CN107779790B - Germanic no without phosphorus large scale palladium base amorphous alloy of nickel of one kind and preparation method thereof - Google Patents
Germanic no without phosphorus large scale palladium base amorphous alloy of nickel of one kind and preparation method thereof Download PDFInfo
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Abstract
A kind of germanic no without phosphorus large scale palladium base amorphous alloy of nickel of the invention and preparation method thereof, the atomic percent of the alloys components are as follows: Pd:73-80%, Cu:0 < b≤8%, Si:0-18%, Ge:2-20%, Ag:0-6%.Main advantages of the present invention have been free from nickel element, and potential bio-toxicity substantially reduces, and improve biocompatibility；Without containing P elements, the method for melting preparation is easy；With strong amorphous formation ability, using the purification of glass fluxing technique media technology and water quenching quick cooling can prepare the palladium base amorphous alloy of critical dimension 1-8mm, wherein the most strong ingredient of glass forming ability can prepare the amorphous alloy that critical dimension is not less than 4mm using the method for electric arc melting copper mold, can prepare the amorphous alloy that critical dimension is not less than 8mm using preparation method 3；With > 3% plastic deformation ability；Supercooling liquid phase region model with 40-60K.
Description
Technical field
The invention belongs to block amorphous alloy fields, and in particular to a kind of germanic no without phosphorus large scale palladium base amorphous alloy of nickel
And preparation method thereof, its critical dimension of related alloy is not less than 3% between 1-8mm, plastic deformation ability.
Technical background
Amorphous alloy (glassy metal) has the arrangement of long-range order different with atom in traditional metal materials, has nothing
The atomic structure for advising arrangement, the feature with longrange disorder shortrange order, there is no crystal boundary, dislocations etc. to lack in its microstructure
It falls into, is that there is the metal materials hoped as structure and function application of new generation in recent years.It is non-compared with traditional crystal alloy
High intensity, high rigidity, high elastic limit, low modulus and the excellent performance such as corrosion-resistant that there is peritectic alloy it cannot achieve.
In addition, amorphous alloy will enter supercooling liquid phase region, the amorphous alloy in supercooling liquid phase region after being heated above glass transformation temperature
Stickiness flow characteristics is shown, superplastic deformation characteristic is showed.This exclusive performance of amorphous alloy makes it in supercooled liquid
It can accurately compression moulding in phase region.These superior performances make amorphous alloy in many fields such as medical equipment, consumption
Electronic product, miniature electronic part even luxury goods etc. have and its wide application prospect.
In recent years, researcher obtains in more than ten alloy systems such as zirconium base, palladium base, lanthanum base, magnesium-based, iron-based, Ni-based
Block amorphous alloy.Although at present the maximum critical dimension of amorphous alloy already exceed 70mm, its suitable amorphous at
Divide and is often limited only in very narrow composition range；In addition, the unique atomic structure of amorphous alloy causes it by masterpiece
The feature of brittleness at room temperature is often shown under, under compression, catastrophic fracture occurs rapidly after reaching elastic limit,
Plastic deformation ability is almost nil.Therefore exploitation has the amorphous alloy component of big glass forming ability and high plastic deformation's ability
Remain the tireless objective of the struggle of researcher.Certain progress is gone in the exploitation of palladium base amorphous alloy component at present,
The critical dimension of Pd-Cu-Ni-P system alloy can achieve 72mm；Pd-Cu-Si system alloy is with certain glass forming ability
On the basis of also have both excellent plastic deformation ability.But according to document and patent retrieval, so far there is not yet open report has both height
Glass forming ability and the germanic palladium base amorphous alloy system of plastic deformation ability, while not phosphorous in design system and nickel alloy
Ingredient helps to simplify the preparation process of palladium-base alloy, and widens its application on wearing luxury goods and bio-medical material
Prospect.
Summary of the invention
The present invention develops a kind of germanic no without phosphorus large scale palladium base amorphous alloy of nickel, it is therefore intended that not only removes to biology
Body has the nickel element of toxic side effect, good biocompatibility, and not phosphorous, preparation process relative ease, has strong amorphous
At ability and plastic deformation ability, to obtain amorphous alloy in the two all good resultant effect of aspect of safety and processability.
The technical scheme is that a kind of germanic no without phosphorus large scale palladium base amorphous alloy of nickel, the original of the amorphous alloy
Sub- percentage expression formula is PdaCubGec, a, b and c respectively indicate the atomic percent of each corresponding element in formula, wherein 73≤a≤
80,0 < b≤8,2≤c≤20, and a+b+c=100.
A kind of germanic no without phosphorus large scale palladium base amorphous alloy of nickel, the atomic percent expression formula of the amorphous alloy is
PdaCubGecSidAge, a, b, c and d respectively indicate the atomic percent of each corresponding element in formula, wherein 73≤a≤80,0 < b≤
8,2≤c≤20,0≤d≤18,0≤e≤6, and a+b+c+d+e=100.
A kind of germanic no without phosphorus large scale palladium base amorphous alloy of nickel, the atomic percent expression formula of the amorphous alloy are
PdaCubGecSidAgeXf, and each component: 73≤a≤80,0 < b≤8,2≤c≤20,0≤d≤18,0≤e≤6,0≤f≤4
And a+b+c+d+e+f=100, wherein X is one of Co, Au, Pt or a variety of.
Further, as a=77.5, b=6, c=16.5, the atomic percent expression formula of amorphous alloy is Pd74.5Cu3Ge16.5。
Further, as a=77.5, b=6, c=8.5, the atomic percent expression formula of d=8, e=0, amorphous alloy are
Pd74.5Cu3Si8Ge8.5。
Further, the atomic percent expression formula of a=77.5, b=5, c=12.5, d=4, e=1, amorphous alloy is
Pd74.5Cu5Si12.5Ge4Ag1；Or a=77.5, b=4, the atomic percent expression formula of c=4, d=12.5, e=2, amorphous alloy are
Pd74.5Cu4Si12.5Ge4Ag2；Or a=77.5, b=3, the atomic percent expression formula of c=4, d=12.5, e=3, amorphous alloy are
Pd74.5Cu3Si12.5Ge4Ag3。Pd74.5Cu3Si12.5Ge4Ag3。
Further, when X is Au, a=73.5, b=5, c=4, d=12.5, e=1, f=4, the atomic percent table of amorphous alloy
It is Pd up to formula74.5Cu3Si12.5Ge4Ag3Au4。
It is a further object of the present invention to provide the preparation method of above-mentioned alloy, this method specifically includes the following steps:
Preparation method (1): non-glass fluxing technique purification prepares master alloy, and amorphous alloy is prepared in a manner of copper mold, step
Suddenly include:
Step 1. ingredient: with purity be the metal Pd of 99.0wt%-99.99wt%, Cu, Ag and nonmetallic Si, Ge according to
The atomic percent of above-mentioned expression formula is converted into quality, and raw material surface scale is removed, and cleans raw material using industrial alcohol,
And it is weighed by respective required quality；
Step 2. foundry alloy melting: step 1 treated raw material is deposited in non-consumable vacuum electric by fusing point sequence
In arc furnace or cold crucible shower furnace, it is lower than 10 in vacuum-3It is filled with after Pa and carries out melting in high-purity argon gas (not less than 99.99%), until
Few melting 4 times, keep the abundant melting of master alloy uniform；
Step 3., which polishes master alloy prepared by melting, is put into the different size water coolings of vacuum arc furnace ignition after scale removal
On copper mold, electric arc furnace cavity is evacuated to lower than 10-30.08MPa high-purity argon gas (not less than 99.99%) is filled with after Pa, with
150A electric current melts master alloy, and continuous heating 15s, and arc current is increased between 200-250A, opens inhale casting rapidly
Master alloy is pressed into water cooled copper mould by air pressure and cooled down, obtains various sizes of amorphous alloy by vacuum valve.
Further, preparation method (2): glass fluxing technique purification prepares master alloy, and amorphous conjunction is prepared in a manner of copper mold
Gold, step include:
Step 1. ingredient: with purity be the metal Pd of 99.0wt%-99.99wt%, Cu, Ag and nonmetallic Si, Ge according to
The atomic percent of above-mentioned expression formula is converted into quality, and raw material surface scale is removed, and cleans raw material using industrial alcohol,
And it is weighed by respective required quality；
Step 2. foundry alloy melting: step 1 treated raw material is deposited in non-consumable vacuum electric by fusing point sequence
In arc furnace or cold crucible shower furnace, it is lower than 10 in vacuum-3It is filled with after Pa and carries out melting in high-purity argon gas (not less than 99.99%), until
Few melting 4 times, keep the abundant melting of master alloy uniform；
The purification of step 3. glass fluxing technique: master alloy and dewatered diboron trioxide medium are placed in various sizes of stone
Ying Guanzhong will be filled with 0.2MPa high-purity argon gas after vacuum in quartz ampoule is evacuated to 10Pa or less, and be placed in quartz ampoule
1100oIt is purified 24 hours in C electric furnace, later by melt furnace cooling；
After step 4. removes the cladding medium of the attachment of the alloy ingot surface after glass fluxing technique purifies with sand paper, it is put into vacuum
On the different size water cooled copper moulds of electric arc furnaces, electric arc furnace cavity is evacuated to lower than 10-30.08MPa high-purity argon gas is filled with after Pa
(being not less than 99.99%), master alloy is melted with 150A electric current, and continuous heating 15s, arc current is increased to 200-250A
Between, it opens inhale casting vacuum valve rapidly, master alloy is pressed into water cooled copper mould by air pressure and is cooled down, is obtained various sizes of
Amorphous alloy.
Further, preparation method (3): glass fluxing technique purification prepares master alloy, and prepares amorphous alloy with water quenching method,
Step includes:
Step 1. ingredient: with purity be the metal Pd of 99.0wt%-99.99wt%, Cu, Ag and nonmetallic Si, Ge according to
The atomic percent of above-mentioned expression formula is converted into quality, and raw material surface scale is removed, and cleans raw material using industrial alcohol,
And it is weighed by respective required quality；
Step 2. foundry alloy melting: step 1 treated raw material is deposited in non-consumable vacuum electric by fusing point sequence
In arc furnace or cold crucible shower furnace, it is lower than 10 in vacuum-3It is filled with after Pa and carries out melting in high-purity argon gas (not less than 99.99%), until
Few melting 4 times, keep the abundant melting of master alloy uniform；
The purification of step 3. glass fluxing technique: master alloy and dewatered diboron trioxide medium are placed in various sizes of stone
Ying Guanzhong will be filled with 0.2MPa high-purity argon gas after vacuum in quartz ampoule is evacuated to 10Pa or less, and be placed in quartz ampoule
1100oIt is purified 24 hours in C electric furnace；
Alloy pig of the step 4. after glass fluxing technique purifies directly is quenched in the molten state is not less than the room of 25wt% into concentration
In warm saline solution, various sizes of amorphous alloy is prepared.
The atomic percent expression formula of the amorphous alloy is PdaCubGec, a, b and c respectively indicate each corresponding element in formula
Atomic percent, wherein 73≤a≤80,0 < b≤8,2≤c≤20, and a+b+c=100.
As a=77.5, b=6, c=16.5, the atomic percent expression formula of amorphous alloy is Pd74.5Cu3Ge16.5, pass through
Preparation method (3) can prepare the amorphous alloy that critical dimension is not less than 1mm.
The atomic percent expression formula of the amorphous alloy is PdaCubGecSid, a, b, c and d respectively indicate each correspondence in formula
The atomic percent of element, wherein 73≤a≤80,0 < b≤8,2≤c≤20,0≤d≤18, and a+b+c+d=100.
As a=77.5, b=6,0≤d≤12.5, c=16.5,4≤e≤16.5, the atomic percent of amorphous alloy is expressed
Formula is Pd77.5Cu6SicGe16.5-c, the amorphous alloy that critical dimension is not less than 1mm can be prepared by preparation method (3).
When the atomic percent expression formula of a=77.5, b=6, d=8.5, c=8, e=0, amorphous alloy are
Pd74.5Cu3Si8Ge8.5, the amorphous alloy that critical dimension is not less than 2mm can be prepared by preparation method (3).
As a=77.5, b=6, c=12.5, d=4, Pd77.5Cu6Si12.5Ge4Alloy, master alloy can be made through preparation method (1)
Standby critical dimension is not less than the amorphous alloy of 2mm；Amorphous of the critical dimension not less than 4mm can be prepared by preparation method (2) to close
Gold, supercooled liquid phase sector width 54K.
The atomic percent expression formula of the amorphous alloy is PdaCubSicGedAge, a, b, c, d and e are respectively indicated respectively in formula
The atomic percent of corresponding element, wherein 73≤a≤80,0 < b≤8,0≤d≤18,2≤c≤20,0≤e≤6, and a+b+c+
d+e=100。
As a=77.5,4≤b≤6, c=4, d=12.5,1≤e≤2, the atomic percent expression formula of amorphous alloy
Pd77.5CubSi12.5Ge4Ag6-b, master alloy through preparation method (1) can prepare critical dimension be not less than 2mm amorphous alloy；Pass through
Preparation method (3) is capable of forming large block amorphous critical dimension not less than 8mm, and plastic strain is not less than 5%.
As a=77.5, b=3, c=4, d=12.5, e=3, the atomic percent expression formula of amorphous alloy is
Pd77.5Cu3Si12.5Ge4Ag3, master alloy through preparation method (1) can prepare critical dimension be not less than 4mm amorphous alloy；Pass through system
Standby mode (3) are capable of forming large block amorphous critical dimension not less than 8mm, and plastic strain is not less than 11%.
The atomic percent of amorphous alloy expresses PdaCubSicGedAgeXf, a, b, c, d and e respectively indicate each correspondence in formula
The atomic percent of element, wherein 73≤a≤80,0 < b≤8,0≤d≤18,2≤c≤20,1≤e≤6,0≤f≤4 and a+b
+ c+d+e+f=100, wherein X is one of Co, Au, Pt or a variety of.
When X is Au, a=73.5, b=5, c=4, d=12.5, when e=1, f=4, the atomic percent expression formula of amorphous alloy is
Pd74.5Cu3Si12.5Ge4Ag3Au4, large block amorphous critical dimension is capable of forming not less than 8mm by preparation method (3).
The amorphous alloy that three kinds of different preparation methods obtain is compared, critical dimension size is preparation method (1) < preparation
Mode (2) < preparation method (3).
The present invention has the advantages that
1. a series of palladium base amorphous alloys according to the present invention have excellent amorphous formation ability, maximum critical ruler
It is very little to be not less than 8mm.
2. a series of palladium base amorphous alloys according to the present invention, alloy essential element is Pd, Cu, Si, Ge, Ag, is free of
There is Ni etc. toxic or to the easy sensitization element of biology, there is preferable biocompatibility.
3. a series of palladium base amorphous alloys according to the present invention, alloy essential element is Pd, Cu, Si, Ge, Ag, is free of
There is volatile P, smelting preparation method is easy.
4. a series of palladium base amorphous alloys according to the present invention, plastic deformation ability is strong, and highest plastic deformation ability is not
Less than 5%.
Detailed description of the invention
Fig. 1 is Pd77.5Cu6Si4Ge8.5Or Pd77.5Cu6Si4Ge8.5The XRD spectrum of amorphous alloy.
Fig. 2 is Pd77.5Cu6Si12.5Ge4The XRD spectrum of amorphous alloy.
Fig. 3 is Pd77.5Cu6Si12.5Ge4The DSC curve of amorphous alloy.
Fig. 4 is Pd77.5Cu6Si12.5Ge4The compression stress strain curve of amorphous alloy.
Fig. 5 is Pd77.5Cu5Si12.5Ge4Ag1, Pd77.5Cu4Si12.5Ge4Ag2The XRD spectrum of amorphous alloy.
Fig. 6 is Pd77.5Cu5Si12.5Ge4Ag1, Pd77.5Cu4Si12.5Ge4Ag2The SEM of amorphous alloy schemes.
Fig. 7 is Pd77.5Cu3Si12.5Ge4Ag3The XRD spectrum of amorphous alloy.
Fig. 8 is Pd77.5Cu3Si12.5Ge4Ag3The SEM of amorphous alloy schemes.
Fig. 9 is Pd77.5Cu5Si12.5Ge4Ag1, Pd77.5Cu4Si12.5Ge4Ag2, Pd77.5Cu3Si12.5Ge4Ag3Amorphous alloy
Compression stress strain curve.
Figure 10 is Pd74.5Cu3Si12.5Ge4Ag3Au4The XRD spectrum of amorphous alloy.
Figure 11 is Pd77.5Cu5Si12.5Ge4Ag1, Pd77.5Cu4Si12.5Ge4Ag2,Pd77.5Cu3Si12.5Ge4Ag3, amorphous alloy
XRD spectrum.
Specific embodiment
Technical scheme is described further combined with specific embodiments below.
A kind of germanic no without phosphorus large scale palladium base amorphous alloy of nickel of the invention, the atomic percent expression formula of the amorphous alloy
For PdaCubGec, a, b and c respectively indicate the atomic percent of each corresponding element in formula, wherein 73≤a≤80,0 < b≤8, and 2
≤ c≤20, and a+b+c=100.
Further, the atomic percent expression formula of the amorphous alloy is PdaCubGecSidAge, a, b, c and d distinguish table in formula
Show the atomic percent of each corresponding element, wherein 73≤a≤80,0 < b≤8,2≤c≤20,0≤d≤18,0≤e≤6, and a
+b+c+d+e =100。
Further, the atomic percent expression formula of the amorphous alloy is PdaCubGecSidAgeXf, and each component: 73≤a≤
80,0 < b≤8,2≤c≤20,0≤d≤18,0≤e≤6,0≤f≤4 and a+b+c+d+e+f=100, wherein X is Co, Au, Pt
One of or it is a variety of.
Further, as a=77.5, b=6, c=16.5, the atomic percent expression formula of amorphous alloy is Pd74.5Cu3Ge16.5。
Further, as a=77.5, b=6, c=8.5, the atomic percent expression formula of d=8, e=0, amorphous alloy are
Pd74.5Cu3Si8Ge8.5。
Further, the atomic percent expression formula of a=77.5, b=5, c=12.5, d=4, e=1, amorphous alloy is
Pd74.5Cu5Si12.5Ge4Ag1；Or a=77.5, b=4, the atomic percent expression formula of c=12.5, d=4, e=2, amorphous alloy are
Pd74.5Cu4Si12.5Ge4Ag2；Or a=77.5, b=3, the atomic percent expression formula of c=12.5, d=4, e=3, amorphous alloy are
Pd74.5Cu3Si12.5Ge4Ag3。Pd74.5Cu3Si12.5Ge4Ag3。
Further, when X is Au, a=73.5, b=5, c=12.5, d=4, e=1, f=4, the atomic percent table of amorphous alloy
It is Pd up to formula74.5Cu3Si12.5Ge4Ag3Au4。
It is a further object of the present invention to provide the preparation method of above-mentioned alloy, this method specifically includes the following steps:
Preparation method (1): non-glass fluxing technique purification prepares master alloy, and amorphous alloy is prepared in a manner of copper mold, step
Suddenly include:
Step 1. ingredient: with purity be the metal Pd of 99.0wt%-99.99wt%, Cu, Ag and nonmetallic Si, Ge according to
The atomic percent of above-mentioned expression formula is converted into quality, and raw material surface scale is removed, and cleans raw material using industrial alcohol,
And it is weighed by respective required quality；
Step 2. foundry alloy melting: step 1 treated raw material is deposited in non-consumable vacuum electric by fusing point sequence
In arc furnace or cold crucible shower furnace, it is lower than 10 in vacuum-3It is filled with after Pa and carries out melting in high-purity argon gas (not less than 99.99%), until
Few melting 4 times, keep the abundant melting of master alloy uniform；
Step 3., which polishes master alloy prepared by melting, is put into the different size water coolings of vacuum arc furnace ignition after scale removal
On copper mold, electric arc furnace cavity is evacuated to lower than 10-30.08MPa high-purity argon gas (not less than 99.99%) is filled with after Pa, with
150A electric current melts master alloy, and continuous heating 15s, and arc current is increased between 200-250A, opens inhale casting rapidly
Master alloy is pressed into water cooled copper mould by air pressure and cooled down, obtains various sizes of amorphous alloy by vacuum valve.
Further, preparation method (2): glass fluxing technique purification prepares master alloy, and amorphous conjunction is prepared in a manner of copper mold
Gold, step include:
Step 1. ingredient: with purity be the metal Pd of 99.0wt%-99.99wt%, Cu, Ag and nonmetallic Si, Ge according to
The atomic percent of above-mentioned expression formula is converted into quality, and raw material surface scale is removed, and cleans raw material using industrial alcohol,
And it is weighed by respective required quality；
Step 2. foundry alloy melting: step 1 treated raw material is deposited in non-consumable vacuum electric by fusing point sequence
In arc furnace or cold crucible shower furnace, it is lower than 10 in vacuum-3It is filled with after Pa and carries out melting in high-purity argon gas (not less than 99.99%), until
Few melting 4 times, keep the abundant melting of master alloy uniform；
The purification of step 3. glass fluxing technique: master alloy and dewatered diboron trioxide medium are placed in various sizes of stone
Ying Guanzhong will be filled with 0.2MPa high-purity argon gas after vacuum in quartz ampoule is evacuated to 10Pa or less, and be placed in quartz ampoule
1100oIt is purified 24 hours in C electric furnace, later by melt furnace cooling；
After step 4. removes the cladding medium of the attachment of the alloy ingot surface after glass fluxing technique purifies with sand paper, it is put into vacuum
On the different size water cooled copper moulds of electric arc furnaces, electric arc furnace cavity is evacuated to lower than 10-30.08MPa high-purity argon gas is filled with after Pa
(being not less than 99.99%), master alloy is melted with 150A electric current, and continuous heating 15s, arc current is increased to 200-250A
Between, it opens inhale casting vacuum valve rapidly, master alloy is pressed into water cooled copper mould by air pressure and is cooled down, is obtained various sizes of
Amorphous alloy.
Further, preparation method (3): glass fluxing technique purification prepares master alloy, and prepares amorphous alloy with water quenching method,
Step includes:
Step 1. ingredient: with purity be the metal Pd of 99.0wt%-99.99wt%, Cu, Ag and nonmetallic Si, Ge according to
The atomic percent of above-mentioned expression formula is converted into quality, and raw material surface scale is removed, and cleans raw material using industrial alcohol,
And it is weighed by respective required quality；
Step 2. foundry alloy melting: step 1 treated raw material is deposited in non-consumable vacuum electric by fusing point sequence
In arc furnace or cold crucible shower furnace, it is lower than 10 in vacuum-3It is filled with after Pa and carries out melting in high-purity argon gas (not less than 99.99%), until
Few melting 4 times, keep the abundant melting of master alloy uniform；
The purification of step 3. glass fluxing technique: master alloy and dewatered diboron trioxide medium are placed in various sizes of stone
Ying Guanzhong will be filled with 0.2MPa high-purity argon gas after vacuum in quartz ampoule is evacuated to 10Pa or less, and be placed in quartz ampoule
1100oIt is purified 24 hours in C electric furnace；
Alloy pig of the step 4. after glass fluxing technique purifies directly is quenched in the molten state is not less than the room of 25wt% into concentration
In warm saline solution, various sizes of amorphous alloy is prepared.
The preparation of embodiment 1:Pd-Cu-Si-Ge system amorphous alloy:
Design PdaCubGecSidAgeAmorphous alloy component, wherein a=77.5, b=6, c=16.5,8.5,4,8,12.5, d=0,
e=0.Obtaining ingredient is Pd77.5Cu6Ge16.5、Pd77.5Cu6Si8Ge8.5、Pd77.5Cu6Si12.5Ge4Alloy.
Fig. 1 is alloy Pd77.5Cu6Ge16.5、Pd77.5Cu6Si8Ge8.5The XRD of 2mm sample by preparation method (3) preparation
Map, Fig. 2 are alloy Pd77.5Cu6Si12.5Ge4The XRD spectrum of 2mm and 4mm sample by preparation method (2) preparation, map
The only typical diffusing scattering peak of amorphous shows that prepared alloy is amorphous phase, which can be made by preparation method (3)
Standby critical dimension is not less than the amorphous alloy of 2mm, Pd77.5Cu6Si12.5Ge4Alloy can prepare critical ruler by preparation method (2)
The very little amorphous alloy not less than 4mm has stronger amorphous formation ability.Fig. 3 is alloy Pd77.5Cu6Si12.5Ge4DSC curve,
Its supercooled liquid phase section is 54K.
Fig. 4 is Pd77.5Cu6Si12.5Ge4The compression stress strain curve of alloy, compression yield strength 1650MPa, pressure
Contracting plasticity 3.5%.
The preparation of embodiment 2:Pd-Cu-Si-Ge-Ag system amorphous alloy:
Design PdaCubGecSidAgeAmorphous alloy component, wherein a=77.5, b=5,4,3, c=4, d=12.5, e=1,2,3.
Obtaining ingredient is Pd77.5Cu5Si12.5Ge4Ag1, Pd77.5Cu4Si12.5Ge4Ag2、Pd77.5Cu3Si12.5Ge4Ag3Alloy.
Fig. 5 is alloy Pd77.5Cu5Si12.5Ge4Ag1, Pd77.5Cu4Si12.5Ge4Ag2The 8mm prepared by preparation method (3)
The XRD spectrum of sample, Fig. 6 are SEM photograph corresponding with Fig. 5, and Fig. 7 is alloy Pd77.5Cu3Si12.5Ge4Ag3By preparation side
The 8mm sample and preparation method (1) of formula (3) preparation prepare the XRD spectrum of 4mm sample, and Fig. 8 is SEM corresponding with Fig. 7
Photo, XRD spectrum only have the typical diffusing scattering peak of amorphous, and corresponding SEM photograph also shows that the single amorphous phase group of alloy
At showing that prepared alloy is amorphous phase, which can prepare critical dimension not less than 8mm's by preparation method (3)
Amorphous passes through preparation method (1) Pd77.5Cu5Si12.5Ge4Ag1, Pd77.5Cu4Si12.5Ge4Ag2Alloy can prepare critical dimension not
Amorphous alloy less than 2mm, Pd77.5Cu3Si12.5Ge4Ag3Alloy can prepare the amorphous alloy that critical dimension is not less than 4mm, have
Strong amorphous formation ability.
Fig. 9 is alloy Pd77.5Cu5Si12.5Ge4Ag1, Pd77.5Cu4Si12.5Ge4Ag2、Pd77.5Cu3Si12.5Ge4Ag3Compression
Stress-strain diagram, wherein alloy Pd77.5Cu5Si12.5Ge4Ag1Compression yield strength be 1602MPa, compression plasticity 11%.
The preparation of embodiment 3:Pd-Cu-Si-Ge-Ag-X system amorphous alloy:
Design PdaCubGecSidAgeXfAmorphous alloy component, wherein X be Au, a=73.5, b=5, c=4, d=12.5, e=
1, f=4.Obtaining ingredient is Pd74.5Cu3Si12.5Ge4Ag3Au4Alloy.
Fig. 5 is Pd74.5Cu3Si12.5Ge4Ag3Au4The XRD spectrum of 8mm sample of the alloy by preparation method (3) preparation,
XRD spectrum only has the typical diffusing scattering peak of amorphous, shows that prepared alloy is amorphous phase, can be prepared by preparation method (3)
Critical dimension is not less than the amorphous alloy of 8mm, has strong amorphous formation ability.
A kind of germanic no without phosphorus large scale palladium base amorphous alloy of nickel of the invention and preparation method thereof, the original of the alloys components
Sub- percentage are as follows: Pd:73-80%, Cu:0 < b≤8%, Si:0-18%, Ge:2-20%, Ag:0-6%.Main advantages of the present invention are
Without containing nickel element, potential bio-toxicity is substantially reduced, and improves biocompatibility；It is prepared without containing P elements, melting
Method is easy；With strong amorphous formation ability, using the purification of glass fluxing technique media technology and water quenching quick cooling can prepare critical ruler
The palladium base amorphous alloy of very little 1-8mm, wherein the most strong ingredient of glass forming ability can be made using the method for electric arc melting copper mold
Standby critical dimension is not less than the amorphous alloy of 4mm, can prepare amorphous of the critical dimension not less than 8mm using preparation method 3 and close
Gold；With > 3% plastic deformation ability；Supercooling liquid phase region model with 40-60K.
Claims (10)
1. a kind of germanic no without phosphorus large scale palladium base amorphous alloy of nickel, which is characterized in that the atomic percent table of the amorphous alloy
It is Pd up to formulaaCubGec, a, b and c respectively indicate the atomic percent of each corresponding element in formula, wherein 73≤a≤80,0 < b≤
8,2≤c≤20, and a+b+c=100.
2. a kind of germanic no without phosphorus large scale palladium base amorphous alloy of nickel, which is characterized in that it is characterized in that, the original of the amorphous alloy
Sub- percentage expression formula is PdaCubGecSidAge, a, b, c, d and e respectively indicate the atomic percent of each corresponding element in formula,
Wherein 73≤a≤80,0 < b≤8,2≤c≤20,0≤d≤18,0≤e≤6, and a+b+c+d+e=100.
3. a kind of germanic no without phosphorus large scale palladium base amorphous alloy of nickel, which is characterized in that the atomic percent table of the amorphous alloy
It is Pd up to formulaaCubGecSidAgeXf, and each component: 73≤a≤80,0 < b≤8,2≤c≤20,0≤d≤18,0≤e≤6,0
≤ f≤4, and a+b+c+d+e+f=100, wherein X is one of Co, Au, Pt or a variety of.
4. the without phosphorus large scale palladium base amorphous alloy of germanic no nickel according to claim 1, which is characterized in that as a=77.5, b=
6, c=16.5, the atomic percent expression formula of amorphous alloy is Pd74.5Cu3Ge16.5。
5. the without phosphorus large scale palladium base amorphous alloy of germanic no nickel according to claim 2, which is characterized in that as a=77.5, b=
6, c=8.5, d=8, e=0, the atomic percent expression formula of amorphous alloy are Pd74.5Cu3Si8Ge8.5。
6. the germanic no without phosphorus large scale palladium base amorphous alloy of nickel according to claim 2, which is characterized in that a=77.5, b=
5, c=4, d=12.5, e=1, the atomic percent expression formula of amorphous alloy are Pd74.5Cu5Si12.5Ge4Ag1；Or a=77.5, b=
4, c=12.5, d=4, e=2, the atomic percent expression formula of amorphous alloy are Pd74.5Cu4Si12.5Ge4Ag2；Or a=77.5, b=
3, c=4, d=12.5, e=3, the atomic percent expression formula of amorphous alloy are Pd74.5Cu3Si12.5Ge4Ag3。
7. the germanic no without phosphorus large scale palladium base amorphous alloy of nickel according to claim 3, which is characterized in that when X be Au, a=
The atomic percent expression formula of 73.5, b=5, c=4, d=12.5, e=1, f=4, amorphous alloy is
Pd74.5Cu3Si12.5Ge4Ag3Au4。
8. a kind of method for preparing the amorphous alloy as described in any in claim 1-7, which is characterized in that specifically include with
Under:
Preparation method (1): non-glass fluxing technique purification prepares master alloy, and amorphous alloy is prepared in a manner of copper mold, step packet
It includes:
Step 1. ingredient: being the metal Pd of 99.0wt%-99.99wt%, Cu, Ag and nonmetallic Si with purity, Ge is according to above-mentioned
The atomic percent of expression formula is converted into quality, and raw material surface scale is removed, and cleans raw material using industrial alcohol, and press
Quality needed for respectively weighs；
Step 2. foundry alloy melting: step 1 treated raw material is deposited in non-consumable arc furnace by fusing point sequence
Or in cold crucible shower furnace, it is lower than 10 in vacuum-3It being filled with after Pa in high-purity argon gas, purity carries out melting not less than 99.99%, until
Few melting 4 times, keep the abundant melting of master alloy uniform；
Step 3., which polishes master alloy prepared by melting, is put into the different size water cooled copper moulds of vacuum arc furnace ignition after scale removal
On, electric arc furnace cavity is evacuated to lower than 10-3The argon gas that 0.08MPa purity is not less than 99.99% is filled with after Pa, with 150A electricity
Stream melts master alloy, and continuous heating 15s, and arc current is increased between 200-250A, opens inhale casting vacuum valve rapidly
Master alloy is pressed into water cooled copper mould by air pressure and cooled down, obtains various sizes of amorphous alloy by door.
9. a kind of method for preparing the amorphous alloy as described in any in claim 1-7, which is characterized in that specifically include with
Under:
Preparation method (2): glass fluxing technique purification prepares master alloy, and amorphous alloy is prepared in a manner of copper mold, and step includes:
Step 1. ingredient: being the metal Pd of 99.0wt%-99.99wt%, Cu, Ag and nonmetallic Si with purity, Ge is according to above-mentioned
The atomic percent of expression formula is converted into quality, and raw material surface scale is removed, and cleans raw material using industrial alcohol, and press
Quality needed for respectively weighs；
Step 2. foundry alloy melting: step 1 treated raw material is deposited in non-consumable arc furnace by fusing point sequence
Or in cold crucible shower furnace, it is lower than 10 in vacuum-3It is filled with after Pa in high-purity argon gas, carries out melting, at least melting 4 times makes female conjunction
Golden sufficiently melting is uniform；
The purification of step 3. glass fluxing technique: master alloy and dewatered diboron trioxide medium are placed in various sizes of quartz ampoule
In, 0.2MPa high-purity argon gas will be filled in quartz ampoule after vacuum in quartz ampoule is evacuated to 10Pa or less, and be placed in 1100oC electricity
It is purified 24 hours in furnace, later by melt furnace cooling；
After step 4. removes the cladding medium of the attachment of the alloy ingot surface after glass fluxing technique purifies with sand paper, it is put into vacuum arc
On the different size water cooled copper moulds of furnace, electric arc furnace cavity is evacuated to lower than 10-30.08MPa purity is filled with after Pa to be not less than
99.99% argon gas is melted master alloy with 150A electric current, and continuous heating 15s, by arc current be increased to 200-250A it
Between, it opens inhale casting vacuum valve rapidly, master alloy is pressed into water cooled copper mould by air pressure and is cooled down, is obtained various sizes of non-
Peritectic alloy.
10. a kind of method for preparing the amorphous alloy as described in any in claim 1-7, which is characterized in that specifically include with
Under:
Preparation method (3): glass fluxing technique purification prepares master alloy, and prepares amorphous alloy with water quenching method, and step includes:
Step 1. ingredient: being the metal Pd of 99.0wt%-99.99wt%, Cu, Ag and nonmetallic Si with purity, Ge is according to above-mentioned
The atomic percent of expression formula is converted into quality, and raw material surface scale is removed, and cleans raw material using industrial alcohol, and press
Quality needed for respectively weighs；
Step 2. foundry alloy melting: step 1 treated raw material is deposited in non-consumable arc furnace by fusing point sequence
Or in cold crucible shower furnace, it is lower than 10 in vacuum-3It is filled with after Pa and is not less than 99.99% argon gas in purity, carry out melting, at least
Melting 4 times, keep the abundant melting of master alloy uniform；
The purification of step 3. glass fluxing technique: master alloy and dewatered diboron trioxide medium are placed in various sizes of quartz ampoule
In, 0.2MPa high-purity argon gas will be filled in quartz ampoule after vacuum in quartz ampoule is evacuated to 10Pa or less, and be placed in 1100oC electricity
It is purified 24 hours in furnace；
The room temperature that alloy pig of the step 4. after glass fluxing technique purifies directly is quenched in the molten state into concentration not less than 25wt% is eaten
In salt water, various sizes of amorphous alloy is prepared.
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| PCT/CN2017/115922 WO2019056595A1 (en) | 2017-09-25 | 2018-02-27 | Germanium-containing nickel-free phosphorus-free large-sized palladium-based amorphous alloy and preparation method therefor |
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| JPS59205434A (en) * | 1983-05-04 | 1984-11-21 | Hitachi Ltd | Pd base amorphous alloy for hydrogen separating and refining membrane material |
| JPS6033382A (en) * | 1983-08-03 | 1985-02-20 | Nippon Pureeteingu Kk | Electrodeposition of amorphous alloy by pulse electrolysis |
| JPH01215938A (en) * | 1988-02-24 | 1989-08-29 | Tokuyama Soda Co Ltd | Palladium alloy for dental use |
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