CN107779790A - A kind of germanic no without phosphorus large scale palladium base non-crystaline amorphous metal of nickel and preparation method thereof - Google Patents
A kind of germanic no without phosphorus large scale palladium base non-crystaline amorphous metal of nickel and preparation method thereof Download PDFInfo
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Abstract
A kind of germanic no without phosphorus large scale palladium base non-crystaline amorphous metal of nickel of the invention and preparation method thereof, the atomic percent of the alloys components is：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 improves biocompatibility；P elements are not contained, method prepared by melting is easy；With strong amorphous formation ability, the 8mm of critical dimension 1 palladium base non-crystaline amorphous metal can be prepared using the purification of glass fluxing technique media technology and water quenching quick cooling, wherein the most strong composition of glass forming ability can prepare non-crystaline amorphous metal of the critical dimension not less than 4mm using the method for electric arc melting copper mold, and non-crystaline amorphous metal of the critical dimension not less than 8mm can be prepared using preparation method 3；Have>3% plastic deformation ability；Supercooling liquid phase region model with 40 60K.
Description
Technical field
The invention belongs to block amorphous alloy field, and in particular to a kind of germanic no without phosphorus large scale palladium base non-crystaline amorphous metal of nickel
And preparation method thereof, its critical dimension of involved alloy is not less than 3% between 1-8mm, plastic deformation ability.
Technical background
Amorphous alloy（Glassy metal）It is different with the arrangement that atom in traditional metal materials has long-range order, there is nothing
The atomic structure of arrangement is advised, the feature with longrange disorder shortrange order, it is scarce that crystal boundary, dislocation etc. are not present in its microstructure
Fall into, be that there is the metal material hoped as 26S Proteasome Structure and Function of new generation application in recent years.It is non-compared with traditional crystal alloy
Peritectic alloy has its high intensity that can not be realized, high rigidity, high elastic limit, low modulus and the excellent performance such as corrosion-resistant.
In addition, non-crystaline amorphous metal will enter supercooling liquid phase region, the non-crystaline amorphous metal in supercooling liquid phase region after being heated above glass transformation temperature
Stickiness flow performance is shown, shows superplastic deformation characteristic.This exclusive performance of non-crystaline amorphous metal makes it in supercooled liquid
Can be accurately compressing in phase region.These superior performances cause 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 zirconium base, palladium base, lanthanum base, magnesium-based, iron-based, Ni-based etc. more than ten plants alloy system
Block amorphous alloy.Although the maximum critical dimension of non-crystaline amorphous metal alreadys exceed 70mm at present, its suitable amorphous into
Divide and be often limited only in very narrow composition range；In addition, unique atomic structure of non-crystaline amorphous metal causes it by masterpiece
The feature of brittleness at room temperature is often shown under, under compression, the rapid calamity that occurs is broken after it reaches elastic limit,
Plastic deformation ability is almost nil.Therefore amorphous alloy component of the exploitation with 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 systems alloy can reach 72mm；Pd-Cu-Si systems alloy is with certain glass forming ability
On the basis of also have excellent plastic deformation ability concurrently.But according to document and patent retrieval, so far there is not yet open report has height concurrently
Glass forming ability and the germanic palladium base non-crystaline amorphous metal system of plastic deformation ability, while not phosphorous in the design system and alloy of nickel
Composition helps to simplify the preparation technology of palladium-base alloy, and widens its application on wearing luxury goods and bio-medical material
Prospect.
The content of the invention
The present invention develops a kind of germanic no without phosphorus large scale palladium base non-crystaline amorphous metal 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 technology relative ease, has strong amorphous
Into ability and plastic deformation ability, to obtain non-crystaline amorphous metal in all good resultant effect of security and the aspect of processability two.
The technical scheme is that：A kind of germanic no without phosphorus large scale palladium base non-crystaline amorphous metal of nickel, the original of the non-crystaline amorphous metal
Sub- percentage expression formula is PdaCubGec, a, b and c represent the atomic percent of each corresponding element respectively 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 non-crystaline amorphous metal of nickel, the atomic percent expression formula of the non-crystaline amorphous metal is
PdaCubGecSidAge, a, b, c and d represent the atomic percent of each corresponding element respectively 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 non-crystaline amorphous metal of nickel, the atomic percent expression formula of the non-crystaline amorphous metal 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 are the one or more in Co, Au, Pt.
Further, as a=77.5, b=6, c=16.5, the atomic percent expression formula of non-crystaline amorphous metal is Pd74.5Cu3Ge16.5。
Further, when a=77.5, b=6, c=8.5, d=8, e=0, the atomic percent expression formula of non-crystaline amorphous metal are
Pd74.5Cu3Si8Ge8.5。
Further, a=77.5, b=5, c=12.5, d=4, e=1, the atomic percent expression formula of non-crystaline amorphous metal are
Pd74.5Cu5Si12.5Ge4Ag1；Or a=77.5, b=4, c=4, d=12.5, e=2, the atomic percent expression formula of non-crystaline amorphous metal are
Pd74.5Cu4Si12.5Ge4Ag2；Or a=77.5, b=3, c=4, d=12.5, e=3, the atomic percent expression formula of non-crystaline amorphous metal 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 non-crystaline amorphous metal
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 following steps：
Preparation method（1）：Non- glass fluxing technique purification prepares foundry alloy, and non-crystaline amorphous metal is prepared in a manner of copper mold, step bag
Include：
Step 1. dispensing：Metal Pd using purity as 99.0wt%-99.99wt%, Cu, Ag and nonmetallic Si, Ge is according to above-mentioned
The atomic percent of expression formula is converted into quality, and raw material surface scale is removed, and using industrial alcohol cleaning raw material, and press
Quality needed for each weighs；
Step 2. foundry alloy melting：Raw material after step 1 is handled is deposited in non-consumable arc furnace by fusing point sequence
Or in cold crucible shower furnace, it is less than 10 in vacuum-3It is filled with after Pa in high-purity argon gas（Not less than 99.99%）Melting is carried out, it is at least molten
Refining 4 times, makes the abundant melting of foundry alloy uniform；
Step 3. will be put into the different size water cooled copper moulds of vacuum arc furnace ignition after foundry alloy prepared by melting polishing scale removal
On, electric arc furnace cavity is evacuated to less than 10-30.08MPa high-purity argon gas is filled with after Pa（Not less than 99.99%）, with 150A electricity
Stream melts foundry alloy, and continuous heating 15s, and between arc current is increased into 200-250A, rapid open inhales casting vacuum valve
Door, foundry alloy is pressed into water cooled copper mould by air pressure and cooled down, obtains various sizes of non-crystaline amorphous metal.
Further, preparation method（2）：Glass fluxing technique purification prepares foundry alloy, and amorphous conjunction is prepared in a manner of copper mold
Gold, step include：
Step 1. dispensing：Metal Pd using purity as 99.0wt%-99.99wt%, Cu, Ag and nonmetallic Si, Ge is according to above-mentioned
The atomic percent of expression formula is converted into quality, and raw material surface scale is removed, and using industrial alcohol cleaning raw material, and press
Quality needed for each weighs；
Step 2. foundry alloy melting：Raw material after step 1 is handled is deposited in non-consumable arc furnace by fusing point sequence
Or in cold crucible shower furnace, it is less than 10 in vacuum-3It is filled with after Pa in high-purity argon gas（Not less than 99.99%）Melting is carried out, it is at least molten
Refining 4 times, makes the abundant melting of foundry alloy uniform；
Step 3. glass fluxing technique purifies：Diboron trioxide medium after foundry alloy and dehydration is positioned over various sizes of quartz ampoule
In, 0.2MPa high-purity argon gas will be filled with quartz ampoule after vacuum in quartz ampoule is evacuated into below 10Pa, and be positioned over 1100oC electricity
Purified 24 hours in stove, afterwards by melt furnace cooling；
After step 4. removes the cladding medium of the alloy pig surface attachment after glass fluxing technique purifies with sand paper, vacuum arc is put into
On the different size water cooled copper moulds of stove, electric arc furnace cavity is evacuated to less than 10-30.08MPa high-purity argon gas is filled with after Pa（No
Less than 99.99%）, foundry alloy is melted with 150A electric currents, and continuous heating 15s, by arc current be increased to 200-250A it
Between, rapid open inhales casting vacuum valve, and foundry alloy is pressed into water cooled copper mould by air pressure is cooled down, and is obtained various sizes of non-
Peritectic alloy.
Further, preparation method（3）：Glass fluxing technique purification prepares foundry alloy, and prepares non-crystaline amorphous metal with water quenching method,
Step includes：
Step 1. dispensing：Metal Pd using purity as 99.0wt%-99.99wt%, Cu, Ag and nonmetallic Si, Ge is according to above-mentioned
The atomic percent of expression formula is converted into quality, and raw material surface scale is removed, and using industrial alcohol cleaning raw material, and press
Quality needed for each weighs；
Step 2. foundry alloy melting：Raw material after step 1 is handled is deposited in non-consumable arc furnace by fusing point sequence
Or in cold crucible shower furnace, it is less than 10 in vacuum-3It is filled with after Pa in high-purity argon gas（Not less than 99.99%）Melting is carried out, it is at least molten
Refining 4 times, makes the abundant melting of foundry alloy uniform；
Step 3. glass fluxing technique purifies：Diboron trioxide medium after foundry alloy and dehydration is positioned over various sizes of quartz ampoule
In, 0.2MPa high-purity argon gas will be filled with quartz ampoule after vacuum in quartz ampoule is evacuated into below 10Pa, and be positioned over 1100oC electricity
Purified 24 hours in stove；
Alloy pig of the step 4. after glass fluxing technique purifies directly is quenched in the molten state to be eaten into room temperature of the concentration not less than 25wt%
In salt solution, various sizes of non-crystaline amorphous metal is prepared.
The atomic percent expression formula of the non-crystaline amorphous metal is PdaCubGec, a, b and c represent each corresponding element respectively in formula
Atomic percent, wherein 73≤a≤80,0 ＜ b≤8,2≤c≤20, and a+b+c=100.
As a=77.5, when b=6, c=16.5, the atomic percent expression formula of non-crystaline amorphous metal is Pd74.5Cu3Ge16.5, pass through
Preparation method（3）The non-crystaline amorphous metal that critical dimension is not less than 1mm can be prepared.
The atomic percent expression formula of the non-crystaline amorphous metal is PdaCubGecSid, a, b, c and d represent each correspondence respectively 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, when c=16.5,4≤e≤16.5, the atomic percent expression of non-crystaline amorphous metal
Formula is Pd77.5Cu6SicGe16.5-c, pass through preparation method（3）The non-crystaline amorphous metal that critical dimension is not less than 1mm can be prepared.
When a=77.5, b=6, d=8.5, c=8, e=0, the atomic percent expression formula of non-crystaline amorphous metal are
Pd74.5Cu3Si8Ge8.5, pass through preparation method（3）The non-crystaline amorphous metal that critical dimension is not less than 2mm can be prepared.
As a=77.5, b=6, c=12.5, during d=4, Pd77.5Cu6Si12.5Ge4Alloy, foundry alloy is through preparation method（1）It can make
Standby critical dimension is not less than 2mm non-crystaline amorphous metal；Pass through preparation method（2）Amorphous of the critical dimension not less than 4mm can be prepared to close
Gold, supercooled liquid phase sector width 54K.
The atomic percent expression formula of the non-crystaline amorphous metal is PdaCubSicGedAge, a, b, c, d and e represent each 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, when d=12.5,1≤e≤2, the atomic percent expression formula of non-crystaline amorphous metal
Pd77.5CubSi12.5Ge4Ag6-b, foundry alloy is through preparation method（1）The non-crystaline amorphous metal that critical dimension is not less than 2mm can be prepared；Pass through
Preparation method（3）Large block amorphous critical dimension can be formed and be not less than 8mm, plastic strain is not less than 5%.
As a=77.5, b=3, c=4, when d=12.5, e=3, the atomic percent expression formula of non-crystaline amorphous metal is
Pd77.5Cu3Si12.5Ge4Ag3, foundry alloy is through preparation method（1）The non-crystaline amorphous metal that critical dimension is not less than 4mm can be prepared；Pass through system
Standby mode（3）Large block amorphous critical dimension can be formed and be not less than 8mm, plastic strain is not less than 11%.
The atomic percent expression Pd of non-crystaline amorphous metalaCubSicGedAgeXf, a, b, c, d and e represent each correspondence respectively 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 are the one or more in Co, Au, Pt.
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 non-crystaline amorphous metal is
Pd74.5Cu3Si12.5Ge4Ag3Au4, pass through preparation method（3）Large block amorphous critical dimension can be formed and be not less than 8mm.
The non-crystaline amorphous metal that three kinds of different preparation methods of contrast obtain, its critical dimension size is preparation method（1）<Prepare
Mode（2）<Preparation method（3）.
The advantage of the invention is that：
1. a series of palladium base non-crystaline amorphous metals involved in the present invention, there is excellent amorphous formation ability, maximum critical dimension is not
Less than 8mm.
2. a series of palladium base non-crystaline amorphous metals involved in the present invention, alloy essential element are Pd, Cu, Si, Ge, Ag, be free of
There is Ni etc. poisonous or to the easy sensitization element of biology, there is preferable biocompatibility.
3. a series of palladium base non-crystaline amorphous metals involved in the present invention, alloy essential element are Pd, Cu, Si, Ge, Ag, be free of
There are volatile P, smelting preparation method simplicity.
4. a series of palladium base non-crystaline amorphous metals involved in the present invention, plastic deformation ability is strong, and highest plastic deformation ability is not
Less than 5%.
Brief description of the drawings
Fig. 1 is Pd77.5Cu6Si4Ge8.5Or Pd77.5Cu6Si4Ge8.5The XRD spectrum of non-crystaline amorphous metal.
Fig. 2 is Pd77.5Cu6Si12.5Ge4The XRD spectrum of non-crystaline amorphous metal.
Fig. 3 is Pd77.5Cu6Si12.5Ge4The DSC curve of non-crystaline amorphous metal.
Fig. 4 is Pd77.5Cu6Si12.5Ge4The compression stress strain curve of non-crystaline amorphous metal.
Fig. 5 is Pd77.5Cu5Si12.5Ge4Ag1, Pd77.5Cu4Si12.5Ge4Ag2The XRD spectrum of non-crystaline amorphous metal.
Fig. 6 is Pd77.5Cu5Si12.5Ge4Ag1, Pd77.5Cu4Si12.5Ge4Ag2The SEM figures of non-crystaline amorphous metal.
Fig. 7 is Pd77.5Cu3Si12.5Ge4Ag3The XRD spectrum of non-crystaline amorphous metal.
Fig. 8 is Pd77.5Cu3Si12.5Ge4Ag3The SEM figures of non-crystaline amorphous metal.
Fig. 9 is Pd77.5Cu5Si12.5Ge4Ag1, Pd77.5Cu4Si12.5Ge4Ag2, Pd77.5Cu3Si12.5Ge4Ag3Non-crystaline amorphous metal
Compression stress strain curve.
Figure 10 is Pd74.5Cu3Si12.5Ge4Ag3Au4The XRD spectrum of non-crystaline amorphous metal.
Figure 11 is Pd77.5Cu5Si12.5Ge4Ag1, Pd77.5Cu4Si12.5Ge4Ag2,Pd77.5Cu3Si12.5Ge4Ag3, non-crystaline amorphous metal
XRD spectrum.
Embodiment
Technical scheme is described further with reference to specific embodiment.
A kind of germanic no without phosphorus large scale palladium base non-crystaline amorphous metal of nickel of the invention, the atomic percent expression formula of the non-crystaline amorphous metal
For PdaCubGec, a, b and c represent the atomic percent of each corresponding element respectively 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 non-crystaline amorphous metal is PdaCubGecSidAge, a, b, c and d difference 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 non-crystaline amorphous metal 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 are Co, Au, Pt
In one or more.
Further, as a=77.5, b=6, c=16.5, the atomic percent expression formula of non-crystaline amorphous metal is Pd74.5Cu3Ge16.5。
Further, when a=77.5, b=6, c=8.5, d=8, e=0, the atomic percent expression formula of non-crystaline amorphous metal are
Pd74.5Cu3Si8Ge8.5。
Further, a=77.5, b=5, c=12.5, d=4, e=1, the atomic percent expression formula of non-crystaline amorphous metal are
Pd74.5Cu5Si12.5Ge4Ag1；Or a=77.5, b=4, c=12.5, d=4, e=2, the atomic percent expression formula of non-crystaline amorphous metal are
Pd74.5Cu4Si12.5Ge4Ag2；Or a=77.5, b=3, c=12.5, d=4, e=3, the atomic percent expression formula of non-crystaline amorphous metal 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 non-crystaline amorphous metal
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 following steps：
Preparation method（1）：Non- glass fluxing technique purification prepares foundry alloy, and non-crystaline amorphous metal is prepared in a manner of copper mold, step bag
Include：
Step 1. dispensing：Metal Pd using purity as 99.0wt%-99.99wt%, Cu, Ag and nonmetallic Si, Ge is according to above-mentioned
The atomic percent of expression formula is converted into quality, and raw material surface scale is removed, and using industrial alcohol cleaning raw material, and press
Quality needed for each weighs；
Step 2. foundry alloy melting：Raw material after step 1 is handled is deposited in non-consumable arc furnace by fusing point sequence
Or in cold crucible shower furnace, it is less than 10 in vacuum-3It is filled with after Pa in high-purity argon gas（Not less than 99.99%）Melting is carried out, it is at least molten
Refining 4 times, makes the abundant melting of foundry alloy uniform；
Step 3. will be put into the different size water cooled copper moulds of vacuum arc furnace ignition after foundry alloy prepared by melting polishing scale removal
On, electric arc furnace cavity is evacuated to less than 10-30.08MPa high-purity argon gas is filled with after Pa（Not less than 99.99%）, with 150A electricity
Stream melts foundry alloy, and continuous heating 15s, and between arc current is increased into 200-250A, rapid open inhales casting vacuum valve
Door, foundry alloy is pressed into water cooled copper mould by air pressure and cooled down, obtains various sizes of non-crystaline amorphous metal.
Further, preparation method（2）：Glass fluxing technique purification prepares foundry alloy, and amorphous conjunction is prepared in a manner of copper mold
Gold, step include：
Step 1. dispensing：Metal Pd using purity as 99.0wt%-99.99wt%, Cu, Ag and nonmetallic Si, Ge is according to above-mentioned
The atomic percent of expression formula is converted into quality, and raw material surface scale is removed, and using industrial alcohol cleaning raw material, and press
Quality needed for each weighs；
Step 2. foundry alloy melting：Raw material after step 1 is handled is deposited in non-consumable arc furnace by fusing point sequence
Or in cold crucible shower furnace, it is less than 10 in vacuum-3It is filled with after Pa in high-purity argon gas（Not less than 99.99%）Melting is carried out, it is at least molten
Refining 4 times, makes the abundant melting of foundry alloy uniform；
Step 3. glass fluxing technique purifies：Diboron trioxide medium after foundry alloy and dehydration is positioned over various sizes of quartz ampoule
In, 0.2MPa high-purity argon gas will be filled with quartz ampoule after vacuum in quartz ampoule is evacuated into below 10Pa, and be positioned over 1100oC electricity
Purified 24 hours in stove, afterwards by melt furnace cooling；
After step 4. removes the cladding medium of the alloy pig surface attachment after glass fluxing technique purifies with sand paper, vacuum arc is put into
On the different size water cooled copper moulds of stove, electric arc furnace cavity is evacuated to less than 10-30.08MPa high-purity argon gas is filled with after Pa（No
Less than 99.99%）, foundry alloy is melted with 150A electric currents, and continuous heating 15s, by arc current be increased to 200-250A it
Between, rapid open inhales casting vacuum valve, and foundry alloy is pressed into water cooled copper mould by air pressure is cooled down, and is obtained various sizes of non-
Peritectic alloy.
Further, preparation method（3）：Glass fluxing technique purification prepares foundry alloy, and prepares non-crystaline amorphous metal with water quenching method,
Step includes：
Step 1. dispensing：Metal Pd using purity as 99.0wt%-99.99wt%, Cu, Ag and nonmetallic Si, Ge is according to above-mentioned
The atomic percent of expression formula is converted into quality, and raw material surface scale is removed, and using industrial alcohol cleaning raw material, and press
Quality needed for each weighs；
Step 2. foundry alloy melting：Raw material after step 1 is handled is deposited in non-consumable arc furnace by fusing point sequence
Or in cold crucible shower furnace, it is less than 10 in vacuum-3It is filled with after Pa in high-purity argon gas（Not less than 99.99%）Melting is carried out, it is at least molten
Refining 4 times, makes the abundant melting of foundry alloy uniform；
Step 3. glass fluxing technique purifies：Diboron trioxide medium after foundry alloy and dehydration is positioned over various sizes of quartz ampoule
In, 0.2MPa high-purity argon gas will be filled with quartz ampoule after vacuum in quartz ampoule is evacuated into below 10Pa, and be positioned over 1100oC electricity
Purified 24 hours in stove；
Alloy pig of the step 4. after glass fluxing technique purifies directly is quenched in the molten state to be eaten into room temperature of the concentration not less than 25wt%
In salt solution, various sizes of non-crystaline amorphous metal is prepared.
Embodiment 1：The preparation of Pd-Cu-Si-Ge systems non-crystaline amorphous metal：
Design PdaCubGecSidAgeAmorphous alloy component, wherein a=77.5, b=6, c=16.5,8.5,4,8,12.5, d=0, e=
0.It is Pd to obtain composition77.5Cu6Ge16.5、Pd77.5Cu6Si8Ge8.5、Pd77.5Cu6Si12.5Ge4Alloy.
Fig. 1 is alloy Pd77.5Cu6Ge16.5、Pd77.5Cu6Si8Ge8.5By preparation method（3）The XRD of the 2mm samples of preparation
Collection of illustrative plates, Fig. 2 are alloy Pd77.5Cu6Si12.5Ge4By preparation method（2）The XRD spectrum of the 2mm and 4mm samples of preparation, collection of illustrative plates
The only typical diffusing scattering peak of amorphous, show that prepared alloy is amorphous phase, the alloy system passes through preparation method（3）It can make
Standby critical dimension is not less than 2mm non-crystaline amorphous metal, Pd77.5Cu6Si12.5Ge4Alloy passes through preparation method（2）Critical chi can be prepared
The very little non-crystaline amorphous metal not less than 4mm, there is 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, its compression yield strength are 1650MPa, pressure
Contracting plasticity 3.5%.
Embodiment 2：The preparation of Pd-Cu-Si-Ge-Ag systems non-crystaline amorphous metal：
Design PdaCubGecSidAgeAmorphous alloy component, wherein a=77.5, b=5,4,3, c=4, d=12.5, e=1,2,3.Obtain
Composition is Pd77.5Cu5Si12.5Ge4Ag1, Pd77.5Cu4Si12.5Ge4Ag2、Pd77.5Cu3Si12.5Ge4Ag3Alloy.
Fig. 5 is alloy Pd77.5Cu5Si12.5Ge4Ag1, Pd77.5Cu4Si12.5Ge4Ag2By preparation method（3）The 8mm of preparation
The XRD spectrum of sample, Fig. 6 are the SEM photograph corresponding with Fig. 5, and Fig. 7 is alloy Pd77.5Cu3Si12.5Ge4Ag3By preparation side
Formula（3）The 8mm samples of preparation, and preparation method（1）The XRD spectrum of 4mm samples is prepared, Fig. 8 is the 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
Into showing that prepared alloy is amorphous phase, the alloy passes through preparation method（3）Critical dimension can be prepared not less than 8mm's
Amorphous, pass through preparation method（1）Pd77.5Cu5Si12.5Ge4Ag1, Pd77.5Cu4Si12.5Ge4Ag2Alloy can prepare critical dimension not
Non-crystaline amorphous metal less than 2mm, Pd77.5Cu3Si12.5Ge4Ag3Alloy can prepare the non-crystaline amorphous metal 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%.
Embodiment 3：The preparation of Pd-Cu-Si-Ge-Ag-X systems non-crystaline amorphous metal：
Design PdaCubGecSidAgeXfAmorphous alloy component, wherein X is Au, a=73.5, b=5, c=4, d=12.5, e=1, f=
4.It is Pd to obtain composition74.5Cu3Si12.5Ge4Ag3Au4Alloy.
Fig. 5 is Pd74.5Cu3Si12.5Ge4Ag3Au4Alloy passes through preparation method（3）The XRD spectrum of the 8mm samples of preparation,
XRD spectrum only has the typical diffusing scattering peak of amorphous, shows that prepared alloy is amorphous phase, passes through preparation method（3）It can prepare
Critical dimension is not less than 8mm non-crystaline amorphous metal, has strong amorphous formation ability.
A kind of germanic no without phosphorus large scale palladium base non-crystaline amorphous metal of nickel of the invention and preparation method thereof, the original of the alloys components
Sub- percentage is：Pd:73-80%, Cu:0 ＜ b≤8%, Si:0-18%, Ge:2-20%, Ag:0-6%.Main advantages of the present invention are
Nickel element is not contained, potential bio-toxicity substantially reduces, and improves biocompatibility；P elements are not contained, prepared by melting
Method is easy；With strong amorphous formation ability, critical chi can be prepared using the purification of glass fluxing technique media technology and water quenching quick cooling
The most strong composition of very little 1-8mm palladium base non-crystaline amorphous metal, wherein glass forming ability can be made using the method for electric arc melting copper mold
Standby critical dimension is not less than 4mm non-crystaline amorphous metal, and can prepare amorphous of the critical dimension not less than 8mm using preparation method 3 closes
Gold；Have>3% plastic deformation ability；Supercooling liquid phase region model with 40-60K.
Claims (10)
- A kind of 1. germanic no without phosphorus large scale palladium base non-crystaline amorphous metal of nickel, it is characterised in that the atomic percent table of the non-crystaline amorphous metal It is Pd up to formulaaCubGec, a, b and c represent the atomic percent of each corresponding element respectively 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 non-crystaline amorphous metal of nickel, it is characterised in that characterized in that, the original of the non-crystaline amorphous metal Sub- percentage expression formula is PdaCubGecSidAge, a, b, c, d and e represent the atomic percent of each corresponding element respectively 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 3. germanic no without phosphorus large scale palladium base non-crystaline amorphous metal of nickel, it is characterised in that the atomic percent table of the non-crystaline amorphous metal 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 are the one or more in Co, Au, Pt.
- 4. the without phosphorus large scale palladium base non-crystaline amorphous metal of germanic no nickel according to claim 1, it is characterised in that as a=77.5, b= 6, c=16.5, the atomic percent expression formula of non-crystaline amorphous metal is Pd74.5Cu3Ge16.5。
- 5. the without phosphorus large scale palladium base non-crystaline amorphous metal of germanic no nickel according to claim 2, it is characterised in that as a=77.5, b= 6, c=8.5, d=8, e=0, the atomic percent expression formula of non-crystaline amorphous metal is Pd74.5Cu3Si8Ge8.5。
- 6. the germanic no without phosphorus large scale palladium base non-crystaline amorphous metal of nickel according to claim 2, it is characterised in that a=77.5, b= 5, c=4, d=12.5, e=1, the atomic percent expression formula of non-crystaline amorphous metal is Pd74.5Cu5Si12.5Ge4Ag1；Or a=77.5, b= 4, c=12.5, d=4, e=2, the atomic percent expression formula of non-crystaline amorphous metal is Pd74.5Cu4Si12.5Ge4Ag2；Or a=77.5, b= 3, c=4, d=12.5, e=3, the atomic percent expression formula of non-crystaline amorphous metal is Pd74.5Cu3Si12.5Ge4Ag3。
- 7. the germanic no without phosphorus large scale palladium base non-crystaline amorphous metal of nickel according to claim 3, it is characterised in that when X is Au, a= 73.5, b=5, c=4, d=12.5, e=1, f=4, the atomic percent expression formula of non-crystaline amorphous metal are Pd74.5Cu3Si12.5Ge4Ag3Au4。
- A kind of 8. method for preparing the non-crystaline amorphous metal as described in any in claim 1-7, it is characterised in that specifically include with Under：Preparation method（1）：Non- glass fluxing technique purification prepares foundry alloy, and non-crystaline amorphous metal is prepared in a manner of copper mold, step bag Include：Step 1. dispensing：Metal Pd using purity as 99.0wt%-99.99wt%, Cu, Ag and nonmetallic Si, Ge is according to above-mentioned The atomic percent of expression formula is converted into quality, and raw material surface scale is removed, and using industrial alcohol cleaning raw material, and press Quality needed for each weighs；Step 2. foundry alloy melting：Raw material after step 1 is handled is deposited in non-consumable arc furnace by fusing point sequence Or in cold crucible shower furnace, it is less than 10 in vacuum-3It is filled with after Pa in high-purity argon gas（Purity is not less than 99.99%）Melting is carried out, extremely Melting 4 times less, makes the abundant melting of foundry alloy uniform；Step 3. will be put into the different size water cooled copper moulds of vacuum arc furnace ignition after foundry alloy prepared by melting polishing scale removal On, electric arc furnace cavity is evacuated to less than 10-30.08MPa high-purity argon gas is filled with after Pa（Purity is not less than 99.99%）, with 150A electric currents melt foundry alloy, and continuous heating 15s, and between arc current is increased into 200-250A, rapid open inhales casting Vacuum valve, foundry alloy is pressed into water cooled copper mould by air pressure and cooled down, obtains various sizes of non-crystaline amorphous metal.
- A kind of 9. method for preparing the non-crystaline amorphous metal as described in any in claim 1-7, it is characterised in that specifically include with Under：Preparation method（2）：Glass fluxing technique purification prepares foundry alloy, and non-crystaline amorphous metal is prepared in a manner of copper mold, and step includes：Step 1. dispensing：Metal Pd using purity as 99.0wt%-99.99wt%, Cu, Ag and nonmetallic Si, Ge is according to above-mentioned The atomic percent of expression formula is converted into quality, and raw material surface scale is removed, and using industrial alcohol cleaning raw material, and press Quality needed for each weighs；Step 2. foundry alloy melting：Raw material after step 1 is handled is deposited in non-consumable arc furnace by fusing point sequence Or in cold crucible shower furnace, it is less than 10 in vacuum-3It is filled with after Pa in high-purity argon gas（Not less than 99.99%）Melting is carried out, it is at least molten Refining 4 times, makes the abundant melting of foundry alloy uniform；Step 3. glass fluxing technique purifies：Diboron trioxide medium after foundry alloy and dehydration is positioned over various sizes of quartz ampoule In, 0.2MPa high-purity argon gas will be filled with quartz ampoule after vacuum in quartz ampoule is evacuated into below 10Pa, and be positioned over 1100oC electricity Purified 24 hours in stove, afterwards by melt furnace cooling；After step 4. removes the cladding medium of the alloy pig surface attachment after glass fluxing technique purifies with sand paper, vacuum arc is put into On the different size water cooled copper moulds of stove, electric arc furnace cavity is evacuated to less than 10-30.08MPa high-purity argon gas is filled with after Pa（No Less than 99.99%）, foundry alloy is melted with 150A electric currents, and continuous heating 15s, by arc current be increased to 200-250A it Between, rapid open inhales casting vacuum valve, and foundry alloy is pressed into water cooled copper mould by air pressure is cooled down, and is obtained various sizes of non- Peritectic alloy.
- A kind of 10. method for preparing the non-crystaline amorphous metal as described in any in claim 1-7, it is characterised in that specifically include with Under：Preparation method（3）：Glass fluxing technique purification prepares foundry alloy, and prepares non-crystaline amorphous metal with water quenching method, and step includes：Step 1. dispensing：Metal Pd using purity as 99.0wt%-99.99wt%, Cu, Ag and nonmetallic Si, Ge is according to above-mentioned The atomic percent of expression formula is converted into quality, and raw material surface scale is removed, and using industrial alcohol cleaning raw material, and press Quality needed for each weighs；Step 2. foundry alloy melting：Raw material after step 1 is handled is deposited in non-consumable arc furnace by fusing point sequence Or in cold crucible shower furnace, it is less than 10 in vacuum-3It is filled with after Pa in high-purity argon gas（Not less than 99.99%）Melting is carried out, it is at least molten Refining 4 times, makes the abundant melting of foundry alloy uniform；Step 3. glass fluxing technique purifies：Diboron trioxide medium after foundry alloy and dehydration is positioned over various sizes of quartz ampoule In, 0.2MPa high-purity argon gas will be filled with quartz ampoule after vacuum in quartz ampoule is evacuated into below 10Pa, and be positioned over 1100oC electricity Purified 24 hours in stove；Alloy pig of the step 4. after glass fluxing technique purifies directly is quenched in the molten state to be eaten into room temperature of the concentration not less than 25wt% In salt solution, various sizes of non-crystaline amorphous metal is prepared.
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