CN105296896A - Antibacterial amorphous alloy and manufacturing method thereof - Google Patents
Antibacterial amorphous alloy and manufacturing method thereof Download PDFInfo
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- CN105296896A CN105296896A CN201510775925.8A CN201510775925A CN105296896A CN 105296896 A CN105296896 A CN 105296896A CN 201510775925 A CN201510775925 A CN 201510775925A CN 105296896 A CN105296896 A CN 105296896A
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- crystaline amorphous
- amorphous metal
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Abstract
The invention discloses antibacterial amorphous alloy which comprises a basic alloy component and an added component. The basic alloy component comprises the elements of, by atom mole percentage, 45% to 60% of Zr, 2% to 7% of Hf, 5% to 12% of Ni, 10% to 20% of Al, 10% to 20% of Cu, 0.2% to 3% of Ag and 0.5% to 3% of Co. The added component comprises one or more of Ce, Y, Er and Nd and the adding amount accounts for 0.5% to 5% of the weight of the basic alloy component. The antibacterial amorphous alloy is good in antibacterial performance and the rate for resisting staphylococcus aureus can reach over 99% optimally.
Description
Technical field
The present invention relates to a kind of non-crystaline amorphous metal, particularly relate to a kind of antibacterial non-crystaline amorphous metal and preparation method thereof.
Background technology
Non-crystaline amorphous metal has many traditional carbon steels, good characteristic less than tool steel, as high rigidity, high strength and good solidity to corrosion, starts to gradually adopt non-crystaline amorphous metal to replace traditional alloy material at present in increasing industry.Such as, at medical device industry, because amorphous alloy material can store very large elastic strain energy, so have extraordinary application prospect in the research of Medical implant, again because non-crystaline amorphous metal has good mechanical property, can also be used for making operational tool.In consumer electronics industry, non-crystaline amorphous metal is also more and more applied to preparing structural part and appearance component.Have the much research for non-crystaline amorphous metal at present, people expect that non-crystaline amorphous metal can possess more fine quality, range of application of the prior art are again expanded.
Antibacterial non-crystaline amorphous metal is an important directions of AMORPHOUS ALLOY, has very important economic worth for medical device industry, consumer electronics industry and bullion industry etc.Zirconium-base amorphous alloy not only possesses the good mechanical characteristic that non-crystaline amorphous metal generally possesses, and possesses high erosion resistance and good biocompatibility, so zirconium-base amorphous alloy is the first-selection in antibacterial non-crystaline amorphous metal architectural study in simulation people liquid solution.Application number is provide one in the Chinese patent of by name " a kind of height with anti-microbial effect base block amorphous/nanometer crystal alloy and preparation method thereof " of 201210202707.1 to consist of Zr
53al
16co
23.25ag
7.75the zirconium-base amorphous alloy possessing antibacterial and preparation method thereof, the zirconium-base amorphous alloy that the method is prepared possesses good sterilizing function.
Summary of the invention
Select a zirconium base as the foundational system of non-crystaline amorphous metal in the present invention, by to the improvement of zirconium base alloy system composition and the choose reasonable of preparation method, a kind of zirconium-base amorphous alloy having anti-microbial effect is provided, improvement is made to the Forming ability of this non-crystaline amorphous metal simultaneously, make the antibacterial non-crystaline amorphous metal in the present invention possess larger use value.
Technical problem to be solved by this invention is achieved by the following technical programs:
1, composition of raw materials
In the present invention, antibacterial non-crystaline amorphous metal comprises base alloy component and addO-on therapy, and the elementary composition and atomic molar percentage composition of base alloy component is Zr45-60%, Hf2-7%, Ni5-12%, Al10-20%, Cu10-20%, Ag0.2-3%, Co0.5-3%; AddO-on therapy is one or more in Ce, Y, Er, Nd, the 0.5-5% of alloy compositions weight based on addition.
Zr-Ni-Al-Cu is the formula of the quaternary zirconium-base amorphous alloy often combinationally used in prior art, and add Hf element and this quad alloy system can be made more stable, the close pile structure that non-crystaline amorphous metal is formed is more substantial full.This alloy system Forming ability is good, and the best Forming ability of adjustment formula can reach 15mm.The present invention makes improvement on this basis, adds bactericidal component Ag element and Co element.
Ag element is generally acknowledged high-efficiency antimicrobial metallic element, adds noble metal and often bring the problem that non-crystaline amorphous metal internal bond strength is not strong, the amorphous formation ability of non-crystaline amorphous metal declines in the system of non-crystaline amorphous metal.And for reaching the object of good sterilization, the addition of the precious metal sterilization elements such as Ag often will more than 6%, even reach 10% and more than, not only make alloy internal bond strength and amorphous formation ability decline, also bring the pressure of very large use cost.
Not only adopt Ag element in the present invention, also adopt the mode of adding Co element to coordinate with it, both additions are all no more than 3%, reduce cost of alloy.Co element not only possesses certain sterilizing ability, and be good adhesion agent in a kind of alloying constituent, not only can improve the weave construction of non-crystaline amorphous metal, make between non-crystaline amorphous metal interior atoms more tight, and be used in combination with Ag element, bactericidal property can be made to strengthen further.In the process applying non-crystaline amorphous metal in the present invention, the present inventor also finds to add wear resistance and the toughness that Co element can also strengthen non-crystaline amorphous metal.
Further preferably, the elementary composition and atomic molar percentage composition of base alloy component is Zr50-55%, Hf5-6%, Ni8-10%, Al10-16%, Cu15-20%, Ag2-3%, Co1-2%.
One or more of adding in Ce, Y, Er, Nd effectively can promote the Forming ability of non-crystaline amorphous metal in the present invention, especially when addO-on therapy is Y and/or Nd element, the lifting of amorphous alloy forming ability is comparatively remarkable, the 2-3% of alloy compositions weight based on the addition of Ce, Y, Er, Nd element the best.
2, preparation method
Step one, the pure metal that raw material choose purity is greater than 99.99% carries out proportioning according to the composition of above-mentioned non-crystaline amorphous metal, and wherein Ag, Co raw material adopts nano-silver powder and nano-cobalt powder, and nano-silver powder and nano-cobalt powder granularity are 10-500nm.Atom particle diameter ratio Zr, Al, Ni, Cu, Hf atom particle diameter of Ag element is large, and macroscopically show as in fusion process fusion performance not good, if raw material particle size is excessive, melt very easily bursts or check surface in process of cooling.Adopt nano level Ag raw material then extraordinaryly can improve this point in the present invention, also adopt nano level Co element to coordinate with it simultaneously, make the inner amalgamation of non-crystaline amorphous metal better.Further preferably, nano-silver powder and nano-cobalt powder granularity select 15-50nm best.
Step 2, nano-silver powder and cobalt powder are positioned over the bottom of other alloy raw materials, other alloy raw materials are mixed and is placed on smelting furnace upper strata, by above-mentioned alloy raw material under vacuum condition or inert atmosphere by the melting mode of arc melting or other conventional non-crystaline amorphous metals by raw material melting, can melt back 1-2 time; Vacuum tightness in fusion process is 10
-1-10
-3pa, inert atmosphere pressure is 0.05MPa, obtains non-crystaline amorphous metal ingot casting after cooling, and the rate of cooling of non-crystaline amorphous metal ingot casting is 10
2-10
3k/s.
Nano-silver powder and cobalt powder are placed in bottom alloy raw material, other alloy raw materials are placed in smelting furnace upper strata, in fusion process, Ag and Co element from bottom smelting furnace gradually disperse to the melt of other alloy raw materials, simultaneously due to the surface tension effects of inner alloy melt, the preferential disperse of element of Ag and Co is outer to alloy melt, and the element of Ag and Co forms concentration ladder from amorphous bath surface to melt heart portion, namely Ag and Co element is high at bath surface content, and in heart portion, content is less.After the cooling period, more sterilization element can be assembled in its surface to the non-crystaline amorphous metal of such formation, promotes the efficiency of sterilization.For making non-crystaline amorphous metal more even, can melt back 1-2 time.The vacuum tightness of fusion process or the pressure of inert atmosphere all can adopt the scope used in prior art, as inert atmosphere adopts argon gas atmosphere.
Step 3, obtains above-mentioned non-crystaline amorphous metal product by inhaling the conventional non-crystaline amorphous metal preparation methods such as casting, die casting.
The bactericidal property that non-crystaline amorphous metal in the present invention has possessed, reaches more than 95% to the antibiotic rate of streptococcus aureus.And the non-crystaline amorphous metal in the present invention uses customary preparation methods to use, can be applicable to the manufacture of consumer electronics product, as phone structural etc. and the product of direct body contact, also can be used for medical device product, as scalpel, artificial joint etc., also can be used for having the aerospace industry of demand, machine instrumentation industry, automotive industry and bullion industry etc. simultaneously.
Forming ability the best of non-crystaline amorphous metal in the present invention can reach 18mm, possesses excellent practicality, can be used for preparing complex component.
The present invention has following beneficial effect:
1, the non-crystaline amorphous metal in the present invention has good antimicrobial property, can reach more than 99% to antibiotic rate the best of streptococcus aureus.
2, the non-crystaline amorphous metal in the present invention has good Forming ability, and best Forming ability reaches 18mm.
Embodiment
Embodiment
The pure metal that raw material choose purity is greater than 99.99%, Ag, Co raw material adopts nano-silver powder and nano-cobalt powder, and granularity is 50nm.
Other alloy raw materials are mixed and are placed on smelting furnace upper strata, by above-mentioned alloy raw material 10 by non-crystaline amorphous metal preparation method: bottom nano-silver powder and cobalt powder being positioned over other alloy raw materials
-3under Pa vacuum tightness bar by arc melting by raw material melting, obtain non-crystaline amorphous metal ingot casting after cooling, the rate of cooling of described non-crystaline amorphous metal ingot casting is 10
2k/s.
After prepared by non-crystaline amorphous metal ingot casting, this non-crystaline amorphous metal is made the circular ingot that thickness is 5mm, diameter is 1cm, will be full of and have concentration to be 10
5the agar block of the staphylococcus aureus diluent of cfu/ml is placed in the circular ingot surface of this amorphous, records the sterilizing rate of staphylococcus aureus under circular for this amorphous ingot is placed in 30 ± 2 DEG C of conditions after observing 24h.
Shown in base alloy component table composed as follows, wherein in table based on numeral alloy component elementary composition between atomic molar percentage composition.
The composition of addO-on therapy and component, test result are as shown in the table, the percentage composition of alloy compositions weight based on the numeral wherein after addO-on therapy.
As can be seen from the result of embodiment, the amorphous alloy forming ability in the present invention is maximum reaches 18mm, possesses extraordinary practicality, and good moldability, can be used for preparing complex component simultaneously.Non-crystaline amorphous metal bactericidal property in the present invention is good, to the killing rate of staphylococcus aureus can reach 99% and more than.
Finally it should be noted that, above embodiment is only in order to illustrate the technical scheme of the embodiment of the present invention but not to be limited, although be described in detail the embodiment of the present invention with reference to preferred embodiment, those of ordinary skill in the art is to be understood that and still can modifies to the technical scheme of the embodiment of the present invention or equivalent replacement, and these are revised or be equal to the scope that replacement also can not make amended technical scheme disengaging embodiment of the present invention technical scheme.
Claims (9)
1. an antibacterial non-crystaline amorphous metal, comprise base alloy component and addO-on therapy, it is characterized in that: the elementary composition and atomic molar percentage composition of base alloy component is Zr45-60%, Hf2-7%, Ni5-12%, Al10-20%, Cu10-20%, Ag0.2-3%, Co0.5-3%; AddO-on therapy is one or more in Ce, Y, Er, Nd, the 0.5-5% of alloy compositions weight based on addition.
2. antibacterial non-crystaline amorphous metal as claimed in claim 1, is characterized in that: the elementary composition and atomic molar percentage composition of described base alloy component is Zr50-55%, Hf5-6%, Ni8-10%, Al10-16%, Cu15-20%, Ag2-3%, Co1-2%.
3. antibacterial non-crystaline amorphous metal as claimed in claim 1, is characterized in that: addO-on therapy is Y and/or Nd element.
4. antibacterial non-crystaline amorphous metal as claimed in claim 1, is characterized in that: the 2-3% of alloy compositions weight based on the addition of addO-on therapy.
5. prepare as arbitrary in claim 1-4 as described in the method for antibacterial non-crystaline amorphous metal, it is characterized in that:
Step one, the pure metal that raw material choose purity is greater than 99.99% carries out proportioning according to the composition of above-mentioned non-crystaline amorphous metal, and wherein Ag, Co raw material adopts nano-silver powder and nano-cobalt powder, and nano-silver powder and nano-cobalt powder granularity are 10-500nm;
Step 2, nano-silver powder and cobalt powder are positioned over the bottom of other alloy raw materials, other alloy raw materials are mixed and is placed on smelting furnace upper strata, by above-mentioned alloy raw material under vacuum condition or inert atmosphere by the melting mode of arc melting or other conventional non-crystaline amorphous metals by raw material melting, can melt back 1-2 time; Vacuum tightness in fusion process is 10
-1-10
-3pa, inert atmosphere pressure is 0.05MPa, obtains non-crystaline amorphous metal ingot casting after cooling;
Step 3, obtains above-mentioned non-crystaline amorphous metal product by inhaling the conventional non-crystaline amorphous metal preparation methods such as casting, die casting.
6. the preparation method of antibacterial non-crystaline amorphous metal as claimed in claim 5, is characterized in that: described nano-silver powder and nano-cobalt powder granularity are 15-50nm.
7. the preparation method of antibacterial non-crystaline amorphous metal as claimed in claim 5, is characterized in that: described inert atmosphere is argon gas atmosphere.
8. the preparation method of antibacterial non-crystaline amorphous metal as claimed in claim 5, is characterized in that: the rate of cooling of described non-crystaline amorphous metal ingot casting is 10
2-10
3k/s.
9. an application for antibacterial non-crystaline amorphous metal as described in as arbitrary in claim 1-4, is characterized in that: described non-crystaline amorphous metal can be applicable in consumer electronics product, medical device product, aerospace industry, machine instrumentation industry, automotive industry and bullion industry.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105714216A (en) * | 2016-02-29 | 2016-06-29 | 宋佳 | High-tenacity and high-plasticity amorphous alloy and preparation method and application thereof |
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| CN100580128C (en) * | 2004-09-06 | 2010-01-13 | 瑞士联邦苏黎世技术大学 | Amorphous alloys on the base of ZR and their use |
| US20130255837A1 (en) * | 2012-03-29 | 2013-10-03 | Atakan Peker | Zirconium based bulk metallic glasses |
| CN103911563A (en) * | 2012-12-31 | 2014-07-09 | 比亚迪股份有限公司 | Zr based amorphous alloy and preparation 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 |
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2015
- 2015-11-13 CN CN201510775925.8A patent/CN105296896B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100580128C (en) * | 2004-09-06 | 2010-01-13 | 瑞士联邦苏黎世技术大学 | Amorphous alloys on the base of ZR and their use |
| US20130255837A1 (en) * | 2012-03-29 | 2013-10-03 | Atakan Peker | Zirconium based bulk metallic glasses |
| CN103911563A (en) * | 2012-12-31 | 2014-07-09 | 比亚迪股份有限公司 | Zr based amorphous alloy and preparation 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 |
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| CN105714216A (en) * | 2016-02-29 | 2016-06-29 | 宋佳 | High-tenacity and high-plasticity amorphous alloy and preparation method and application thereof |
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