of high frequency furnace -3Pa fills vacuum tightness to 0.5 * 10 that high-purity (99.999%) argon gas makes Vakuumkammer then 5Pa;
Under temperature sensor 1350K, be molded in the copper mold behind the smelting time 1.5min, and promptly make the Zr of diameter 16mm with the copper mold cooling 53Al 16Co 24.8Ag 6.2The block amorphous alloy bar.
Step 4: the structure that characterizes bulk amorphous alloy with X-ray diffraction method
The Zr that embodiment 1 is made 53Al 16Co 24.8Ag 6.2The X-ray diffraction test is carried out in its longitudinal section of block amorphous alloy bar intercepting, and its X ray diffracting spectrum is seen Fig. 1.X-coordinate is 2 θ angles among the figure, and ordinate zou is diffraction intensity (intensity); Can find out that from diffracting spectrum this sample is a non-crystal structure.
Step 5: utilize DSC (DSC) to carry out heat analysis
The Zr that embodiment 1 is made 53Al 16Co 24.8Ag 6.2Its heart portion pocket of block amorphous alloy bar intercepting carries out hot analytical test to it, obtains thermodynamical coordinate.Its DSC curve is seen Fig. 2, and X-coordinate is temperature (unit K) among the figure; Ordinate zou is heat (heat flow), and downward direction is heat release (Exothermic), its glass transition temp (T g) be 754K, crystallization temperature (T x) be 792K, supercooling liquid phase region (T x-T g) 38K, liquidus temperature (T 1) 1234K, reduction glass transformation temperature (T Rg) 0.611.
Step 6: adopt testing machine for mechanical properties test Zr 53Al 16Co 24.8Ag 6.2The room temperature compression mechanical property of block amorphous alloy, the stress-strain(ed) curve of its compression process is as shown in Figure 3.Can find out that this alloy ys is 2000MPa, Young's modulus is 93GPa, amount of plastic deformation 1.4%.
Step 7: to Zr 53Al 16Co 24.8Ag 6.2The tabular sample of non-crystaline amorphous metal has carried out the anti-microbial property test, and its antibiotic rate to streptococcus aureus is 83%.
Embodiment 3:
Adopt copper mold casting method to prepare the Zr that diameter is 20mm 53Al 16Co 23.25Ag 7.75Block amorphous alloy
Step 1: batching
Press Zr 53Al 16Co 23.25Ag 7.75Nominal composition take by weighing raw material;
Wherein, the mass percent purity of zirconium (Zr) is 99.8%; The mass percent purity of cobalt (Co) is 99.98%; The mass percent purity of aluminium (Al) is 99.9%; The mass percent purity of silver (Ag) is 99.9%.
Step 2: melting system Zr 53Al 16Co 23.25Ag 7.75Mother alloy
With step 1 claim raw material put into vacuum arc fumace;
Regulate the vacuum tightness 4 * 10 of the Vakuumkammer of vacuum arc fumace -3Pa fills vacuum tightness to 0.5 * 10 that high-purity (99.999%) argon gas makes Vakuumkammer then 5Pa;
Behind arc melting 300s, current interruption forms first alloy pig;
First alloy pig that overturns, behind arc melting 180s, current interruption forms second alloy pig;
Second alloy pig that overturns, behind arc melting 240s, current interruption forms the 3rd alloy pig;
The 3rd alloy pig that overturns, behind arc melting 120s, current interruption, furnace cooling takes out, and makes mother alloy;
Step 3: the preparation diameter is the Zr of 20mm 53Al 16Co 23.25Ag 7.75Block amorphous alloy
The mother alloy that step 2 makes is put into high frequency furnace;
Regulate the vacuum tightness 3 * 10 of the Vakuumkammer of high frequency furnace -3Pa fills vacuum tightness to 0.5 * 10 that high-purity (99.999%) argon gas makes Vakuumkammer then 5Pa;
Under temperature sensor 1300K, be molded in the copper mold behind the smelting time 2min, and promptly make the Zr of diameter 20mm with the copper mold cooling 53Al 16Co 24.8Ag 6.2The block amorphous alloy bar.
Step 4: the structure that characterizes bulk amorphous alloy with X-ray diffraction method
The Zr that embodiment 1 is made 53Al 16Co 23.25Ag 7.75The X-ray diffraction test is carried out in its longitudinal section of block amorphous alloy bar intercepting, and its X ray diffracting spectrum is seen Fig. 1.X-coordinate is 2 θ angles among the figure, and ordinate zou is diffraction intensity (intensity); Can find out that from diffracting spectrum this sample is a non-crystal structure.
Step 5: utilize DSC (DSC) to carry out heat analysis
The Zr that embodiment 1 is made 53Al 16Co 23.25Ag 7.75Its heart portion pocket of block amorphous alloy bar intercepting carries out hot analytical test to it, obtains thermodynamical coordinate.Its DSC curve is seen Fig. 2, and X-coordinate is temperature (unit K) among the figure; Ordinate zou is heat (heat flow), and downward direction is heat release (Exothermic), its glass transition temp (T g) be 755K, crystallization temperature (T x) be 791K, supercooling liquid phase region (T x-T g) 36K, liquidus temperature (T 1) 1234K, reduction glass transformation temperature (T Rg) 0.612.
Step 6: adopt testing machine for mechanical properties test Zr 53Al 16Co 23.25Ag 7.75The room temperature compression mechanical property of block amorphous alloy, the stress-strain(ed) curve of its compression process is as shown in Figure 3.Can find out that this alloy ys is 2000MPa, Young's modulus is 94GPa, amount of plastic deformation 1.2%.
Step 7: to Zr 53Al 16Co 23.25Ag 7.75The tabular sample of non-crystaline amorphous metal has carried out the anti-microbial property test, and its antibiotic rate to streptococcus aureus is 90%.
Embodiment 4:
Adopt heat treating process to prepare Zr 53Al 16Co 23.25Ag 7.75Bulk amorphous alloy/nanometer crystal alloy
Adopt embodiment 3 step 1～step 3 method to prepare Zr 53Al 16Co 23.25Ag 7.75Block amorphous alloy,
Step 4: crystallization and thermal treatment prepares Zr 53Al 16Co 23.25Ag 7.75Bulk amorphous alloy/nanometer crystal alloy sample
The non-crystaline amorphous metal that step 3 prepares is put into vacuum heat treatment furnace, and with non-crystaline amorphous metal thermal treatment 10min under 813K, furnace cooling promptly makes bulk amorphous alloy/nanometer crystal alloy sample then.
Step 5: to the Zr after the thermal treatment 53Al 16Co 23.25Ag 7.75Alloy sample carries out the transmission electron microscope test, and its transmission electron microscope photo is shown in Fig. 4 (a), it is thus clear that in the noncrystal substrate of alloy, separated out F.C.C. (fcc)-Ag of 5～30nm.
Step 6: to the Zr behind the thermal treatment 10min under 813K 53Al 16Co 23.25Ag 7.75The tabular sample of non-crystaline amorphous metal has carried out the anti-microbial property test, and its antibiotic rate to streptococcus aureus is 99%.
Embodiment 5:
Adopt heat treating process to prepare Zr 53Al 16Co 23.25Ag 7.75Bulk amorphous alloy/nanometer crystal alloy
Adopt embodiment 3 step 1～step 3 method to prepare Zr 53Al 16Co 23.25Ag 7.75Block amorphous alloy,
Step 4: crystallization and thermal treatment prepares Zr 53Al 16Co 23.25Ag 7.75Bulk amorphous alloy/nanometer crystal alloy sample
The non-crystaline amorphous metal that step 3 prepares is put into vacuum heat treatment furnace, and with non-crystaline amorphous metal thermal treatment 10min under 843K, furnace cooling promptly makes bulk amorphous alloy/nanometer crystal alloy sample then.
Step 5: to the Zr after the thermal treatment 53Al 16Co 23.25Ag 7.75Alloy sample carries out the transmission electron microscope test, and its transmission electron microscope photo is shown in Fig. 4 (a), it is thus clear that in the noncrystal substrate of alloy, separated out F.C.C. (fcc)-Ag of 5～50nm.
Step 5: to the Zr behind the thermal treatment 10min under the 843K 53Al 16Co 23.25Ag 7.75The tabular sample of non-crystaline amorphous metal has carried out the anti-microbial property test, and its antibiotic rate to streptococcus aureus is 99%.
Need to prove that according to the above embodiment of the present invention, those skilled in the art are the four corners that can realize claim 1 of the present invention and appurtenance fully, implementation procedure and method be with above-mentioned each embodiment.
In a word, block amorphous alloy of the present invention (1) contains antiseptic elements Ag efficiently, has good antibiotic or bacteria resistance function; (2) to after the block amorphous alloy thermal treatment at a certain temperature, separate out other F.C.C. of nm level (fcc)-Ag in the non-crystaline amorphous metal matrix, this alloy with amorphous/nanocrystalline structure has better anti-microbial property; (3) have strong amorphous formation ability, adopt copper mold casting method can prepare the zirconium-base amorphous alloy that critical diameter is not less than 8mm; (4) with traditional bio-medical alloy phase ratio, have higher ys, lower Young's modulus, the mechanics biocompatibility is better.Therefore, this series amorphous/nanocrystalline alloy has broad application prospects in fields such as structured material, biomaterial and medicine equipments.The antibiotic alloy of the present invention's exploitation except being used to resist the postoperative infectation of bacteria at biomedicine field; The every field that also can be used for daily life comprises kitchen guarding's apparatus (like water tumbler, tank), communal facility (like bus handle, elevator push button), food safety field (like foodstuff production, transportation) etc.

Claims (8)

1. zirconium-based bulk amorphous/nanometer crystal alloy with anti-microbial effect, it is characterized in that: said alloy composition composition is atomic percent: Zr aAl bCo cAg d, wherein a:50%～55%, b:15%～17.5%, c:22.5%～30%, d:3%～10%, its antibiotic rate to streptococcus aureus reaches 74-99%.
2. a kind of zirconium-based bulk amorphous/nanometer crystal alloy with anti-microbial effect according to claim 1 is characterized in that: said alloy Zr aAl bCo cAg dThe atomic percent of moity is: a:53%, b:16%, c:27.9%, d:3.1%, the critical formation size that can prepare non-crystaline amorphous metal is greater than 8mm, and the antibiotic rate of streptococcus aureus is reached more than 74%.
3. a kind of zirconium-based bulk amorphous/nanometer crystal alloy with anti-microbial effect according to claim 1 is characterized in that: said alloy Zr aAl bCo cAg dThe atomic percent of moity is: a:53%, b:16%, c:24.8%, d:6.2%, the critical formation size that can prepare non-crystaline amorphous metal is greater than 16mm, and the antibiotic rate of streptococcus aureus is reached more than 83%.
4. a kind of zirconium-based bulk amorphous/nanometer crystal alloy with anti-microbial effect according to claim 1 is characterized in that: said alloy Zr aAl bCo cAg dThe atomic percent of moity is: a:53%, b:16%, c:23.25%, d:7.75%, the critical formation size that can prepare non-crystaline amorphous metal is greater than 20mm, and the antibiotic rate of streptococcus aureus is reached more than 90%.
5. according to one of any described a kind of zirconium-based bulk amorphous/nanometer crystal alloy with anti-microbial effect of claim 1-4, it is characterized in that: said alloy has the compression yield strength of 1990MPa～2000MPa, Young's modulus 93GPa～94GPa.
6. according to one of any described a kind of zirconium-based bulk amorphous/nanometer crystal alloy of claim 1-4 with anti-microbial effect; It is characterized in that: said alloy is through thermal treatment under 803～853K; Can obtain to contain the amorphous/nanocrystalline alloy of F.C.C. (fcc)-Ag of 5～50nm; This amorphous/nanocrystalline alloy reaches more than 99% the antibiotic rate of streptococcus aureus.
According to claim 1-4 one of any described a kind of have anti-microbial effect zirconium-based bulk amorphous/nanometer crystal alloy, it is characterized in that: the mass percent purity of said zirconium (Zr) is 99.8%; The mass percent purity of cobalt (Co) is 99.98%; The mass percent purity of aluminium (Al) is 99.9%; The mass percent purity of silver (Ag) is 99.9%.
8. preparation method with zirconium-based bulk amorphous/nanometer crystal alloy of anti-microbial effect is characterized in that step is following:
Step 1: according to the said batching of claim 1
Press Zr aAl bCo cAg dNominal composition take by weighing each element;
Step 2: melting system Zr aAl bCo cAg dMother alloy
With step 1 claim desired raw material put into vacuum arc fumace;
Regulate the vacuum tightness 2 * 10 of the Vakuumkammer of vacuum arc fumace -3Pa～5 * 10 -3Pa fills vacuum tightness to 0.1 * 10 that 99.999% high-purity argon gas makes Vakuumkammer then 5Pa～0.8 * 10 5Pa;
Behind arc melting 120～300s, current interruption forms first alloy pig;
First alloy pig that overturns, behind arc melting 120～300s, current interruption forms second alloy pig;
Second alloy pig that overturns, behind arc melting 120～300s, current interruption, furnace cooling takes out, and makes mother alloy;
Step 3: copper mold casting method prepares the block amorphous alloy sample
The mother alloy that step 2 prepares is put into high frequency furnace;
Regulate the vacuum tightness 2 * 10 of the Vakuumkammer of high frequency furnace -3Pa～5 * 10 -3Pa fills vacuum tightness to 0.1 * 10 that 99.999% high-purity argon gas makes Vakuumkammer then 5Pa～0.8 * 10 5Pa; Under temperature sensor 1200～1500K, be poured in the copper mold behind smelting time 1～3min, and promptly make the block amorphous alloy bar with the copper mold cooling;
Step 4: crystallization and thermal treatment prepares bulk amorphous alloy/nanometer crystal alloy sample
The non-crystaline amorphous metal that step 3 prepares is put into vacuum heat treatment furnace;
With non-crystaline amorphous metal thermal treatment 5～10min under 803～853K, furnace cooling promptly makes bulk amorphous alloy/nanometer crystal alloy sample then.
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