CN110093523A - A kind of new medical metal material and its super-pressure preparation method - Google Patents
A kind of new medical metal material and its super-pressure preparation method Download PDFInfo
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- CN110093523A CN110093523A CN201910339950.XA CN201910339950A CN110093523A CN 110093523 A CN110093523 A CN 110093523A CN 201910339950 A CN201910339950 A CN 201910339950A CN 110093523 A CN110093523 A CN 110093523A
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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
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F3/00—Changing the physical structure of non-ferrous metals or alloys by special physical methods, e.g. treatment with neutrons
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Abstract
A kind of new medical metal material and its super-pressure preparation method, it belongs to medical metal material.The technical problem to be solved in the present invention is to improve the performance of medical alloy material.The present invention weighs the pure magnesium ingot of certain mass respectively, pure zinc granule, mass percent ingredient is the first intermediate alloy of Mg-30Zr, the second intermediate alloy that mass percent ingredient is Mg-30Gd is in resistance furnace under protective atmosphere, melting is carried out in sequence, it is poured into after melting in the metal die for being preheated to 200 DEG C, obtain sample, utilize pyrophyllite block, graphite-pipe carries out high-voltage samples assembling, assembling is placed in high-pressure installation under the pressure of 2~6GPa, 20~30min is kept to carry out High Pressure Solidification processing at 950~980 DEG C, then after pressure maintaining is cooled to 300 DEG C, heat-insulation pressure keeping 5~60 minutes, it is cooled to room temperature or is warmed to room temperature in dwell condition decline, medical metal material is made.The present invention significantly improves corrosion resistance and surface hardness.
Description
Technical field
The invention belongs to medical metal materials；More particularly to a kind of new medical metal material and its super-pressure preparation side
Method.
Background technique
Medical metal material magnesium alloy good biocompatibility, comprehensive mechanical property is excellent, degradable, therefore as fracture
Internal fixation material has significant advantage, becomes research hotspot, but magnesium alloy degradation speed is too fast, causes mechanical properties decrease mistake
Fastly, it is difficult to meet the requirement as implantation material.
For the degradation speed for reducing magnesium alloy, domestic and international researcher made numerous studies, such as alloyage process, using mentioning
High corrosion stability of magnesium alloy can improve alloy corrosion resisting property and intensity in body fluid with nontoxic alloying element；Heat treatment also can
Corrosion resistance of the alloy in human body environment is improved, mechanism is to weaken or eliminate the relatively corrosive negative effect of cathode；Become
Shape processing can reduce cathode phase size, to improve the corrosion resistance and mechanical property of alloy with the micropipe in soldering alloy；
Surface treatment includes that the methods of differential arc oxidation, anodic oxidation, laser modified, electrophoresis, electro-deposition all significantly reduce magnesium alloy in body
Corrosion rate in liquid, but mechanical property cannot be improved.
It is that rising in recent years prepares MATERIALS METHODS that high pressure, which prepares material, under high pressure effect, the diffusion process of atom and
Phase driving force will change, thus will solidified structure to metal material, the tissue after heat treatment and performance cause it is bright
Development is rung, and high pressure influences magnesium alloy and performance significantly, to solidification under condition of high voltage or to be heat-treated obtained magnesium alloy, alloy member
The solid solubility of element improves, and the microhardness and corrosion resisting property of alloy are all improved, but single processing mode is to performance
It improves limited.
Summary of the invention
It is an object of the present invention to provide a kind of new medical metal material and its super-pressure preparation methods.
The invention is realized by the following technical scheme:
A kind of super-pressure preparation method of new medical metal material, includes the following steps:
Step 1, the pure magnesium ingot for weighing certain mass respectively, pure zinc granule, mass percent ingredient be Mg-30Zr first in
Between alloy, mass percent ingredient be Mg-30Gd the second intermediate alloy, for use；
Step 2, the Ar in resistance furnace2And SF6Under protective atmosphere, by pure magnesium ingot load weighted in step 1, pure zinc granule, quality
The first intermediate alloy that percent composition is Mg-30Zr, the second intermediate alloy that mass percent ingredient is Mg-30Gd are according to suitable
Sequence carries out melting, is poured into the metal die for being preheated to 200 DEG C after melting, obtains sample, for use；
Step 3, the sample for obtaining step 2, using pyrophyllite block, graphite-pipe carries out high-voltage samples assembling, assembles postposition
In high-pressure installation under the pressure of 2~6GPa, 20~30min is kept to carry out High Pressure Solidification processing at 950~980 DEG C, then
After pressure maintaining is cooled to 300 DEG C, heat-insulation pressure keeping 5~60 minutes, it is cooled to room temperature or is warmed to room temperature in dwell condition decline, institute is made
A kind of new medical metal material stated.
A kind of super-pressure preparation method of new medical metal material of the present invention, zinc accounts for a kind of novel in step 1
6~8wt% of the gross mass of medical metal material, Zr account for a kind of gross mass of new medical metal material 0.5~
1.0wt%, Gd account for a kind of 0.5~1.0wt% of the gross mass of new medical metal material, and surplus is magnesium.
A kind of super-pressure preparation method of new medical metal material of the present invention, zinc accounts for a kind of novel in step 1
The 6wt% of the gross mass of medical metal material, Zr account for a kind of 0.5wt% of the gross mass of new medical metal material, and Gd accounts for one
The 0.5wt% of the gross mass of kind new medical metal material, surplus is magnesium.
A kind of super-pressure preparation method of new medical metal material of the present invention, resistance furnace temperature is in step 2
It 730~750 DEG C, is firstly added pure magnesium ingot and carries out melting, pure zinc granule is pressed into Serum Magnesium liquid after its fusing, and with graphite bell jar
Under face, after addition, static 10min, with graphite bell jar by the first intermediate alloy of Mg-30Zr indentation alloy melt liquid level it
Under, after static 15min, with graphite bell jar by under the second intermediate alloy indentation alloy melt liquid level of Mg-30Gd, stir
After 10min, degassing processing is carried out using rotary blowing, 5min is stood, is poured into metal die.
A kind of super-pressure preparation method of new medical metal material of the present invention, the group of step 3 mesohigh sample
Dress method are as follows: first wrapped up with the sample that cold press obtains step 2 with boron nitride powder, graphite bottom of the tube place one with
The identical cylindrical pyrophyllite block of its internal diameter, the sample after package are close to cured piece of bottom leaf and are put into graphite-pipe, then wrapping up
Sample top afterwards is put into a same cylindrical pyrophyllite block, then is sealed the top of graphite-pipe with a graphite flake；It seals
The graphite-pipe of sample is put into middle position in the circular hole among a cube pyrophyllite block, and two conductions are placed at graphite-pipe both ends
Then ring is put thermocouple wire for conductive heater sample in the punching of cube pyrophyllite block right angle until touching sample
Enter and touch sample, the other end of thermocouple is temperature recording unit, completes high-voltage samples assembling.
A kind of super-pressure preparation method of new medical metal material of the present invention, thermocouple temperature measurement dress in step 3
It sets, is that from outside to inside, thermocouple wire is put into graphite-pipe by punching, but hole cannot extend through and be put into BN, prevent pressure from making BN
Or metal liquid outflow.
A kind of super-pressure preparation method of new medical metal material of the present invention, step 3 mesohigh device are CS-
1B type cubic hinge press.
A kind of super-pressure preparation method of new medical metal material of the present invention, the high pressure after assembling in step 3
Sample is placed on the cavity position of high-pressure installation, the laggard horizontal high voltage solidification processing of tup centering.
A kind of super-pressure preparation method of new medical metal material of the present invention, the pressure of step 3 mesohigh device
Power is 4GPa, is heated to 950 DEG C of heat-insulation pressure keepings 25 minutes in 4GPa pressure maintaining, after pressure maintaining is cooled to 300 DEG C, heat-insulation pressure keeping 30 divides
Clock, pressure maintaining are cooled to room temperature.
A kind of a kind of new medical metal material of the super-pressure preparation method preparation of new medical metal material, it is described
A kind of mass percentage composition of new medical metal material is 6~8wt% of zinc, 0.5~1.0wt% of zirconium, gadolinium 0.5~
1.0wt%, surplus are magnesium.
A kind of a kind of new medical gold of the super-pressure preparation method preparation of new medical metal material of the present invention
Belong to material, a kind of microhardness of new medical metal material is 61.25~63.14HV.
A kind of a kind of new medical gold of the super-pressure preparation method preparation of new medical metal material of the present invention
Belong to material, high-purity zinc granule that high-purity magnesium ingot that pure magnesium ingot used is 99.99wt%, pure zinc granule are 99.99wt%.
A kind of a kind of new medical gold of the super-pressure preparation method preparation of new medical metal material of the present invention
Belong to material, in step 2 in resistance furnace Ar2And SF6Protective atmosphere is the SF that high-purity argon gas adds 0.5wt%6。
The invention has the benefit that
A kind of new medical metal material of the super-pressure preparation method preparation of new medical metal material of the present invention
Material, corrosion rate are 0.28mm/.
A kind of super-pressure preparation method of new medical metal material of the present invention, integrated use High Pressure Solidification and height
Autoclaving synergistic effect, a kind of new medical metal material of preparation significantly improve corrosion resisting property and surface hardness.
Detailed description of the invention
Fig. 1 is the one of the super-pressure preparation method preparation of a kind of new medical metal material described in specific embodiment one
The metallographic microstructure photo of kind new medical metal material；
Fig. 2 is the one of the super-pressure preparation method preparation of a kind of new medical metal material described in specific embodiment one
The stereoscan photograph of kind new medical metal material；
Fig. 3 is the one of the super-pressure preparation method preparation of a kind of new medical metal material described in specific embodiment two
The stereoscan photograph of kind new medical metal material；
Fig. 4 is a kind of super-pressure of new medical metal material described in specific embodiment one and specific embodiment two
A kind of XRD correlation curve of new medical metal material of preparation method preparation；
Fig. 5 is the one of the super-pressure preparation method preparation of a kind of new medical metal material described in specific embodiment three
The metallographic microstructure photo of kind new medical metal material；
Fig. 6 is the one of the super-pressure preparation method preparation of a kind of new medical metal material described in specific embodiment three
The stereoscan photograph of kind new medical metal material；
Fig. 7 is the one of the super-pressure preparation method preparation of a kind of new medical metal material described in specific embodiment three
The EDS of kind new medical metal material analyzes curve；
Fig. 8 is a kind of a kind of novel doctor of the super-pressure preparation method preparation of new medical metal material of the present invention
Schemed with the hardness balance of metal material；
Fig. 9 is to coagulate in a kind of super-pressure preparation method cubic hinge press of new medical metal material of the present invention
Gu sample assembling schematic diagram；1- pyrophillite in figure, 2- conducting ring, 3- graphite-pipe, 4-BN, 5- magnesium alloy sample, 6- hammer.
Specific embodiment
Specific embodiment 1:
A kind of super-pressure preparation method of new medical metal material, includes the following steps:
Step 1, the pure magnesium ingot for weighing certain mass respectively, pure zinc granule, mass percent ingredient be Mg-30Zr first in
Between alloy, mass percent ingredient be Mg-30Gd the second intermediate alloy, for use；
Step 2, the Ar in resistance furnace2And SF6Under protective atmosphere, by pure magnesium ingot load weighted in step 1, pure zinc granule, quality
The first intermediate alloy that percent composition is Mg-30Zr, the second intermediate alloy that mass percent ingredient is Mg-30Gd are according to suitable
Sequence carries out melting, is poured into the metal die for being preheated to 200 DEG C after melting, obtains sample, for use；
Step 3, the sample for obtaining step 2, using pyrophyllite block, graphite-pipe carries out high-voltage samples assembling, assembles postposition
In high-pressure installation under the pressure of 4GPa, 20~30min is kept to carry out High Pressure Solidification processing, then pressure maintaining at 950~980 DEG C
After being cooled to 300 DEG C, heat-insulation pressure keeping 5~10 minutes, it is cooled to room temperature, a kind of new medical metal material is made.
A kind of super-pressure preparation method of new medical metal material described in present embodiment, zinc accounts for one kind in step 1
The 6wt% of the gross mass of new medical metal material, Zr account for the 0.5wt%, Gd of a kind of gross mass of new medical metal material
A kind of 0.5wt% of the gross mass of new medical metal material is accounted for, surplus is magnesium.
A kind of super-pressure preparation method of new medical metal material described in present embodiment, resistance furnace temperature in step 2
Degree is 730~750 DEG C, is firstly added pure magnesium ingot and carries out melting, melts pure zinc granule indentation magnesium after its fusing, and with graphite bell jar
Under body fluid face, after addition, the first intermediate alloy of Mg-30Zr is pressed into alloy melt liquid level with graphite bell jar by static 10min
Under, after static 15min, with graphite bell jar by under the second intermediate alloy indentation alloy melt liquid level of Mg-30Gd, stir
After 10min, degassing processing is carried out using rotary blowing, 5min is stood, is poured into metal die.
A kind of super-pressure preparation method of new medical metal material, step 3 mesohigh sample described in present embodiment
Assemble method are as follows: first wrapped up with the sample that cold press obtains step 2 with boron nitride powder, graphite bottom of the tube place one
A cylindrical pyrophyllite block identical with its internal diameter, the sample after package are close to cured piece of bottom leaf and are put into graphite-pipe, then exist
Sample top after package is put into a same cylindrical pyrophyllite block, then is sealed the top of graphite-pipe with a graphite flake；
The graphite-pipe for sealing sample is put into middle position in the circular hole among a cube pyrophyllite block, and graphite-pipe both ends are placed two and led
Electric ring is punched in cube pyrophyllite block right angle until touching sample, then by thermocouple wire for conductive heater sample
It is put into and touches sample, the other end of thermocouple is temperature recording unit, completes high-voltage samples assembling.
A kind of super-pressure preparation method of new medical metal material, step 3 mesohigh device described in present embodiment
For CS-1B type cubic hinge press.
A kind of super-pressure preparation method of new medical metal material described in present embodiment, after assembling in step 3
High-voltage samples are placed on the cavity position of high-pressure installation, the laggard horizontal high voltage solidification processing of tup centering.
A kind of a kind of novel doctor of the super-pressure preparation method preparation of new medical metal material described in present embodiment
With metal material, high-purity zinc granule that high-purity magnesium ingot that pure magnesium ingot used is 99.99wt%, pure zinc granule are 99.99wt%.
A kind of a kind of novel doctor of the super-pressure preparation method preparation of new medical metal material described in present embodiment
With metal material, in step 2 in resistance furnace Ar2And SF6Protective atmosphere is the SF that high-purity argon gas adds 0.5wt%6。
A kind of a kind of novel doctor of the super-pressure preparation method preparation of new medical metal material described in present embodiment
With the metallographic microstructure photo of metal material as shown in Figure 1, from FIG. 1, it can be seen that a kind of new medical metal
The secondary dendrite spacing of material is much smaller than normal pressure identical component cast alloy, and size is in herring-bone form dendrite, pattern at 30-50 μm.
A kind of a kind of new medical of the super-pressure preparation method preparation of new medical category material described in present embodiment
The stereoscan photograph of metal material is as shown in Fig. 2, phase amount significant decrease is precipitated in the solidification of alloy, and size significantly reduces, axis
Half is reduced compared to normal pressure identical component cast alloy to size and radial dimension.
Specific embodiment 2:
A kind of super-pressure preparation method of new medical metal material, includes the following steps:
Step 1, the pure magnesium ingot for weighing certain mass respectively, pure zinc granule, mass percent ingredient be Mg-30Zr first in
Between alloy, mass percent ingredient be Mg-30Gd the second intermediate alloy, for use；
Step 2, the Ar in resistance furnace2And SF6Under protective atmosphere, by pure magnesium ingot load weighted in step 1, pure zinc granule, quality
The first intermediate alloy that percent composition is Mg-30Zr, the second intermediate alloy that mass percent ingredient is Mg-30Gd are according to suitable
Sequence carries out melting, is poured into the metal die for being preheated to 200 DEG C after melting, obtains sample, for use；
Step 3, the sample for obtaining step 2, using pyrophyllite block, graphite-pipe carries out high-voltage samples assembling, assembles postposition
In high-pressure installation under the pressure of 4GPa, 25min is kept to carry out High Pressure Solidification processing at 950 DEG C, then pressure maintaining is cooled to 300
After DEG C, after heat-insulation pressure keeping 30 minutes, pressure maintaining is cooled to room temperature, and a kind of new medical metal material is made.
A kind of super-pressure preparation method of new medical metal material described in present embodiment, zinc accounts for one kind in step 1
The 6wt% of the gross mass of new medical metal material, Zr account for the 0.5wt%, Gd of a kind of gross mass of new medical metal material
A kind of 0.5wt% of the gross mass of new medical metal material is accounted for, surplus is magnesium.
A kind of super-pressure preparation method of new medical metal material described in present embodiment, resistance furnace temperature in step 2
Degree is 730~750 DEG C, is firstly added pure magnesium ingot and carries out melting, melts pure zinc granule indentation magnesium after its fusing, and with graphite bell jar
Under body fluid face, after addition, the first intermediate alloy of Mg-30Zr is pressed into alloy melt liquid level with graphite bell jar by static 10min
Under, after static 15min, with graphite bell jar by under the second intermediate alloy indentation alloy melt liquid level of Mg-30Gd, stir
After 10min, degassing processing is carried out using rotary blowing, 5min is stood, is poured into metal die.
A kind of super-pressure preparation method of new medical metal material, step 3 mesohigh sample described in present embodiment
Assemble method are as follows: first wrapped up with the sample that cold press obtains step 2 with boron nitride powder, graphite bottom of the tube place one
A cylindrical pyrophyllite block identical with its internal diameter, the sample after package are close to cured piece of bottom leaf and are put into graphite-pipe, then exist
Sample top after package is put into a same cylindrical pyrophyllite block, then is sealed the top of graphite-pipe with a graphite flake；
The graphite-pipe for sealing sample is put into middle position in the circular hole among a cube pyrophyllite block, and graphite-pipe both ends are placed two and led
Electric ring is punched in cube pyrophyllite block right angle until touching sample, then by thermocouple wire for conductive heater sample
It is put into and touches sample, the other end of thermocouple is temperature recording unit, completes high-voltage samples assembling.
A kind of super-pressure preparation method of new medical metal material, step 3 mesohigh device described in present embodiment
For CS-1B type cubic hinge press.
A kind of super-pressure preparation method of new medical metal material described in present embodiment, after assembling in step 3
High-voltage samples are placed on the cavity position of high-pressure installation, the laggard horizontal high voltage solidification processing of tup centering.
A kind of a kind of novel doctor of the super-pressure preparation method preparation of new medical metal material described in present embodiment
With metal material, high-purity zinc granule that high-purity magnesium ingot that pure magnesium ingot used is 99.99wt%, pure zinc granule are 99.99wt%.
A kind of a kind of novel doctor of the super-pressure preparation method preparation of new medical metal material described in present embodiment
With metal material, in step 2 in resistance furnace Ar2And SF6Protective atmosphere is the SF that high-purity argon gas adds 0.5wt%6。
A kind of a kind of novel doctor of the super-pressure preparation method preparation of new medical metal material described in present embodiment
It is as shown in Figure 3 with the sem analysis photo of metal material, it is known that the high voltage driving IC after High Pressure Solidification can further decrease
Phase amount is precipitated in the solidification of alloy, and eliminates dendritic segregation phenomenon.
A kind of a kind of novel doctor of the super-pressure preparation method preparation of new medical metal material described in present embodiment
It is weak with the XRD correlation curve of metal material as shown in figure 4, from Fig. 4, it can be seen that peak Mg2Zn11 in High Pressure Solidification alloy
Change, after continuing high voltage driving IC, the peak Mg2Zn11 disappears.
A kind of a kind of novel doctor of the super-pressure preparation method preparation of new medical metal material described in present embodiment
With metal material, electrochemical corrosion performance test, test method are carried out are as follows: corrosive medium is using analysis pure chemistry reagent and distillation
Hank ' the s mixed solution that water is prepared, specific ingredient are (g/L): 8.0NaCl, 0.4KCl, 0.06Na2HPO4, 0.06KH2PO4,
0.35NaHCO3, 0.2MgSO4.7H2O and 0.14CaCl2.Activation polarization experiment uses standard three electrode system: reference
Electrode is saturated calomel electrode, auxiliary electrode is platinum electrode, sample as working electrode, and scanning speed is 3 × 10-4V/s.Polarization
Experiment carries out in the beaker for filling 300mlHank ' s solution, and solution temperature is controlled at 37 ± 1 DEG C.Electrochemical sample is from above-mentioned
It is cut on ingot casting, through epoxy resin closed set, exposed surface area 1cm2, surface is successively polished with 200-1200# sand paper, is surveyed
Test result is as shown in table 1:
A kind of electrochemical corrosion data of new medical metal material described in 1 specific embodiment two of table
, it can be seen that a kind of new medical metal material and common preparation method system described in present embodiment from table 1
Standby medical metal material is compared, and corrosion rate is 0.28mm/, is significantly reduced compared to commonsense method corrosion rate, former
Reason makes matrix spread prompt drop for a kind of preparation method of new medical metal material described in present embodiment under high pressure effect
Low, the solid solubility of Zn and Zr in matrix significantly improve, and the raising of Zn content makes a kind of the blunt of new medical metal material
Change the stability of film, to improve a kind of corrosive nature of new medical metal material, and High Pressure Solidification condition
It is lower to carry out subsequent high voltage driving IC and significantly reduce microsegregation, and promote solidifying phase broken under stress and dissolution, make described
A kind of new medical metal material micro cell effect reduce, reduce corrosion tendency.
Specific embodiment 3:
A kind of super-pressure preparation method of new medical metal material, includes the following steps:
Step 1, the pure magnesium ingot for weighing certain mass respectively, pure zinc granule, mass percent ingredient be Mg-30Zr first in
Between alloy, mass percent ingredient be Mg-30Gd the second intermediate alloy, for use；
Step 2, the Ar in resistance furnace2And SF6Under protective atmosphere, by pure magnesium ingot load weighted in step 1, pure zinc granule, quality
The first intermediate alloy that percent composition is Mg-30Zr, the second intermediate alloy that mass percent ingredient is Mg-30Gd are according to suitable
Sequence carries out melting, is poured into the metal die for being preheated to 200 DEG C after melting, obtains sample, for use；
Step 3, the sample for obtaining step 2, using pyrophyllite block, graphite-pipe carries out high-voltage samples assembling, assembles postposition
In high-pressure installation under the pressure of 2~6GPa, 20~30min is kept to carry out High Pressure Solidification processing at 950~980 DEG C, then
After pressure maintaining is cooled to 300 DEG C, heat-insulation pressure keeping 5~10 minutes, it is cooled to room temperature, a kind of new medical metal material is made
Material.
A kind of super-pressure preparation method of new medical metal material described in present embodiment, zinc accounts for one kind in step 1
The 8wt% of the gross mass of new medical metal material, Zr account for the 0.5wt%, Gd of a kind of gross mass of new medical metal material
A kind of 0.5wt% of the gross mass of new medical metal material is accounted for, surplus is magnesium.
A kind of super-pressure preparation method of new medical metal material described in present embodiment, resistance furnace temperature in step 2
Degree is 730~750 DEG C, is firstly added pure magnesium ingot and carries out melting, melts pure zinc granule indentation magnesium after its fusing, and with graphite bell jar
Under body fluid face, after addition, the first intermediate alloy of Mg-30Zr is pressed into alloy melt liquid level with graphite bell jar by static 10min
Under, after static 15min, with graphite bell jar by under the second intermediate alloy indentation alloy melt liquid level of Mg-30Gd, stir
After 10min, degassing processing is carried out using rotary blowing, 5min is stood, is poured into metal die.
A kind of super-pressure preparation method of new medical metal material, step 3 mesohigh sample described in present embodiment
Assemble method are as follows: first wrapped up with the sample that cold press obtains step 2 with boron nitride powder, graphite bottom of the tube place one
A cylindrical pyrophyllite block identical with its internal diameter, the sample after package are close to cured piece of bottom leaf and are put into graphite-pipe, then exist
Sample top after package is put into a same cylindrical pyrophyllite block, then is sealed the top of graphite-pipe with a graphite flake；
The graphite-pipe for sealing sample is put into middle position in the circular hole among a cube pyrophyllite block, and graphite-pipe both ends are placed two and led
Electric ring is punched in cube pyrophyllite block right angle until touching sample, then by thermocouple wire for conductive heater sample
It is put into and touches sample, the other end of thermocouple is temperature recording unit, completes high-voltage samples assembling.
A kind of super-pressure preparation method of new medical metal material, step 3 mesohigh device described in present embodiment
For CS-1B type cubic hinge press.
A kind of super-pressure preparation method of new medical metal material described in present embodiment, after assembling in step 3
High-voltage samples are placed on the cavity position of high-pressure installation, the laggard horizontal high voltage solidification processing of tup centering.
A kind of super-pressure preparation method of new medical metal material described in present embodiment, a kind of novel doctor
It is 63.14HV with the microhardness of metal material.
A kind of a kind of novel doctor of the super-pressure preparation method preparation of new medical metal material described in present embodiment
With metal material, high-purity zinc granule that high-purity magnesium ingot that pure magnesium ingot used is 99.99wt%, pure zinc granule are 99.99wt%.
A kind of a kind of novel doctor of the super-pressure preparation method preparation of new medical metal material described in present embodiment
With metal material, in step 2 in resistance furnace Ar2And SF6Protective atmosphere is the SF that high-purity argon gas adds 0.5wt%6。
A kind of a kind of novel doctor of the super-pressure preparation method preparation of new medical metal material described in present embodiment
With metal material, Fig. 5 is one of a kind of super-pressure preparation method preparation of new medical metal material described in present embodiment
The metallograph of the High Pressure Solidification of kind new medical metal material, a kind of super-pressure preparation of new medical metal material
The transgranular secondary dendrite of most of primary tiller is in arranged in parallel and primary main in a kind of new medical metal material of method preparation
Bar dendrite and surrounding secondary dendrite arranged in parallel constitute herring-bone form pattern, it is known that secondary dendrite shape occurs after High Pressure Solidification
Significant changes become the distribution that is parallel to each other from radial distribution, and intergranular is away from being significantly reduced to 10-30 μm or so.
A kind of a kind of novel doctor of the super-pressure preparation method preparation of new medical metal material described in present embodiment
With metal material, Fig. 6 is one of a kind of super-pressure preparation method preparation of new medical metal material described in present embodiment
The SEM photograph of the High Pressure Solidification of kind new medical metal material, a kind of super-pressure preparation of new medical metal material
Solidification precipitate size is significantly lower than the as cast condition of identical component normal pressure solidification in a kind of new medical metal material of method preparation
Alloy, secondary dendrite spacing are substantially reduced, and are bordering between secondary dendrite parallel.
A kind of a kind of novel doctor of the super-pressure preparation method preparation of new medical metal material described in present embodiment
With metal material, Fig. 7 is one of a kind of super-pressure preparation method preparation of new medical metal material described in present embodiment
The EDS analysis of the High Pressure Solidification of kind new medical metal material, a kind of super-pressure preparation of new medical metal material
After a kind of new medical metal material solidification of method preparation, the solid solubility of Zn and Gd in the base in alloy is apparently higher than phase
The cast alloy of congruent normal pressure solidification.
A kind of a kind of novel doctor of the super-pressure preparation method preparation of new medical metal material described in present embodiment
With the microhardness of metal material.As Fig. 8 finds out the aobvious of the Mg-6Zn-0.5Zr-0.5Gd alloy prepared using the method for the present invention
Microhardness is apparently higher than identical component normal pressure as cast condition solidified superalloy, and Mg-6Zn-0.5Zr-0.5Gd alloy carries out not after High Pressure Solidification
With the high voltage driving IC of time, the increase of microhardness at any time is significantly improved, and the high voltage driving IC in short-term after High Pressure Solidification
The microhardness of Mg-8Zn-0.5Zr-0.5Gd alloy be also apparently higher than identical component normal pressure as cast condition solidified superalloy.This embodiment party
A kind of new medical metal material of formula method preparation has highest microhardness, and reason mainly has two aspects, on the one hand high
Pressure solidification and subsequent high voltage driving IC have refined crystal grain, and the effect of refined crystalline strengthening makes a kind of new medical metal material
Microhardness is improved, and has been dissolved a certain amount of Zn, Gd in a kind of new medical metal material matrix described in another aspect
And Zr, High Pressure Solidification and subsequent high voltage driving IC can significantly improve in matrix Zn and Zr solid solubility in the base, caused crystalline substance
Lattice distortion is improved the microhardness of alloy.
A kind of super-pressure preparation method of new medical metal material, the mechanism of action are as follows: formula described in present embodiment
It (1) is nucleating work, relational expression between metal volume variation after pressure and fusing, when pressure increase arrives GPa, volume increasing when fusing
Big substance, pressure cause nucleating work to reduce, and can be more easier forming core, and pressure increase promotes degree of supercooling to increase, to increase
Add number of nuclei, Shi Zhong ⊿ GvFor nucleating work, P is pressure；VαFor liquid phase volume, VβFor solid volume after solidification；It is pressed at GPa grades
Diffusion coefficient D when being solidified under powerpWith solidify diffusion coefficient D under normal pressureoRatio be formula (2) shown in, in formula, P be solidification pressure
Power；V0For the original molal volume of liquid phase；R is gas constant, and T is melt temperature.Pressure increase will reduce diffusion coefficient, solidification
Rate is accelerated, and setting time shortens.In addition, the diffusion of atom is suppressed under high pressure, increases the diffusion activation energy of atom, also make
The activation energy of crystal increases, thus the pressure reduction growth rate of crystal, the comprehensive function of three of the above effect cause
The interdendritic of alloy is away from being reduced.
Dp/Do=exp(-PV0/RT) (2)
Specific embodiment four
A kind of super-pressure preparation method of new medical metal material, includes the following steps:
Step 1, the pure magnesium ingot for weighing certain mass respectively, pure zinc granule, mass percent ingredient be Mg-30Zr first in
Between alloy, mass percent ingredient be Mg-30Gd the second intermediate alloy, for use；
Step 2, the Ar in resistance furnace2And SF6Under protective atmosphere, by pure magnesium ingot load weighted in step 1, pure zinc granule, quality
The first intermediate alloy that percent composition is Mg-30Zr, the second intermediate alloy that mass percent ingredient is Mg-30Gd are according to suitable
Sequence carries out melting, is poured into the metal die for being preheated to 200 DEG C after melting, obtains sample, for use；
Step 3, the sample for obtaining step 2, using pyrophyllite block, graphite-pipe carries out high-voltage samples assembling, assembles postposition
In high-pressure installation under the pressure of 2~6GPa, 20~30min is kept to carry out High Pressure Solidification processing at 950~980 DEG C, then
After pressure maintaining is cooled to 300 DEG C, heat-insulation pressure keeping 5~60 minutes, it is cooled to room temperature or is warmed to room temperature in dwell condition decline, institute is made
A kind of new medical metal material stated.
Specific embodiment 5:
A kind of super-pressure preparation method of new medical metal material according to specific embodiment four, in step 1
Zinc accounts for a kind of 6~8wt% of the gross mass of new medical metal material, and Zr accounts for a kind of gross mass of new medical metal material
0.5~1.0wt%, Gd account for a kind of 0.5~1.0wt% of the gross mass of new medical metal material, and surplus is magnesium.
Specific embodiment 6:
A kind of super-pressure preparation method of new medical metal material according to specific embodiment four, in step 1
Zinc accounts for a kind of 6wt% of the gross mass of new medical metal material, and Zr accounts for a kind of gross mass of new medical metal material
0.5wt%, Gd account for a kind of 0.5wt% of the gross mass of new medical metal material, and surplus is magnesium.
Specific embodiment 7:
A kind of super-pressure preparation method of new medical metal material according to specific embodiment four, in step 2
Resistance furnace temperature is 730~750 DEG C, is firstly added pure magnesium ingot and carries out melting, after its fusing, and with graphite bell jar by pure zinc granule
It is pressed under Serum Magnesium liquid level, after addition, the first intermediate alloy of Mg-30Zr is pressed into alloy with graphite bell jar by static 10min
Under melt liquid level, after static 15min, with graphite bell jar by the second intermediate alloy of Mg-30Gd indentation alloy melt liquid level it
Under, after stirring 10min, degassing processing is carried out using rotary blowing, 5min is stood, is poured into metal die.
Specific embodiment 8:
A kind of super-pressure preparation method of new medical metal material according to specific embodiment four, in step 3
The assemble method of high-voltage samples are as follows: first wrapped up with the sample that cold press obtains step 2 with boron nitride powder, graphite-pipe bottom
A cylindrical pyrophyllite block identical with its internal diameter is placed in portion, and the sample after package is close to cured piece of bottom leaf and is put into graphite-pipe
In, then the sample top after package is put into a same cylindrical pyrophyllite block, then with a graphite flake by graphite-pipe
Top seals；The graphite-pipe for sealing sample is put into middle position, graphite-pipe both ends in the circular hole among a cube pyrophyllite block
Two conducting rings are placed, for conductive heater sample, are punched until touching sample, then in cube pyrophyllite block right angle
Thermocouple wire is put into and is touched sample, the other end of thermocouple is temperature recording unit, completes high-voltage samples assembling.
Specific embodiment 9:
A kind of super-pressure preparation method of new medical metal material according to specific embodiment four, in step 3
High-pressure installation is CS-1B type cubic hinge press.
Specific embodiment 10:
A kind of super-pressure preparation method of new medical metal material according to specific embodiment four, in step 3
High-voltage samples after assembling are placed on the cavity position of high-pressure installation, the laggard horizontal high voltage solidification processing of tup centering.
Specific embodiment 11:
A kind of super-pressure preparation method of new medical metal material according to specific embodiment four, in step 3
The pressure of high-pressure installation is 4GPa, and the pressure of step 3 mesohigh device is 4GPa, is heated to 950 DEG C of heat preservations in 4GPa pressure maintaining and protects
Pressure 25 minutes, after pressure maintaining is cooled to 300 DEG C, heat-insulation pressure keeping 30 minutes, pressure maintaining was cooled to room temperature.
Specific embodiment 12:
The one of the super-pressure preparation method preparation of a kind of new medical metal material according to specific embodiment four
Kind new medical metal material, a kind of mass percentage composition of new medical metal material are 6~8wt% of zinc, zirconium
0.5~1.0wt%, 0.5~1.0wt% of gadolinium, surplus are magnesium.
Specific embodiment 13:
The one of the super-pressure preparation method preparation of a kind of new medical metal material according to specific embodiment four
Kind new medical metal material, a kind of microhardness of new medical metal material are 61.25~63.14HV.
Claims (10)
1. a kind of super-pressure preparation method of new medical metal material, characterized by the following steps:
Step 1, the pure magnesium ingot for weighing certain mass respectively, pure zinc granule, the first centre that mass percent ingredient is Mg-30Zr are closed
Gold, the second intermediate alloy that mass percent ingredient is Mg-30Gd, for use；
Step 2, the Ar in resistance furnace2And SF6Under protective atmosphere, by pure magnesium ingot load weighted in step 1, pure zinc granule, quality percentage
Than the first intermediate alloy that ingredient is Mg-30Zr, the second intermediate alloy that mass percent ingredient is Mg-30Gd in sequence into
Row melting pours into the metal die for being preheated to 200 DEG C after melting, obtains sample, for use；
Step 3, the sample for obtaining step 2, using pyrophyllite block, graphite-pipe carries out high-voltage samples assembling, and assembling is placed on height
In pressure device under the pressure of 2~6GPa, 20~30min is kept to carry out High Pressure Solidification processing, then pressure maintaining at 950~980 DEG C
It after being cooled to 300 DEG C, heat-insulation pressure keeping 5~60 minutes, is cooled to room temperature or is warmed to room temperature in dwell condition decline, be made described
A kind of new medical metal material.
2. a kind of super-pressure preparation method of new medical metal material according to claim 1, it is characterised in that: step
Zinc accounts for a kind of 6~8wt% of the gross mass of new medical metal material in 1, and Zr accounts for a kind of total matter of new medical metal material
0.5~1.0wt% of amount, Gd account for a kind of 0.5~1.0wt% of the gross mass of new medical metal material, and surplus is magnesium.
3. a kind of super-pressure preparation method of new medical metal material according to claim 1, it is characterised in that: step
Zinc accounts for a kind of 6wt% of the gross mass of new medical metal material in 1, and Zr accounts for a kind of gross mass of new medical metal material
0.5wt%, Gd account for a kind of 0.5wt% of the gross mass of new medical metal material, and surplus is magnesium.
4. a kind of super-pressure preparation method of new medical metal material according to claim 1, it is characterised in that: step
Resistance furnace temperature is 730~750 DEG C in 2, is firstly added pure magnesium ingot and carries out melting, after its fusing, and will be pure with graphite bell jar
Zinc granule is pressed under Serum Magnesium liquid level, and after addition, the first intermediate alloy of Mg-30Zr is pressed by static 10min with graphite bell jar
Under alloy melt liquid level, after static 15min, the second intermediate alloy of Mg-30Gd is pressed into alloy melt liquid with graphite bell jar
Under face, after stirring 10min, degassing processing is carried out using rotary blowing, 5min is stood, is poured into metal die.
5. a kind of super-pressure preparation method of new medical metal material according to claim 1, it is characterised in that: step
The assemble method of 3 mesohigh samples are as follows: first wrapped up with the sample that cold press obtains step 2 with boron nitride powder, graphite
Bottom of the tube places a cylindrical pyrophyllite block identical with its internal diameter, and the sample after package is close to cured piece of bottom leaf and is put into graphite
Guan Zhong, then the sample top after package is put into a same cylindrical pyrophyllite block, then with a graphite flake by graphite-pipe
Top seal；The graphite-pipe for sealing sample is put into middle position, graphite-pipe two in the circular hole among a cube pyrophyllite block
Two conducting rings are placed at end, for conductive heater sample, are punched until touching sample, so in cube pyrophyllite block right angle
Thermocouple wire is put into afterwards and is touched sample, the other end of thermocouple is temperature recording unit, completes high-voltage samples assembling.
6. a kind of super-pressure preparation method of new medical metal material according to claim 1, it is characterised in that: step
3 mesohigh devices are CS-1B type cubic hinge press.
7. a kind of super-pressure preparation method of new medical metal material according to claim 5 or 6, it is characterised in that:
High-voltage samples after assembling in step 3 are placed on the cavity position of high-pressure installation, the laggard horizontal high voltage solidification processing of tup centering.
8. a kind of super-pressure preparation method of new medical metal material according to claim 5 or 6, it is characterised in that:
The pressure of step 3 mesohigh device is 4GPa, is heated to 950 DEG C of heat-insulation pressure keepings 25 minutes in 4GPa pressure maintaining, pressure maintaining is cooled to 300
After DEG C, heat-insulation pressure keeping 30 minutes, pressure maintaining was cooled to room temperature.
9. a kind of one kind of the super-pressure preparation method preparation of new medical metal material described in a kind of one of claim 1-8
New medical metal material, it is characterised in that: a kind of mass percentage composition of new medical metal material be zinc 6~
8wt%, 0.5~1.0wt% of zirconium, 0.5~1.0wt% of gadolinium, surplus are magnesium.
10. one kind prepared by a kind of super-pressure preparation method of new medical metal material according to claim 9 is novel
Medical metal material, it is characterised in that: a kind of microhardness of new medical metal material is 61.25~63.14HV.
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Application publication date: 20190806 |