CN103328674A - Ni and Cu-free Pd-based metallic glasses - Google Patents
Ni and Cu-free Pd-based metallic glasses Download PDFInfo
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- CN103328674A CN103328674A CN2011800658307A CN201180065830A CN103328674A CN 103328674 A CN103328674 A CN 103328674A CN 2011800658307 A CN2011800658307 A CN 2011800658307A CN 201180065830 A CN201180065830 A CN 201180065830A CN 103328674 A CN103328674 A CN 103328674A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/003—Amorphous alloys with one or more of the noble metals as major constituent
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
Abstract
The invention is directed to Pd-based metallic glass alloys useful in biomedical applications having no Ni or Cu. Exemplary metallic glass alloys are represented by AaBb{(Si)ioo-c(D)c} d, where A may be selected from Pd, and combinations of Pd and Pt, B may be selected from Ag, Au, Co, Fe, and combinations thereof, and D may be selected from P, Ge, B, S. Also, a, b, c and d are atomic percentages, and a ranges from about 60 to about 90, b ranges from about 2 to about 18, d ranges from about 5 to about 25, and c is greater than 0 and less than 100.
Description
Technical field
Present invention is directed at the Pd base metal glass that does not contain Ni and Cu.More specifically, the present invention is directed to Pd base glass useful aspect biomedical applications and form alloy.
Background technology
Metallic glass is different from conventional crystal alloy, has the structure of the amorphous that causes unique chemistry, machinery and rheological property or unordered atomic scale.Because its atomic structure, metallic glass generally shows than the better erosion resistance of general crystal alloy, higher hardness, intensity and elasticity, and when being higher than its glass transformation temperature (T
g) can soften and flow when relaxing, this is the feature that allows goodish processing characteristics.Before, owing to need to cool off to avoid crystallization fast from liquid state, so metallic glass only can be produced at submicron-scale (thin strip, sheet material, wire rod or powder).But, form production that immediate development aspect the alloy made metal system can form greatly several centimeter scale under crystallization power very slowly glass in bulk glass and become possibility.These development allow the introducing of metallic glass in many engineering application facet, need chemistry and the mechanical properties of its uniqueness in these are used, and comprise that good erosion resistance, high strength and hardness and large elastic extension are needs.
To form metal system be the Pd-Ni-Cu-P alloy to the glass of the most durable (robust) so far, and it can form the amorphous parts that have greatly to 7 centimetres thickness.The ability of metallic glass spindle that production has the thickness of such raising has caused the interest in many application facet.But, because the Pd(precious metal) and restrictive expensive, most such application are still out of reach.The expensive application of regarding obstacle as with this precious metal (for example Pd) does not comprise Jewelry ﹠ Watches and biomedical applications (for example application of shaping and dentistry/dentistry rectification).What is interesting is, the feature of Pd precious metal is so that Pd base glass is attractive especially for these application facet.But the only Pb base metal glass of known acquisition more than several millimeters comprises a kind of of Ni and Cu or both in alloy composition.In fact, general extensive glass forming ability known and that admit metal depends on comprising of in alloy Ni and/or Cu to a great extent, and comprising so that the exploitation of so durable glass-former becomes possibility of these metals just.Therefore, it is necessary accepting extensively and comprising of Ni and Cu glass being formed alloy, and those skilled in the art creates at least a good glass formation alloy that does not comprise these metals with hoping to succeed.
Although Ni and Cu are suitable and acceptable in comprising of metallic glass when this glass is used for the engineering application, these metals are high cell toxicities, and this is not suitable for biomedical applications so that comprise the metallic glass of these metals.Especially, Ni and Cu are highly electronegative, and this allows them to exist in blood flow as free radical.Such free radical is the triggering agent of the bad reputation of the serious biological respinse that is harmful in the body.Therefore, extensively Ni and Cu are understood and think bio-compatible not, and any metallic glass that comprises these metals is understood similarly also and regards abiotic compatibility as.Because the glass forming ability of amorphous metallic alloy depends on comprising of Ni and/or Cu strongly, the exploitation that therefore is suitable for the Pb base metal glass of biomedical applications proves extremely challenging, and also not yet obtains suitable such metallic glass.
Summary of the invention
In certain embodiments, present invention is directed at the metallic glass alloys that is represented by formula 1.
A
aB
b{(Si)
100-c(D)
c}
d (1)
In formula 1, A can be Pd, or the combination of Pd and Pt, and B can be selected from Ag, Au, Co, Fe and combination thereof, and D can be selected from P, Ge, B, S.In addition, a, b, c and d are atomic percent, and a is about 60-approximately 90, and b is about 2-approximately 18, and d is about 5-approximately 25, and c is greater than 0 and less than 100.
In other embodiments, present invention is directed at the metallic glass alloys that is represented by formula 2.
Pd
aX
bSi
cP
dGe
e (2)
Wherein X is a kind of or its combination among Ag or the Au, and wherein subscript represents atomic percent, and to have following restriction: a be 74-86, preferred 78.5-81.5, and more preferably 79; B is 2-5, preferred 2.75-4.25, and more preferably 3.5; C is 8-10, preferred 8.75-9.75, and more preferably 9.5; D is 4-8, preferred 5-7, and more preferably 6; With e be 0-3, preferred 1.5-2.5, and more preferably 2.
In other embodiment of the present invention, form three-dimensional object by the alloys of through type 1 and 2 expressions.This three-dimensional body, bar for example has greater than the diameter of 3mm and can have greatly diameter to 6mm.In certain embodiments, for example, three-dimensional body can be has the about bar of the diameter of 4mm greater than 1mm-.In other embodiments, the object of three-dimensional dimension can have the size greater than 6mm.
Description of drawings
When considering with accompanying drawing, with reference to following detailed explanation these and other the feature and advantage that the present invention may be better understood, wherein:
The glassy Pd of 1mm that Fig. 1 is as produces by capillary water quenching (capillary water-quenching) method in embodiment 3
77.5Ag
6Si
9P
7.5The photo of wire rod;
Fig. 2 is the figure of the scanning result of the dsc of the alloy that relatively prepares with comparative example 1 according to embodiment 2 and 15;
Fig. 3 is the X-ray diffractogram according to the alloy of embodiment 1-3 preparation;
Fig. 4 is for relatively according to embodiment 30 and 32 and the figure of the scanning result of the dsc of the prepared alloy of comparative example 2;
Fig. 5 is the X-ray diffractogram according to the alloy of embodiment 30 preparations;
Fig. 6 is the amorphous Pd with diameter of 3-6mm
79Ag
3.5P
6Si
9.5Ge
2The figure of bar;
Fig. 7 is amorphous Pd
79Ag
3.5P
6Si
9.5Ge
2(arrow from left to right shows glass transformation temperature T to the data and curves figure of the dsc research of sample
g=337 ℃, Tc T
x=370 ℃, solidus temperature T
s=691 ℃, and liquidus temperature T
l=793 ℃);
Fig. 8 is the amorphous Pd with 3-6mm diameter
79Ag
3.5P
6Si
9.5Ge
2The data and curves figure of the X-ray diffraction analysis of bar;
Fig. 9 is the glassy Pd such as preparation among the embodiment 3
77.5Ag
6Si
9P
7.5The picture of the stress under compression-strain-responsive of sample; With
Figure 10 is the curved glass shape Pd such as the vicissitudinous thickness of tool that passes through the production of capillary water quenching method among the embodiment 3
77.5Ag
6Si
9P
7.5The photo of wire rod.
Detailed Description Of The Invention
In order to be formed on the useful metallic glass in biomedical applications aspect, glass formation alloy should be the glassy parts of (greater than 1mm) bio-compatible and that can form enough big scales to make needed biomedical member.And this glass should have the feature of low Young's modulus and high tenacity.Metallic glass with these features can be in biomedical applications, such as being useful especially in shaping and orthodontics implant and the stationary member (wire rod, nail, sheet material, screw etc.).
Although the Pd base metal glass generally has desired modulus and toughness characteristics, and can be formed for the 3-dimensional metal glass object of the adequate thickness of biomedical applications, but these metallic glasss comprise Ni and Cu at least a (and often comprising both), may be abiotic compatibility, and therefore not be suitable for biomedical applications.But, because the Pd base metal glass has needed modulus and toughness characteristics, therefore present invention is directed at the Pd base metal glass that does not comprise Ni and Cu.
Except being used for biomedical applications, the alloy of the present invention that does not comprise Ni and Cu can be useful aspect jewelry product and the wrist-watch also.Because known Ni and Cu produce anaphylaxis at a lot of person, be particularly suitable for use in Jewelry ﹠ Watches is used so get rid of the alloy of the present invention of these metals.
In certain embodiments of the invention, metallic glass comprises the alloy by the bio-compatible of formula 1 expression
A
aB
b{(Si)
100-c(D)
c}
d (1)
In formula 1, A can be Pd, or the combination of Pd and Pt, and B can be selected from Ag, Au, Co, Fe and combination thereof, and D can be selected from P, Ge, B, S and combination thereof.In addition, a, b, c and d are atomic percent, and a is about 60-approximately 90, and b is about 2-approximately 18, and d is about 5-approximately 25, and c is greater than 0 and less than 100.In one embodiment, B is selected from Au, Ag and combination thereof.In another embodiment, D is selected from P, Ge and combination thereof.
The indefiniteness embodiment that satisfies the suitable alloy of formula 1 comprises Pd
77.5Ag
6Si
14P
2.5, Pd
77.5Ag
6Si
11.5P
5, Pd
77.5Ag
6Si
9P
7.5, Pd
77.5Ag
6Si
6.5P
10, Pd
77.5Ag
6Si
4P
12.5, Pd
79.5Ag
4Si
9P
7.5, Pd
78.5Ag
5Si
11.5P
5, Pd
76.5Ag
7Si
11.5P
5, Pd
75.5Ag
8Si
9P
7.5, Pd
75.5Ag
8Si
11.5P
5, Pd
75Ag
8.5Si
11.5P
5, Pd
73.5Ag
10Si
11.5P
5, Pd
76.85Ag
8.14Si
10.45P
4.55, Pd
74.14Ag
7.86Si
12.55P
5.45, Pd
75.5Ag
8Si
9Ge
2.5P
5, Pd
75.5Ag
8Si
9.5Ge
2P
5, Pd
75Ag
8.5Si
9.5Ge
2P
5, Pd
76Ag
7.5Si
9.5Ge
2P
5, Pd
75.5Ag
8Si
10.5Ge
2P
4, Pd
75.5Ag
8Si
8.5Ge
2P
6, Pd
75.5Ag
8Si
6.5Ge
5P
5, Pd
75.5Ag
8Si
4Ge
7.5P
5, Pd
75.5Ag
8Si
2.5Ge
9P
5, Pd
73Ag
8Ge
14P
5, Pd
75.5Ag
8Ge
11.5P
5, Pd
77Ag
8Ge
10P
5, Pd
75.5Ag
8Si
9P
5S
2.5, Pd
75.5Ag
8Si
2.5Ge
7P
5S
2, Pd
79Au
4Si
12P
5, Pd
79Au
4Si
12Ge
5, Pd
79Au
4Si
9.5Ge
2.5P
5And Pd
75.5Ag
8Si
2.5Ge
7P
5S
2
Suc as formula represented and listed above exemplary alloy in 1, the element that the Si in the alloy is selected from P, Ge, B, S and combination thereof partly replaces.This part replacement of Si avoids the required critical cooling rate of crystallization to improve glass forming ability by reduction in alloy, has improved thus the obtainable size by the three-dimensional body of non-crystaline amorphous metal preparation.In addition, the part of Si replaces the thermoplasticity processing characteristics that can improve by the temperature range between raising glass transition and the crystallization non-crystaline amorphous metal, has improved thus the workability window in the supercooled liquid zone.In addition, the replacement of the Si in alloy also can by reducing shearing modulus and improving the mechanical property that Poisson is recently improved alloy, improve fracture toughness property and ductility thus.
In certain embodiments, can comprise the additional alloy element of atomic percent in about 2% impurity level by the alloy of formula 1 expression.
A kind of illustrative methods of the alloy for the production of being represented by formula 1 is included in the alloying constituent of the appropriate amount of induction melting in silica tube under the inert atmosphere.But, for the alloy that comprises high density P, at first produce the prealloy without P by the alloying constituent (except P) of the appropriate amount in the fused quartz pipe under inert atmosphere, and then (this silica tube is airtight under inert atmosphere) adds P in the silica tube by P and prealloy are sealed in.Then sealed tube is placed stove and the temperature that raises intermittently.
According to another embodiment of the invention, the alloy that is represented by formula 1 can be configured as three-dimensional body useful in many application.Except engineering and machine applications, also because metallic glass of the present invention (does not for example contain the known element that causes the biological respinse that is harmful to, Ni and Cu), thus know from experience the thing compatibility of making a living by the three-dimensional article of this alloy preparation, and therefore in many biomedical applications, be useful.For example, for example wire rod, nail, sheet material or screw can be useful this three-dimensional body as the implant of shaping and/or orthodontics and stationary member.
Alloy according to the present invention can be used for being configured as three-dimensional block object, for example has greater than the about bar of 1mm diameter.Fig. 1 is the glassy 1mm Pd as using capillary water quenching method as described below to produce among the embodiment 3
77.5Ag
6Si
9P
7.5Photo.Especially, can form to have with this alloy and be up to the approximately three-dimensional body of the diameter of 5mm.In many embodiments, for example this alloy production has the three-dimensional body of the diameter of 2-4mm.Because it is generally acknowledged that in Ni and the Cu any alloy for the three-dimensional body that obtains to have such block diameter all be essential, so the ability that forms the object with such diameter according to the alloy that does not contain Ni and Cu of embodiment of the present invention is wonderful especially.
A kind of production has 50%(at least by volume) illustrative methods of the three-dimensional block object of amorphous phase comprises at first in silica tube the dehydration B of induction melting and fusing under inert atmosphere
2O
3The alloy of sheet contact.Then, with the fusing dehydration B
2O
3Contact time, this whole alloy is being enough to suppress to be cooled to be lower than from being higher than its temperature of fusion under the speed that forms mutually more than 50% crystalline state the temperature of its glass transformation temperature.
Only propose for illustrative purposes following examples, and do not limit the scope of the invention.In an embodiment, use have approximately 99.9% or more highly purified element prepare this alloy by the capillary water quenching method.Particularly, the weighing element is to approximately in 0.1% of the quality of calculating, and before fusing, with its ultrasonic cleaning in acetone and ethanol.At the induction melting that in airtight silica tube, carries out element under the part argon atmospher.Subsequently with the spindle of alloying dehydration B
2O
3Flux is processed (flux).Flux is processed and is undertaken by following: in silica tube, and induction melting spindle and dehydration B under argon
2O
3, the spindle that keeps fusing is being higher than the approximately temperature approximately 15 minutes of 50 degree of alloy melting point, and the most at last this spindle water quenching.The spindle that uses quartz capillary that flux is processed is cast into glassy bar.Spindle is placed the silica tube that is connected on the kapillary, in stove under vacuum with its fusing, use 1.5 atmospheric argons to be injected in the kapillary, and final water quenching.Use the amorphous character of the glassy bar of at least a proof in the following methods: (a) X-ray diffraction (if diffraction pattern does not represent the crystal peak then proved non-crystalline state); (b) dsc (if this scanning shows after the glass transition event crystallization event when heating from room temperature then proved non-crystalline state); (c) microscopic examination of bar failure characteristics (if the shear zone network has been disclosed in the viscous deformation zone, and fracture surface has represented sharply marginated bright facet and then proved non-crystalline state).In table 1 and 2, listed the composition of each embodiment and comparative example.
It is that quick cooling material makes it avoid the result who forms stable crystalline structure and freeze accordingly (similar liquids atomic structure) that glass forms.Relatively good glass-former is the alloy that the relatively low rate of cooling of requirement forms vitreous state, or as an alternative, can form for given rate of cooling relatively thick glassy part.Therefore, quantize the glass forming ability of alloy according to the size (being called " critical casting yardstick ") of alloy restricted part when removing under the speed cooling in certain heat.Because the alloy of example quenches in quartz capillary, internal diameter and the wall thickness of this quartz capillary change, and because known quartz is the heat conductor that hinders the difference of heat transfer, the quartz capillary wall thickness should also be the factor that determines the glass forming ability of exemplary alloy.Therefore the glass forming ability of different exemplary alloy is decided by can form glass maximum diameter of rod based on given capillary wall thickness.In table 1, list the critical diameter of rod and relevant capillary wall thickness of some exemplary alloy, and in table 2, reported thermodynamic property.In table 1, DSC refers to dsc, and XRD refers to X-ray diffraction, and INSP refers to microcosmic detection.In table 2, T
gBe glass transformation temperature, T
xBe Tc, Δ H
XBe crystallization enthalpy, T
sBe solidus temperature, T
lBe liquidus temperature, and Δ H
mBe fusion enthalpy.In table 2, provided the T that is called as " glass transition of reduction " with absolute Kelvin unit
gTo T
sRatio.
Table 1
Table 2
Use at least a amorphous character of having studied the composition of embodiment and comparative example in X-ray diffraction, dsc and the microscopic inspection.Fig. 2 has compared the scanning result of dsc of the composition of comparative example 1 and embodiment 2 and 14.The glass transition and the liquidus temperature that in Fig. 2, have shown every kind of alloy.Fig. 2 has shown the X-ray diffractogram of the composition of embodiment 1-3.As seen in fig. 3, on diffractogram, do not detect the crystal peak, this shows the amorphous character of alloy.Fig. 4 has compared the scanning result of comparative example 2 with the dsc of the composition of embodiment 30 and 32.In Fig. 4, show glass transition and liquidus temperature, and as shown in it, do not detected the glass transition of the composition of comparative example 2.Fig. 5 has shown the diffractogram of X ray of the composition of embodiment 30.As shown in Figure 5, in diffractogram, do not detect the crystal peak, proved thus the amorphous character of alloy.
As table 1 and 2 and Fig. 2-5 as shown in, the composition of embodiment 1-32 is amorphous or at least part of amorphous, and the composition of comparative example 2 is not amorphous.Although the composition of comparative example 1 is amorphous, as can be seen from Table 2, the composition of comparative example 1 has higher glass transformation temperature and solidus temperature.Be used for to quantize glass forming ability the earliest and one of the standard of accepting extensively most based on the comparison between glass transformation temperature and fusing (solid phase or the liquid phase) temperature (with absolute Kelvin unit).According to this standard, glass transformation temperature (be lower than its then hydrodynamics solidify) is easily to avoid crystallization and form measuring of amorphous phase to the ratio (being called as " glass transformation temperature of reduction ") of temperature of fusion (be lower than its then dominant crystalline phase-change be thermodynamically stable).Therefore, according to this standard, the alloy with glass transformation temperature of high reduction will represent higher glass forming ability.As in the table 1 as seen, P and Ge are incorporated in the composition of embodiment alloy and have caused slight lower glass transformation temperature, but also caused significantly lower solidus temperature with regard to comparative example.This has caused the comprehensively glass transformation temperature (showing that it is elevated to up to 0.64 from 0.59) of higher reduction.Aspect the glass transformation temperature that reduces this raise comprehensively well approximate explain by P and Ge are incorporated into obtain in forming of comparative example in the improvement aspect the glass forming ability.
Although above discussion has concentrated on the wide in range base composition by formula 1 explanation, found now to have a particularly preferred compositing range, the glass forming ability of alloy is maximized in this scope.Correspondingly, in a preferred embodiment, can be by forming the glass forming ability that is optimized that forms by formula 2 expressions:
Pd
aX
bSi
cP
dGe
e
Wherein X is a kind of among Ag or the Au, or its combination, and wherein subscript represents that atomic percent and its have following restriction:
A is 74-86, preferred 78.5-81.5, and more preferably 79;
B is 2-5, preferred 2.75-4.25, and more preferably 3.5;
C is 8-10, preferred 8.75-9.75, and more preferably 9.5;
D is 4-8, preferred 5-7, and more preferably 6; With
E is 0-3, preferred 1.5-2.5, and more preferably 2.
Find when in the silica tube of the wall thickness with 0.5mm, adding man-hour by the water quenching melt, formed according to the composition of formula 2 and have greater than 3mm and be up to 6mm or larger glassy bar.Produced the exemplary alloy with the composition that satisfies disclosed composition formula 2 by the elemental composition that induction melting has an appropriate amount of 99.9% above purity under inert atmosphere in silica tube.Then, in silica tube, under inert atmosphere, by the remelting spindle spindle of alloying is carried out flux with the dehydration boron oxide and process, alloy melt is contacted with the boron oxide melt, and make approximately 1000s of two fusant reactions, and subsequently it is carried out water quenching.Then, under inert atmosphere, having alloy spindle and the rapid water processed by this flux of remelting in the silica tube of the thick wall of 0.5mm and quenching, forming glassy bar from alloy.Below provided the observations of the character of these alloys in the table 3.
Table 3
By determining to add as previously discussed the glass forming ability that the maximum diameter that can form the bar of amorphous man-hour comes every kind of alloy in the evaluation table 3 (character that should be noted that the alloy of in above table 1 and 2, summarizing be use have the alloy that the melt in the silica tube of 0.1-0.5mm wall thickness processes by water quenching obtain).Composition from the best glass forming ability of having of the alloy in table 1 and 2 is Pd
75.5Ag
8Si
9P
5Ge
2.5Find when adding man-hour this alloy and can form and have the at the most amorphous bar of the diameter of 3mm by in the silica tube of the wall thickness with 0.15mm, melt being carried out water quenching.But, in the silica tube of the wall thickness with 0.5mm, adding man-hour, this alloy only can form has the at the most amorphous bar of 2mm diameter.The reason of this difference is that thicker quartzy tube wall has reduced critical diameter of rod significantly, removes speed because quartzy low-down thermal conductivity has limited heat.
Add the cost alloy by water quenching melt in the silica tube with 0.5mm wall thickness, and find that this alloy can form and has at least 3mm diameter and at the most 6mm or larger amorphous bar.As shown in Figure 3, alloy Pd
79Ag
3.5Si
9.5P
6Ge
2Can form the amorphous bar with 6mm at the most or larger diameter.Fig. 6 has provided and has described the amorphous Pd with 3-6mm diameter
79Ag
3.5Si
9.5P
6Ge
2The image of bar.Dsc and X-ray diffraction analysis have proved respectively the block Pd in Fig. 7 and 8
79Ag
3.5Si
9.5P
6Ge
2Non-crystal structure.
The research of elasticity and mechanical property
The pulse echo that has a 5MHz piezoelectric transducer by use overlap measure shear and vertically velocity of wave and use the Archimedes method measuring density and ultrasonic measurement glassy Pd
77.5Ag
6Si
9P
7.5The elastic constant of column sample (diameter 3mm, height 6mm).Measure shearing modulus, modulus of volume expansion and Young's modulus and be respectively 30GPa, 169GPa, and 85GPa, and find that Poisson's ratio is 0.42.Use has the servo-hydraulic material testing system of 50kN load cell and studies glassy Pd
77.5Ag
6Si
9P
7.5The compressive load response of column sample (diameter 3mm, height 6mm).Apply l * 10
-4s
-1Strain rate.Use the differential transformer monitor strain of linear change.Shown the stress-strain response of this alloy that records among Fig. 9, it has disclosed the approximately yield strength of 1450MPa, approximately 1.7% recoverable strain and approximately 2% plastix strain.
It is obviously higher and can compare with the crystalline state metallic biomaterial or higher hardness, intensity and elasticity than general crystalline state engineering metal that high-yield strength and low Young's modulus show that this class alloy has represented.In addition, the Poisson's ratio that these alloys are very high one of (be actually in the measured metallic glass the highest) shows that these alloys can represent high tenacity.In fact, as shown in Figure 10, the bending of glass wire rod can be under up to the diameter of 1.5mm viscous deformation and avoid cracking.Be combined with the about yield strength of 1500MPa in the bend ductility of 1.5mm part, shown approximately 100MPa-m
1/2Very high fracture toughness property.Because high rigidity, intensity, elasticity and toughness are the highly character of needs for the suitable bio-mechanical effect of implant member, so this shows that alloy of the present invention can be understood to the attractive substitute of present load-bearing implant material.
Vitro cytotoxicity research
In the compatible research of the external biological that is undertaken by NAMSA (Northwood, OH), estimate glassy Pd
77.5Ag
6Si
9P
7.5The cytotoxicity of test article.Carry out this and study to determine Cytotoxic possibility, and should study based on International Standards Organization 10993: biological assessment the 5th part of medical apparatus: be used for Cytotoxic test: in vitro method instructs.
Use is supplemented with the minimum unique extract that must medium prepares test article of the single intensity of 5% blood plasma and 2% microbiotic (1X MEM).Particularly, with the partly usefulness 16ml1X MEM covering of 3.1g of test article, and be accompanied by at 37 ℃ of unique prepared products of lower 24 hours stirrings extraction.The Test extraction thing is placed three independent L-929 mouse fibroblast cell (CO 5%
2Middle breeding) on the individual layer.Prepare three independent individual layers and be used for reagent contrast, negative control and positive control.The reagent contrast comprises the single aliquots containig of the 1X MEM that does not contain any test material, and it is stood the extraction conditions identical such as test article.Use high density polyethylene(HDPE) as negative control.With single 30.8cm
2The negative control material of part covers with 10ml1X MEM, and prepared product is stood identical extract condition such as test article.Use the polyvinyl chloride of tin stabilization as positive control.With single 60.8cm
2The positive control material of part covers with the 1XMEM of 20ml, and is accompanied by the stirring of carrying out 24 hours under 37 ℃ it is extracted.
At 5%CO
2Atmosphere surrounding in comprise in the open bore of 1X MEM breeding and keep L-929 mouse fibroblast cell (ATCC CCL1, the NCTC clone 929 in bacterial strain L or source of equal value).For this research, inoculation 10cm
2The hole, and the mark number of going down to posterity and date, and under 37 ℃ at 5% CO
2The cell monolayer of middle incubation to obtain before use to owe to converge.Selection comprises the in triplicate culture hole of the cell monolayer of owing to converge.Substitute the growth medium that is included in the in triplicate culture with 2ml Test extraction thing.Similarly, adopt reagent contrast, negative control and the positive control of 2ml to substitute in triplicate culture.Porose all under 37 ℃ at 5% CO
2Existence under incubation 48 hours.
After cultivation, microcosmic detection (100X) culture is to estimate cell characteristic and dissolving percentage ratio.Also observed the color of tested media.Color transition to yellow is relevant with the acid pH scope, and the color transition to red-purple to purple is relevant with the alkaline pH scope.Dissolving percentage ratio and the cell characteristic of each culture hole have been estimated based on the measuring scale that provides in the table 4.
Table 4
The parameter of this test need to be assessed as rank 0 with negative control and reagent control, and positive control is assessed as rank 3 or 4, and specimen is assessed as rank 2 or lower.
Under the condition of in vitro study, 1X MEM Test extraction thing does not have to show the evidence that causes cell decomposition or toxicity.This reagent, anode and negative control show to such an extent that as was expected, and specimen is assessed as and is less than grade 2, meet thus the requirement of test.Especially, each test cultures all is assessed as 0, shows according to the alloy right and wrong of embodiment of the present invention Cytotoxic.
In vivo cytotoxicity research
In the body that is undertaken by NAMSA (Northwood, OH), estimate glassy Pd in the bio-compatible Journal of Sex Research
77.5Ag
6Si
9P
7.5The cytotoxicity of test article.Test article is implanted in the muscle tissue of rabbit.Requirement based on International Standards Organization 10993: biological assessment the 6th part of medical apparatus: implant rear test to local influence, for the evidence of stimulation or toxicity is estimated muscle tissue.
The minimum value of four parts of the test article of each rabbit, each is 1mm * 10mm approximately, loads on No. 14 pins.For each rabbit, the minimum value load of four negative control samples is entered in No. 14 pins.Use the high density polyethylene(HDPE) part of 1mm * 10mm as negative control.
Weighing rabbit and it is cut be that the other muscle of backbone top is without hair.With the dosage of the 0.6ml/kg intramuscular injection general anesthesia to the combination (34mg/kg+5mg/kg) of each animal administration of ketamine to hydrochloride and xylazine.Each rabbit is the buprenorphine of subcutaneous injection 0.02mg/kg subsequently.After anesthesia is worked, clean surgery location with germicidal soaps, dye with 70% isopropyl alcohol and with povidone iodine.
On each side of back, make an otch by skin and the lumbar region that is parallel to backbone.Probe is placed the center of load pin.Skin is moved on to desired location and pin is inserted in the muscle with 45 ° by otch.Above probe, fetch pin, sample is stayed in the juxtaspinal muscle.4 test article partly are implanted in the muscle on each right side of rabbit backbone.Place the test article part with the suitable interval that separates.In relative muscle, similarly four negative controls are partly implanted.Adopt tissue glue's sealing skin incision.After the implantation, monitor rabbit from anesthesia recovery, and after the first administration, after at least 4 hours, use the buprenorphine of another dosage.Implant one day after, carry out for the third time buprenorphine injection.
Carry out the observation of holistic health every day to rabbit, and record its body weight before implantation and when finishing.Behind the fortnight weighing rabbit its then make its euthanasia by the intravenous injection of vetanarcol base medicine.Juxtaspinal muscle freely cut open and be fixed in 10% neutral buffered formalin (NBF) to promote cutting.After fixing, cut systematically muscle with assignment test and contrast product location.All tests and contrast product location have been considered.Use low ratio of enlargement and macroscopic observation microscope to form as capsule or other stimulation sign marking, and marking is listed in the table 5.Table 5
| | Condition | |
| 0 | Without capsule, without adverse reaction (except minimum hemorrhage) | |
| 1 | The at the most capsule of 0.5mm or |
|
| 2 | 0.6-1.0mm capsule or |
|
| 3 | 1.1-2.0mm capsule or |
|
| 4 | The capsule of＞2.0mm or conversion zone |
On a macro scale, there is not the visible reaction in any test or control site.In fact, classify each test and control site as 0, show that it is unconspicuous or non-existent organizing haptic stimutus.
Excision reserves enough zones from the representative anatomic implants position (test and contrast) of each rabbit near the position of suitable histology preparation.These parts are processed (embedding, cut apart and seal and dye) for the microcosmic evaluation with histology in phenodin (hemotoxylin) and eosin.Carry out the microcosmic evaluation of representational implant position and further determine any tissue response.Estimated by titular pathologist.Be displayed in Table 6 the result of the microcosmic evaluation of test and control site.
Table 6
As shown in table 6, test position shows equally well with contrast, or even better.Correspondingly, with the negative control ratio, test article is classified as nonirritating.Because the result of research is Cytotoxic according to the alloy right and wrong of embodiment of the present invention in external and the body, and therefore be suitable for the biomedical applications aspect.
Although explain and illustrated the present invention with reference to the embodiment of some example, those of ordinary skill in the art understands and can make various modifications and change and do not deviate from by the spirit and scope of the present invention defined by the following claims illustrated embodiment.
Claims (18)
1. metallic glass, it comprises the alloy by the bio-compatible of formula 1 expression:
Pd
aX
bSi
cP
dGe
e (1)
Wherein:
X is Ag, Au, the perhaps combination of Ag and Au,
A is about about 86 the atomic percent of 74-,
B is about about 5 the atomic percent of 2-,
C is about about 10 the atomic percent of 8-,
D is about about 8 the atomic percent of 4-, and
E is about about 3 the atomic percent of 0-.
2. the metallic glass of claim 1, wherein a is 78.5-81.5, and b is 2.75-4.25, and c is 8.75-9.75, and d is 5-7, and e is 1.5-2.5.
3. the metallic glass of claim 1, wherein X is Ag.
4. the metallic glass of claim 1, wherein this alloy is selected from Pd
78.5Ag
5Si
8.5P
6Ge
2, Pd
79Ag
4.5Si
8.5P
6Ge
2, Pd
79.5Ag
4Si
8.5P
6Ge
2, Pd
80Ag
3.5Si
8.5P
6Ge
2, Pd
80.5Ag
3Si
8.5P
6Ge
2, Pd
81Ag
2.5Si
8.5P
6Ge
2, Pd
79Ag
3Si
10P
6Ge
2, Pd
80Ag
3Si
9P
6Ge
2, Pd
79Ag
4Si
9P
6Ge
2, Pd
79.5Ag
3.5Si
9P
6Ge
2, Pd
79.5Ag
3Si
9.5P
6Ge
2And Pd
79Ag
3.5Si
9.5P
6Ge
2
5. the three-dimensional body that is formed by metallic glass comprises the alloy by the bio-compatible of formula 1 expression:
Pd
aX
bSi
cP
dGe
e (1)
Wherein:
X is the combination of Ag, Au or Ag and Au,
A is about about 86 the atomic percent of 74-,
B is about about 5 the atomic percent of 2-,
C is about about 10 the atomic percent of 8-,
D is that approximately 4-is about 8 atomic percent, and
E is about about 3 the atomic percent of 0-.
6. the three-dimensional body of (original) claim 5, wherein this three-dimensional body has greater than the about critical cast thickness of 3mm.
7. the three-dimensional body of (original) claim 5, wherein this three-dimensional body has approximately the approximately critical cast thickness of 6mm of 3mm-.
8. the three-dimensional body of (original) claim 5, wherein this three-dimensional body has the critical cast thickness greater than 6mm.
9. the three-dimensional body of (original) claim 5, wherein this three-dimensional body is biomedical member.
10. the three-dimensional body of (original) claim 9 should the biomedicine member be dentistry or orthodontics member wherein.
11. the three-dimensional body of claim 9, wherein biomedical member is the shaping member.
The three-dimensional body of (12. original) claim 9, wherein biomedical member is implant or stationary installation.
The three-dimensional body of (13. original) claim 9, wherein biomedical parts are dentistry correction bracket or wire rod.
The three-dimensional body of (14. original) claim 5, wherein this three-dimensional body is jewelry product.
15. the three-dimensional body of claim 5, wherein this three-dimensional body is watch parts or device.
16. the three-dimensional body of claim 5, wherein a is 78.5-81.5, and b is 2.75-4.25, and c is 8.75-9.75, and d is 5-7, and e is 1.5-2.5.
17. the three-dimensional body of claim 5, wherein X is Ag.
18. the three-dimensional body of claim 5, wherein the bio-compatible alloy is selected from Pd
78.5Ag
5Si
8.5P
6Ge
2, Pd
79Ag
4.5Si
8.5P
6Ge
2, Pd
79.5Ag
4Si
8.5P
6Ge
2, Pd
80Ag
3.5Si
8.5P
6Ge
2, Pd
80.5Ag
3Si
8.5P
6Ge
2, Pd
81Ag
2.5Si
8.5P
6Ge
2, Pd
79Ag
3Si
10P
6Ge
2, Pd
80Ag
3Si
9P
6Ge
2, Pd
79Ag
4Si
9P
6Ge
2, Pd
79.5Ag
3.5Si
9P
6Ge
2, Pd
79.5Ag
3Si
9.5P
6Ge
2, and Pd
79Ag
3.5Si
9.5P
6Ge
2
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US42330410P | 2010-12-15 | 2010-12-15 | |
| US61/423,304 | 2010-12-15 | ||
| US13/306,311 | 2011-11-29 | ||
| US13/306,311 US20120168036A1 (en) | 2007-07-12 | 2011-11-29 | Ni and cu free pd-based metallic glasses |
| PCT/US2011/065208 WO2012083044A1 (en) | 2010-12-15 | 2011-12-15 | Ni and cu free pd-based metallic glasses |
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|---|---|
| EP (1) | EP2652165A1 (en) |
| JP (1) | JP2014505164A (en) |
| KR (1) | KR20130109201A (en) |
| CN (1) | CN103328674A (en) |
| WO (1) | WO2012083044A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107779790A (en) * | 2017-09-25 | 2018-03-09 | 北京科技大学 | A kind of germanic no without phosphorus large scale palladium base non-crystaline amorphous metal of nickel and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130224676A1 (en) * | 2012-02-27 | 2013-08-29 | Ormco Corporation | Metallic glass orthodontic appliances and methods for their manufacture |
| CN103911562B (en) * | 2014-04-10 | 2016-07-06 | 大连理工大学 | Without phosphorus palladio block metal glass with wide supercooling liquid phase region and preparation method thereof |
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| JPS55145138A (en) * | 1979-04-26 | 1980-11-12 | Seiko Epson Corp | Exterior parts for watch |
| CN1743492A (en) * | 2004-08-30 | 2006-03-08 | 北京航空航天大学 | High-content noble metal base non-crystal state alloy |
| WO2006045106A1 (en) * | 2004-10-15 | 2006-04-27 | Liquidmetal Technologies, Inc | Au-base bulk solidifying amorphous alloys |
| US20080135136A1 (en) * | 2006-02-24 | 2008-06-12 | California Institute Of Technology | Metallic glass alloys of palladium, copper, cobalt, and phosphorus |
| US20090162629A1 (en) * | 2007-07-12 | 2009-06-25 | Demetriou Marios D | Ni and cu free pd-based metallic glasses |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3738076B2 (en) * | 1995-11-15 | 2006-01-25 | 帝国ピストンリング株式会社 | Noble metal based amorphous alloy with excellent plastic workability and applicable to large parts |
| JP2000256813A (en) * | 1999-03-05 | 2000-09-19 | Ykk Corp | Personal ornament |
| WO2002012576A1 (en) * | 2000-08-07 | 2002-02-14 | Tanaka Kikinzoku Kogyo K.K. | Noble-metal-based amorphous alloys |
| JP4617465B2 (en) * | 2005-09-27 | 2011-01-26 | 国立大学法人東北大学 | Precious metal-based metallic glass alloy for in-vivo components |
-
2011
- 2011-12-15 WO PCT/US2011/065208 patent/WO2012083044A1/en active Application Filing
- 2011-12-15 CN CN2011800658307A patent/CN103328674A/en active Pending
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55145138A (en) * | 1979-04-26 | 1980-11-12 | Seiko Epson Corp | Exterior parts for watch |
| CN1743492A (en) * | 2004-08-30 | 2006-03-08 | 北京航空航天大学 | High-content noble metal base non-crystal state alloy |
| WO2006045106A1 (en) * | 2004-10-15 | 2006-04-27 | Liquidmetal Technologies, Inc | Au-base bulk solidifying amorphous alloys |
| US20080135136A1 (en) * | 2006-02-24 | 2008-06-12 | California Institute Of Technology | Metallic glass alloys of palladium, copper, cobalt, and phosphorus |
| US20090162629A1 (en) * | 2007-07-12 | 2009-06-25 | Demetriou Marios D | Ni and cu free pd-based metallic glasses |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107779790A (en) * | 2017-09-25 | 2018-03-09 | 北京科技大学 | A kind of germanic no without phosphorus large scale palladium base non-crystaline amorphous metal of nickel and preparation method thereof |
| WO2019056595A1 (en) * | 2017-09-25 | 2019-03-28 | 北京科技大学 | Germanium-containing nickel-free phosphorus-free large-sized palladium-based amorphous alloy and preparation method therefor |
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|---|---|
| KR20130109201A (en) | 2013-10-07 |
| WO2012083044A1 (en) | 2012-06-21 |
| JP2014505164A (en) | 2014-02-27 |
| EP2652165A1 (en) | 2013-10-23 |
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