CN104745971A - Amorphous alloy and preparation method thereof - Google Patents
Amorphous alloy and preparation method thereof Download PDFInfo
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- CN104745971A CN104745971A CN201310733326.0A CN201310733326A CN104745971A CN 104745971 A CN104745971 A CN 104745971A CN 201310733326 A CN201310733326 A CN 201310733326A CN 104745971 A CN104745971 A CN 104745971A
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Abstract
The invention discloses an amorphous alloy and a preparation method thereof. The composition of the amorphous alloy is shown in the formula (Zr1-xHfx)aCubAlcMdAgeREf, wherein M is at least one selected from the group consisting of Fe, Co, Mn, Ti and Nb, RE is at least one selected from rare earth elements, a, b, c, d, e and f represent corresponding atomic percentages of every element in the zirconium-based amorphous alloy, a is no less than 40 and no more than 70, b is no less than 15 and no more than 35, c is no less than 5 and no more than 15, d is no less than 3 and no more than 15, e is more than 0 and no more than 3, f is more than 0 and no more than 2, and an atomic mol ratio of Zr to Hf satisfies the equation that x is greater than 0 and less than 0.02. The amorphous alloy has improved critical dimension and increased antibacterial effect.
Description
Technical field
The present invention relates to a kind of non-crystaline amorphous metal and preparation method thereof, particularly, relate to and a kind of there is zirconium-base amorphous alloy of large critical size and bacteria resistance function and preparation method thereof.
Background technology
Traditional anti-biotic material is divided into natural biological type, organic type and inorganic type.Chitosan is topmost natural bio-antimicrobial agents, but its commercial applications is limited by its production technique level, is difficult to apply.Many organic antibacterial agents are widely applied in fields such as sterilization, anticorrosion, mildew-resistant, have efficient, resistance to feature of waiting so long, but there is biosafety issues, have the shortcoming such as poor heat resistance, facile hydrolysis.Inorganic antibacterial material is divided into two kinds substantially, i.e. metal and photocatalyst, and most metal ions all has anti-microbial effect.Consider bactericidal property and human safety, silver, copper and zinc are most suitable metal antibacterial material.But in this metalloid, silver is too valuable, be difficult to directly adopt; Copper and zinc, comprehensive mechanical performance and erosion resistance are difficult to the application scenario meeting some high requests, as the mechanism member etc. of consumable electronic product.For photocatalyst class, be mainly TiO
2, it can make bacterium, mould, virus even cancer cells inactivation, but the rear separation of suspension liquid beaded catalyst is a major defect of this material.Therefore, need to develop a kind of alloy material that not only there is very good mechanical properties but also there is anti-microbial effect, greatly will enrich the selection of anti-biotic material.
Non-crystaline amorphous metal, due to special weave construction, makes it have high strength, high rigidity, the excellent material behavior such as corrosion-resistant.Therefore, non-crystaline amorphous metal is applied to the fields such as consumer electronics, military project, medicine equipment, chemical industry, sports equipment just gradually, is a kind of type material with potential commercial application value.
Non-crystaline amorphous metal being improved to have fungistatic effect, undoubtedly by expanding the Application Areas of this type material, also can increase the selection of anti-biotic material.But due to the particular requirement of non-crystaline amorphous metal self, only in non-crystaline amorphous metal composition, add the non-crystaline amorphous metal that the metal with antibacterial effect can not obtain having real application value simply, also need the non-crystaline amorphous metal prepared to have large critical size.Therefore need to provide one not only to have large critical size but also have excellent fungistatic effect, and be applicable to the non-crystaline amorphous metal of heavy industrialization manufacture.
Summary of the invention
The object of the invention is not only there is large critical size but also have excellent fungistatic effect to obtain, and be applicable to the non-crystaline amorphous metal of heavy industrialization manufacture, provide a kind of non-crystaline amorphous metal and preparation method thereof.
To achieve these goals, the invention provides a kind of non-crystaline amorphous metal, wherein, consisting of of this non-crystaline amorphous metal: (Zr
1-xhf
x)
acu
bal
cm
dag
erE
f; Wherein, M is selected from least one in Fe, Co, Mn, Ti and Nb; RE is at least one in rare earth element; A, b, c, d, e and f are the atomic percent that each element is corresponding in this zirconium-base amorphous alloy, are respectively: 40≤a≤70,15≤b≤35,5≤c≤15,3≤d≤15,0 < e≤3,0 < f≤2; Atomic molar between Zr and Hf is than meeting 0 < x < 0.02.
The present invention also provides a kind of method preparing non-crystaline amorphous metal; under the method is included in protection of inert gas or under vacuum condition; the raw material of non-crystaline amorphous metal is carried out melting and cooling forming; wherein; the raw material of described non-crystaline amorphous metal comprises Zr, Hf, Cu, Al, M, Ag and RE, consisting of of the non-crystaline amorphous metal formed by the raw material of described non-crystaline amorphous metal: (Zr
1-xhf
x)
acu
bal
cm
dag
erE
f, wherein, M is selected from least one in Fe, Co, Mn, Ti and Nb; RE is at least one in rare earth element; A, b, c, d, e and f are the atomic percent that each element is corresponding in this zirconium-base amorphous alloy, are respectively: 40≤a≤70,15≤b≤35,5≤c≤15,3≤d≤15,0 < e≤3,0 < f≤2; Atomic molar between Zr and Hf is than meeting 0 < x < 0.02.
In the composition of non-crystaline amorphous metal provided by the invention, the Ag added is specified quantitative, and Zr and Hf combines with specified proportion, both can improve the critical size of non-crystaline amorphous metal, can increase again the fungistatic effect of non-crystaline amorphous metal.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of non-crystaline amorphous metal, wherein, consisting of of this non-crystaline amorphous metal: (Zr
1-xhf
x)
acu
bal
cm
dag
erE
f; Wherein, M is selected from least one in Fe, Co, Mn, Ti and Nb; RE is at least one in rare earth element; A, b, c, d, e and f are the atomic percent that each element is corresponding in this zirconium-base amorphous alloy, are respectively: 40≤a≤70,15≤b≤35,5≤c≤15,3≤d≤15,0 < e≤3,0 < f≤2; Atomic molar between Zr and Hf is than meeting 0 < x < 0.02.
According to the present invention, in the composition of described non-crystaline amorphous metal, by combined for appropriate Ag and Zr and the Hf that combines with specified proportion, the fungistatic effect of non-crystaline amorphous metal can be strengthened and have and can obtain large size non-crystaline amorphous metal.More preferably, by appropriate Ag, Cu and Zr and the Hf that combines with specified proportion combined, the while of having a better fungistatic effect, non-crystaline amorphous metal can have larger critical size.The wherein excessive amorphous formation ability that can affect non-crystaline amorphous metal of elements A g, also increases the cost of alloy simultaneously.In the present invention, select the atomic percent of Ag in described non-crystaline amorphous metal for being greater than 0 and less than 3%.
In the present invention, combined with specified proportion by element Hf and Zr, element Hf is introduced in described non-crystaline amorphous metal, do not cause the reduction of the amorphous formation ability of described non-crystaline amorphous metal, and the zirconium metal using technical grade can be allowed, can industrial production cost be reduced.
According to the present invention, can add appropriate rare earth element, can allow to there is a small amount of impurity element in described non-crystaline amorphous metal, under preferable case, described RE is Y.Wherein, the atomic percent of rare earth element in described non-crystaline amorphous metal is preferably less than 2%.
According to the present invention, can allow to there is a small amount of impurity in described non-crystaline amorphous metal, under preferable case, with the total amount of described non-crystaline amorphous metal for benchmark, in described non-crystaline amorphous metal, the atomic percent of metallic impurity elements is less than 2%, and the atomic percent of nonmetallic impurity element is less than 1%.
According to the preferred embodiment of the present invention, under preferable case, consisting of of described non-crystaline amorphous metal: (Zr
0.9904hf
0.0096)
52cu
29al
10co
5fe
2ag
1y
1, (Zr
0.9904hf
0.0096)
52cu
29al
10co
4fe
2ag
2.5y
0.5, (Zr
0.9918hf
0.0082)
61cu
20al
10co
4fe
2ag
2.5y
0.5or (Zr
0.9904hf
0.0096)
52cu
27al
10co
6fe
1nb
1ti
1ag
1y
1.
In the present invention, in described zirconium-base amorphous alloy composition, when M is a kind of element, d represents the atomic percent that this element is corresponding in described zirconium-base amorphous alloy.When M is selected from element of more than two kinds, d represents the atomic percent sum of often kind of element correspondence in this zirconium-base amorphous alloy that M selects, as (Zr
0.9904hf
0.0096)
52cu
27al
10co
6fe
1nb
1ti
1ag
1y
1, wherein M is selected from Co, Fe, Nb and Ti, d be the atomic percent 6,1,1 and 1 that Co, Fe, Nb and Ti are respectively corresponding in zirconium-base amorphous alloy and, i.e. d=6+1+1+1=9.
According to the present invention, described non-crystaline amorphous metal not only has better fungistatic effect but also has larger critical size simultaneously, and under preferable case, the critical size of described non-crystaline amorphous metal is more than 5mm; Preferably, the critical size of described non-crystaline amorphous metal is 5-15mm.
Present invention also offers a kind of method preparing non-crystaline amorphous metal; under the method is included in protection of inert gas or under vacuum condition; non-crystaline amorphous metal raw material is carried out melting and cooling forming; wherein; described non-crystaline amorphous metal raw material comprises Zr, Hf, Cu, Al, M, Ag and RE, consisting of of the non-crystaline amorphous metal formed by described non-crystaline amorphous metal raw material: (Zr
1-xhf
x)
acu
bal
cm
dag
erE
f, wherein, M is selected from least one in Fe, Co, Mn, Ti and Nb; RE is at least one in rare earth element; A, b, c, d, e and f are the atomic percent that each element is corresponding in this zirconium-base amorphous alloy, are respectively: 40≤a≤70,15≤b≤35,5≤c≤15,3≤d≤15,0 < e≤3,0 < f≤2; Atomic molar between Zr and Hf is than meeting 0 < x < 0.02.
According to the present invention, under preferable case, preferred described RE is Y.
According to the present invention, the raw material of described non-crystaline amorphous metal can select the starting material of the non-crystaline amorphous metal of low-purity to carry out the manufacturing of described non-crystaline amorphous metal, and under preferable case, the purity of described raw material can be more than 97 % by weight.As zirconium material can select the zirconium sponge of technical grade, zirconium hafnium purity can be more than 99.4 % by weight.And provide the starting material of Cu, Al and M metal can adopt purity be more than 99 % by weight technical grade raw material metal.In addition, rare earth metal also can choose the raw material of low-purity, and its purity can be preferably more than 98 % by weight.Consider that rare earth element is oxidizable element, mix for ease of carrying out smelting with mother alloy, preferably add rare earth element with the form of master alloy, be more preferably AlRE alloy, RE is rare earth element y simultaneously.
According to the present invention, described protection of inert gas or vacuum condition are to make alloy raw material obtain protection in fusion process, avoiding oxidized.The antioxidant property of non-crystaline amorphous metal raw material of the present invention is better, therefore lower to the requirement of protection of inert gas or vacuum condition.Described rare gas element is one or more in the periodic table of elements in neutral element gas.The purity of described rare gas element is not less than 95% volume percent, such as, can be 95-99.99% volume percent.Under preferable case, the vacuum tightness of described vacuum condition can be 0.1-500Pa; More preferably 0.1-100Pa.
According to the present invention, the method of described melting can be the melting method of various routine in this area, as long as by abundant for non-crystaline amorphous metal raw material melting, under preferable case, described melting can be vacuum induction melting, vacuum arc melting or the melting of vacuum consumable formula electrode.Described melting can be carried out in melting equipment, and smelting temperature and smelting time have some changes with the raw-material difference of non-crystaline amorphous metal, and in the present invention, smelting temperature can be 1000-1500 DEG C; Smelting time can be 10-500 minute, is preferably 10-30 minute.Described melting equipment can be conventional melting equipment, such as vacuum arc melting furnace, vacuum induction melting furnace or vacuum resistance furnace.
In the present invention, the glass-forming ability of the zirconium-base amorphous alloy provided is strong, and described cooling forming can adopt the pressure die casting forming method of various routine in this area, such as, alloy material (melt) pressure die casting of melting in mould, is then cooled.Described pressure casting processes can be gravitational casting, negative pressure casting, malleation casting, any one in high-pressure casting, and casting condition, if casting pressure is conventionally known to one of skill in the art, such as, the pressure of high-pressure casting can be 2-20MPa.Described gravity casting refers to and utilizes the action of gravity of melt itself to be cast in mould.The concrete operation method of described casting is conventionally known to one of skill in the art.Such as, moulding stock can for copper alloy, stainless steel and thermal conductivity be that 30-400W/mK(is preferably 50-200W/mK) various die steel materials.Mould can carry out water-cooled, oil cooling.Do not specially require the degree of cooling, as long as can be shaped to non-crystaline amorphous metal of the present invention, rate of cooling can be more than 500K/s.
Below will be described the present invention by embodiment.
XRD diffractometer (Rigaku D/Max2200PC) is adopted to analyze whether the alloy prepared in following examples and comparative example is amorphous.Analysis condition is copper target, incident wavelength
acceleration voltage is 40kV, and electric current is 20mA, and adopt step-scan, scanning step is 0.04 °.
Adopt XRD diffractometer (Rigaku D/Max2500PC) to analyze the critical size of the non-crystaline amorphous metal of preparation, angle of diffraction 2 θ is between 20 °-60 °, and sweep velocity is 4 °/min, and sweep voltage is 40kV, and electric current is 200mA.
According to inductively coupled plasma emission spectrography, adopt the composition in the non-crystaline amorphous metal of Induction Couple Plasma (ICP-AES) (Thermo Electron Corp. of the U.S., model TEVA) analysis preparation.
Embodiment 1
The present embodiment illustrates non-crystaline amorphous metal (Zr provided by the invention
0.9904hf
0.0096)
52cu
29al
10co
5fe
2ag
1y
1preparation method.
Each component raw material is dropped in vacuum melting furnace, and vacuumizes as 50Pa, then to pass into purity be that the argon gas of 99.99% volume percent is as shielding gas; carry out vacuum induction melting; smelting temperature is 1100 DEG C, and smelting time is 15 minutes, makes the abundant melting of alloy raw material.Then turn over molten 3 times, make its abundant alloying.Smelting temperature in fusion process adopts infrared measurement of temperature test to obtain.
Metallic element all adopts elemental metals, all adopts the industrial raw materials that purity is greater than 99 % by weight except zr element.Zirconium adopts the zirconium sponge of technical grade, and zirconium hafnium purity is for being greater than 99.4 % by weight.
The alloy sample of melting is casted into (wherein, pressure 20MPa, moulding stock SKD61) in metal die by the method for high-pressure casting, and cool with the rate of cooling of 1000K/s, acquisition diameter is 4-15mm, and height is the truncated cone-shaped metal founding of 20mm, is designated as alloy sample A1.
Alloy sample A1 is carried out XRD powder diffraction analysis, in the XRD spectra obtained, occurs that peak type is the diffraction peak at steamed bun peak, illustrate that alloy sample A1 is non-crystaline amorphous metal.
Measure the critical size of alloy sample A1, the results are shown in Table 1.
The moiety of beta alloy sample A1, the massfraction being analyzed contained metallic element in the alloy that obtains by ICP-AES is converted into atomic percent, and the results are shown in Table 1 for the amorphous alloy component of alloy sample A1.
Embodiment 2
The present embodiment illustrates non-crystaline amorphous metal (Zr provided by the invention
0.9904hf
0.0096)
52cu
29al
10co
4fe
2ag
2.5y
0.5preparation method.
Each component raw material is dropped in vacuum melting furnace, and vacuumizes as 50Pa, then to pass into purity be that the argon gas of 99.99% volume percent is as shielding gas; carry out vacuum induction melting; smelting temperature is 1100 DEG C, and smelting time is 15 minutes, makes the abundant melting of alloy raw material.Then turn over molten 3 times, make its abundant alloying.Smelting temperature in fusion process adopts infrared measurement of temperature test to obtain.
Metallic element all adopts elemental metals, all adopts the industrial raw materials that purity is greater than 99 % by weight except zr element.Zirconium adopts the zirconium sponge of technical grade, and zirconium hafnium purity is for being greater than 99.4 % by weight.
The alloy sample of melting is casted into (wherein, pressure 20MPa, moulding stock SKD61) in metal die by the method for high-pressure casting, and cool with the rate of cooling of 1000K/s, acquisition diameter is 2-15mm, and height is the truncated cone-shaped metal founding of 20mm, is designated as alloy sample A2.
Alloy sample A2 is carried out XRD powder diffraction analysis, in the XRD spectra obtained, occurs that peak type is the diffraction peak at steamed bun peak, illustrate that alloy sample A3 is non-crystaline amorphous metal.
Measure the critical size of alloy sample A2, the results are shown in Table 1.
The moiety of beta alloy sample A2, the massfraction being analyzed contained metallic element in the alloy that obtains by ICP-AES is converted into atomic percent, and the results are shown in Table 1 for the amorphous alloy component of alloy sample A2.
Embodiment 3
The present embodiment illustrates non-crystaline amorphous metal (Zr provided by the invention
0.9918hf
0.0082)
61cu
20al
10co
4fe
2ag
2.5y
0.5preparation method.
Each component raw material is dropped in vacuum melting furnace, and vacuumizes as 50Pa, then to pass into purity be that the argon gas of 99.99% volume percent is as shielding gas; carry out vacuum induction melting; smelting temperature is 1100 DEG C, and smelting time is 15 minutes, makes the abundant melting of alloy raw material.Then turn over molten 3 times, make its abundant alloying.Smelting temperature in fusion process adopts infrared measurement of temperature test to obtain.
Metallic element all adopts elemental metals, all adopts the industrial raw materials that purity is greater than 99 % by weight except zr element.Zirconium adopts the zirconium sponge of technical grade, and zirconium hafnium purity is for being greater than 99.4 % by weight.
The alloy sample of melting is casted into (wherein, pressure 20MPa, moulding stock SKD61) in metal die by the method for high-pressure casting, and cool with the rate of cooling of 1000K/s, acquisition diameter is 2-15mm, and height is the truncated cone-shaped metal founding of 20mm, is designated as alloy sample A3.
Alloy sample A3 is carried out XRD powder diffraction analysis, in the XRD spectra obtained, occurs that peak type is the diffraction peak at steamed bun peak, illustrate that alloy sample A3 is non-crystaline amorphous metal.
Measure the critical size of alloy sample A3, the results are shown in Table 1.
The moiety of beta alloy sample A3, the massfraction being analyzed contained metallic element in the alloy that obtains by ICP-AES is converted into atomic percent, and the results are shown in Table 1 for the amorphous alloy component of alloy sample A3.
Embodiment 4
The present embodiment illustrates non-crystaline amorphous metal (Zr provided by the invention
0.9904hf
0.0096)
52cu
27al
10co
6fe
1nb
1ti
1ag
1y
1preparation method.
Each component raw material is dropped in vacuum melting furnace, and vacuumizes as 50Pa, then to pass into purity be that the argon gas of 99.99% volume percent is as shielding gas; carry out vacuum induction melting; smelting temperature is 1100 DEG C, and smelting time is 15 minutes, makes the abundant melting of alloy raw material.Then turn over molten 3 times, make its abundant alloying.Smelting temperature in fusion process adopts infrared measurement of temperature test to obtain.
Metallic element all adopts elemental metals, all adopts the industrial raw materials that purity is greater than 99 % by weight except zr element.Zirconium adopts the zirconium sponge of technical grade, and zirconium hafnium purity is for being greater than 99.4 % by weight.
The alloy sample of melting is casted into (wherein, pressure 20MPa, moulding stock SKD61) in metal die by the method for high-pressure casting, and cool with the rate of cooling of 1000K/s, acquisition diameter is 15mm, and height is the truncated cone-shaped metal founding of 20mm, is designated as alloy sample A4.
Alloy sample A4 is carried out XRD powder diffraction analysis, in the XRD spectra obtained, occurs that peak type is the diffraction peak at steamed bun peak, illustrate that alloy sample A4 is non-crystaline amorphous metal.
Measure the critical size of alloy sample A4, the results are shown in Table 1.
The moiety of beta alloy sample A4, the massfraction being analyzed contained metallic element in the alloy that obtains by ICP-AES is converted into atomic percent, and the results are shown in Table 1 for the amorphous alloy component of alloy sample A4.
Comparative example 1
According to the method for embodiment 1, unlike, with " non-crystaline amorphous metal (Zr
0.9904hf
0.0096)
52cu
25al
10co
5fe
2ag
5y
1" substitute " non-crystaline amorphous metal (Zr
0.9904hf
0.0096)
52cu
29al
10co
5fe
2ag
1y
1".
Obtained alloy sample D1.Critical size and the moiety of alloy the results are shown in Table 1.
Comparative example 2
According to the method for embodiment 1, unlike, with " non-crystaline amorphous metal (Zr
0.9904hf
0.0096)
52cu
30al
10co
5fe
2y
1" substitute " non-crystaline amorphous metal (Zr
0.9904hf
0.0096)
52cu
29al
10co
5fe
2ag
1y
1".
Obtained alloy sample D2.Critical size and the moiety of alloy the results are shown in Table 1.
Comparative example 3
According to the method for embodiment 1, unlike, substitute " non-crystaline amorphous metal (Zr with " stainless steel 304 "
0.9904hf
0.0096)
52cu
29al
10co
5fe
2ag
1y
1".Be sample D3.
Comparative example 4
According to the method for embodiment 1, unlike, with " non-crystaline amorphous metal (Zr
0.904hf
0.096)
52cu
29al
10co
5fe
2ag
1y
1" substitute " non-crystaline amorphous metal (Zr
0.9904hf
0.0096)
52cu
29al
10co
5fe
2ag
1y
1".
Obtained alloy sample D4.Critical size and the moiety of alloy the results are shown in Table 1.
Antibiotic rate test 1-8
(1) control sample.Control sample adopts sanitation-grade high density polyethylene(HDPE), control sample is prepared into the flat board of 50mm × 50mm × 1mm, with its surface of 70% ethanolic soln wiping, and distilled water flushing, seasoning.
Get the nutrient agar inclined-plane 18 hour fresh culture thing of the streptococcus aureus kind third generation to the 8th generation, wash lower lawn with phosphate buffered saline buffer, be diluted to suitable concentration with 0.03mol/l phosphate buffered saline buffer, be prepared into experimental bacteria liquid.
Control sample is put into sterilizing vessel, draw 0.2mL-0.5mL experimental bacteria drop and be added in tested sample surfaces, pick up mulch film with sterilizing tweezers and cover sample surfaces respectively, make experimental bacteria liquid uniform contact sample, under 37 DEG C with relative humidity 90% condition, contact cultivation 20 hours.
The contact cultivation sample of 20 hours adds 20mL elutriant, and wash-out 3 times, moves into elutriant in triangular flask repeatedly, shake up and dilute, the parallel inoculation of every sample experimental bacteria liquid 2 plates, pour into 50 DEG C of nutrient agars dissolved, and wait nutrient agar to solidify rear upset flat board.Above-mentioned flat board is placed in 37 DEG C of constant incubators, does viable bacteria and cultivate counting.
(2) test sample.Sample A1-A4 and D1-D4 of embodiment 1-4 and comparative example 1-4 is prepared into the flat board of 50mm × 50mm × 1mm, adopts sanitation-grade high density polyethylene(HDPE), and its surface of 70% ethanolic soln wiping all used by sample, distilled water flushing, seasoning.
Sample A1-A4 and D1-D4 is put into sterilizing vessel respectively, drawing 0.2mL-0.5mL experimental bacteria liquid drips at tested sample surfaces respectively, pick up mulch film with sterilizing tweezers and cover sample surfaces respectively, make experimental bacteria liquid uniform contact sample, under 37 DEG C with relative humidity 90% condition, contact cultivation 20 hours.
The contact cultivation sample of 20 hours adds 20mL elutriant respectively, wash-out 3 times repeatedly, elutriant is moved in triangular flask, shake up and dilute, the parallel inoculation of every sample experimental bacteria liquid 2 plates, pour into 50 DEG C of nutrient agars dissolved, and wait nutrient agar to solidify rear upset flat board, above-mentioned flat board is placed in 37 DEG C of constant incubators, does viable bacteria and cultivate counting.
Calculate bacteriostasis rate as follows:
Bacteriostasis rate R=(M-N)/M × 100%
M is that control sample contacts average bacterial count recovered after certain hour with tested bacterium;
N is that test sample contacts average bacterial count recovered after certain hour with tested bacterium.
Table 1
| Numbering | Composition | Critical size (mm) | Bacteriostasis rate |
| Embodiment 1 | (Zr 0.9904Hf 0.0096) 52Cu 29Al 10Co 5Fe 2Ag 1Y 1 | 15 | 95% |
| Embodiment 2 | (Zr 0.9904Hf 0.0096) 52Cu 29Al 10Co 4Fe 2Ag 2.5Y 0.5 | 11 | 98% |
| Embodiment 3 | (Zr 0.9918Hf 0.0082) 61Cu 20Al 10Co 4Fe 2Ag 2.5Y 0.5 | 6 | 99% |
| Embodiment 4 | (Zr 0.9904Hf 0.0096) 52Cu 27Al 10Co 6Fe 1Nb 1Ti 1Ag 1Y 1 | 8 | 96% |
| Comparative example 1 | (Zr 0.9904Hf 0.0096) 52Cu 25Al 10Co 5Fe 2Ag 5Y 1 | 2 | 90% |
| Comparative example 2 | (Zr 0.9904Hf 0.0096) 52Cu 30Al 10Co 5Fe 2Y 1 | 9 | 40% |
| Comparative example 3 | Stainless steel 304 | / | 10% |
| Comparative example 4 | (Zr 0.904Hf 0.096) 52Cu 29Al 10Co 5Fe 2Ag 1Y 1 | 2 | 80% |
As can be seen from the data results of table 1, embodiment 1-4 adopts non-crystaline amorphous metal provided by the invention can have better fungistatic effect and has large critical size simultaneously.And although Ag content excessive in comparative example 1 also has good fungistatic effect, the critical size of non-crystaline amorphous metal is less than normal, and the non-crystaline amorphous metal obtained is unsuitable for industrialization manufacture.In comparative example 4, Zr and Hf combination is not in specific limited range of the present invention, and the alloy sample critical size obtained is little and bacteriostasis rate is low.
Non-crystaline amorphous metal provided by the invention, relative to existing zirconium-base amorphous alloy, namely has large critical size, and technical grade starting material can be adopted again to carry out industrialization manufacture, has excellent fungistatic effect simultaneously; Relative to traditional metal material as stainless steel 304, then have more outstanding fungistatic effect, therefore non-crystaline amorphous metal of the present invention is a kind of metallic substance with excellent functionality, be with a wide range of applications, be particularly suitable for the special dimensions such as medicine equipment, consumer electronics product, fine chemistry industry.
Claims (10)
1. a non-crystaline amorphous metal, is characterized in that, consisting of of this non-crystaline amorphous metal: (Zr
1-xhf
x)
acu
bal
cm
dag
erE
f; Wherein, M is selected from least one in Fe, Co, Mn, Ti and Nb; RE is at least one in rare earth element; A, b, c, d, e and f are the atomic percent that each element is corresponding in this zirconium-base amorphous alloy, are respectively: 40≤a≤70,15≤b≤35,5≤c≤15,3≤d≤15,0 < e≤3,0 < f≤2; Atomic molar between Zr and Hf is than meeting 0 < x < 0.02.
2. non-crystaline amorphous metal according to claim 1, wherein, described RE is Y.
3. non-crystaline amorphous metal according to claim 2, wherein, consisting of of described non-crystaline amorphous metal: (Zr
0.9904hf
0.0096)
52cu
29al
10co
5fe
2ag
1y
1, (Zr
0.9904hf
0.0096)
52cu
29al
10co
4fe
2ag
2.5y
0.5, (Zr
0.9918hf
0.0082)
61cu
20al
10co
4fe
2ag
2.5y
0.5or (Zr
0.9904hf
0.0096)
52cu
27al
10co
6fe
1nb
1ti
1ag
1y
1.
4. according to the non-crystaline amorphous metal in claim 1-3 described in any one, wherein, with the total amount of described non-crystaline amorphous metal for benchmark, in described non-crystaline amorphous metal, the atomic percent of metallic impurity elements is less than 2%, and the atomic percent of nonmetallic impurity element is less than 1%.
5. according to the non-crystaline amorphous metal in claim 1-3 described in any one, wherein, the critical size of described non-crystaline amorphous metal is more than 5mm.
6. prepare the method for non-crystaline amorphous metal for one kind; under the method is included in protection of inert gas or under vacuum condition; the raw material of non-crystaline amorphous metal is carried out melting and cooling forming; it is characterized in that; the raw material of described non-crystaline amorphous metal comprises Zr, Hf, Cu, Al, M, Ag and RE, consisting of of the non-crystaline amorphous metal formed by the raw material of described non-crystaline amorphous metal: (Zr
1-xhf
x)
acu
bal
cm
dag
erE
f, wherein, M is selected from least one in Fe, Co, Mn, Ti and Nb; RE is at least one in rare earth element; A, b, c, d, e and f are the atomic percent that each element is corresponding in this zirconium-base amorphous alloy, are respectively: 40≤a≤70,15≤b≤35,5≤c≤15,3≤d≤15,0 < e≤3,0 < f≤2; Atomic molar between Zr and Hf is than meeting 0 < x < 0.02.
7. method according to claim 6, wherein, described RE is Y.
8. method according to claim 6, wherein, the purity of described raw material is more than 97 % by weight.
9. method according to claim 6, wherein, described melting is vacuum induction melting, vacuum arc melting or the melting of vacuum consumable formula electrode; It is 1000-1500 DEG C that the condition of described melting comprises smelting temperature, and smelting time is 10-50 minute.
10. method according to claim 6, wherein, the vacuum tightness of described vacuum environment is 0.1-500Pa.
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