CN110449579B - Preparation method of controllable degradation zinc-magnesium gradient material - Google Patents
Preparation method of controllable degradation zinc-magnesium gradient material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 71
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 15
- 230000015556 catabolic process Effects 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 59
- 229910002804 graphite Inorganic materials 0.000 claims description 59
- 239000010439 graphite Substances 0.000 claims description 59
- 239000000843 powder Substances 0.000 claims description 50
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 45
- 238000000498 ball milling Methods 0.000 claims description 42
- 238000005245 sintering Methods 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 24
- 238000003825 pressing Methods 0.000 claims description 23
- 229910052786 argon Inorganic materials 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 13
- 239000011777 magnesium Substances 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 238000011049 filling Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 230000000630 rising effect Effects 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000011812 mixed powder Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000000498 cooling water Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000002490 spark plasma sintering Methods 0.000 claims description 3
- 244000137852 Petrea volubilis Species 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 33
- 238000005260 corrosion Methods 0.000 abstract description 33
- 210000000988 bone and bone Anatomy 0.000 abstract description 11
- 239000007943 implant Substances 0.000 abstract description 10
- 238000005452 bending Methods 0.000 abstract description 9
- 238000002513 implantation Methods 0.000 abstract description 8
- 210000001519 tissue Anatomy 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 239000012620 biological material Substances 0.000 abstract description 5
- 238000002791 soaking Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract 1
- 229910009369 Zn Mg Inorganic materials 0.000 description 6
- 229910007573 Zn-Mg Inorganic materials 0.000 description 6
- 238000010586 diagram Methods 0.000 description 4
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- 230000008439 repair process Effects 0.000 description 3
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- 239000000956 alloy Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000001054 cortical effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- 208000010392 Bone Fractures Diseases 0.000 description 1
- 206010017076 Fracture Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000001514 detection method Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007281 self degradation Effects 0.000 description 1
- 239000012890 simulated body fluid Substances 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 230000000472 traumatic effect Effects 0.000 description 1
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—Materials at least partially resorbable by the body
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
- B22F3/03—Press-moulding apparatus therefor
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
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- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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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
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0408—Light metal alloys
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0483—Alloys based on the low melting point metals Zn, Pb, Sn, Cd, In or Ga
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
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Abstract
The invention relates to a preparation method of a controllable degradable zinc-magnesium gradient material, belongs to the technical field of preparation and application of medical biomaterials, and aims to solve the problem that a single homogeneous material is difficult to meet the application requirement of diversity of a degradable implant material. The density of the material is 3.58g/cm3The compactness reaches 98.2 percent, the compressive strength is 261MPa, the bending strength is 114MPa, the bending modulus is 7.1GPa, and the composite material is matched with the performance of human bone tissues, so that the stress shielding effect can be effectively avoided, and the performance requirement of the human hard tissue implant can be met; meanwhile, the gradient material shows good corrosion resistance in the early stage through soaking corrosion, and the corrosion rate in the later stage is obviously increased, so that the special functional requirements of corrosion resistance of the outer layer material in the early stage of implantation, mechanical property guarantee and rapid degradation in the later stage of implantation can be realized.
Description
Technical Field
The invention relates to a preparation method of a controllable degradable zinc-magnesium gradient material, belonging to the technical field of preparation and application of medical biomaterials.
Background
The hard tissue structure repair support material is a biological material which is developed earlier, has mature technology and is studied deeply. It is generally used as a bone filler material to reconstruct a defective portion of human bone tissue, and is very effective in restoring physiological functions of diseased and traumatic bone defects. The traditional hard tissue structure repair supporting materials mainly comprise titanium alloy, stainless steel, cobalt-based alloy and pure metal (tantalum and niobium), which have good corrosion resistance, but have a plurality of adverse effects after being implanted in a human body for a long time. Titanium alloys and stainless steel have a much higher modulus of elasticity than natural human bone and can cause severe "stress shielding". The fixed frame is not matched with the original bone tissue in stress, so that the fracture risk exists, and the operation failure is caused. The cobalt-based alloy and the pure metal are implanted into a human body, and need to be taken out for the second time after the bone is healed, so that the pain of a patient is increased.
At present, the biodegradable medical metal material has unique self-degradation characteristics, so that the biodegradable medical metal material is widely researched and applied as a hard tissue structure repair support material. Among them, zinc and magnesium have good biocompatibility and biodegradability, which become research hotspots. However, magnesium degrades too fast in human body, resulting in release of a large amount of ions, which not only affects biocompatibility, but also deteriorates mechanical properties of materials; when the zinc is used as an implant to be implanted, although the degradation rate is slow, the mechanical property is seriously insufficient. The ideal degradable biomaterial meets the characteristics that the mechanical property and the corrosion speed are slowly reduced in the early treatment period, the degradation is fast in the later treatment period, and the corrosion products are not accumulated around the implant. The biomedical material is in contact reaction with human tissues and body fluid in a working environment inside a human body, so that the material is required to have good biocompatibility and corrosion resistance; meanwhile, the implant also needs to be subjected to repeated external force action in an internal environment for a long time, and the uniform mechanical property is still maintained in the degradation process, so that stress shielding is avoided.
The single homogeneous material is difficult to meet the application requirement of the diversity of the degradable implant material, and the corrosion resistance, the mechanical property and the biocompatibility cannot be simultaneously enhanced. Therefore, a controllable degradable zinc-magnesium gradient material combining different characteristics and functions needs to be developed, so that the whole material has good biocompatibility, corrosion resistance and appropriate mechanical properties, and the treatment effect of the biological material is improved.
Disclosure of Invention
Object of the Invention
The invention aims to develop a controllable degradable zinc-magnesium gradient material combining different characteristics and functions aiming at the problem that a single homogeneous material is difficult to meet the application requirement of the diversity of degradable implant materials. The material can realize the corrosion resistance of the outer layer material at the early stage of implantation, ensure the overall mechanical property and meet the unique functional requirement of rapid degradation at the later stage of implantation. The magnesium powder and the zinc powder are used as raw materials and are prepared by powder preparation, ball milling and powder mixing, powder laying, prepressing forming and spark plasma sintering.
Technical scheme
The chemical substance materials used in the invention are as follows: zinc powder, magnesium powder, deionized water, absolute ethyl alcohol, graphite blocks, graphite cushion blocks, graphite pressing blocks, graphite paper and sand paper, wherein the combined preparation dosage is as follows: in mm, g, ml, micron and cm3As a unit of measure
Zinc powder: 238.48g + -0.001 g Zn with purity of 99.9% and particle size of 5-10 μm
Magnesium powder: 10.1g of Mg +/-0.001 g of 99.8% purity and 100-150 μm of particle diameter
Anhydrous ethanol: c2H6O600 mL +/-10 mL, purity 99.7%
Deionized water: h2O3000 mL +/-10 mL, purity 99%
Graphite paper: phi 50mm is multiplied by 1mm, 2 pieces;
the preparation method comprises the following steps:
(1) weighing and filling the powder
Weighing 101.2g +/-0.001 g of zinc powder and 2.62g +/-0.001 g of magnesium powder according to the volume percentage of 90% of Zn and 10% of Mg, filling the zinc powder and the magnesium powder into a first ball milling tank, putting agate balls into the first ball milling tank, and sealing the first ball milling tank at a ball-to-material ratio of 3: 1;
secondly, 78.46g +/-0.001 g of zinc powder and 8.18g +/-0.001 g of magnesium powder are respectively weighed according to the volume percentage of 70 percent of Zn and 30 percent of Mg, the weighed zinc powder and the magnesium powder are put into a second ball milling tank, agate balls are put into the second ball milling tank, the ball-to-material ratio is 3:1, and the second ball milling tank is sealed;
thirdly, according to the volume percentage of 40 percent of Zn and 60 percent of Mg, respectively weighing 44.84g +/-0.001 g of zinc powder and 16.38g +/-0.001 g of magnesium powder, putting the zinc powder and the magnesium powder into a third ball-milling tank, putting agate balls into the third ball-milling tank, and sealing the third ball-milling tank at a ball-to-material ratio of 3: 1;
weighing 5.6g +/-0.001 g of zinc powder and 12.28g +/-0.001 g of magnesium powder according to the volume percentage of 10% of Zn and 90% of Mg, respectively, filling the zinc powder and the magnesium powder into a fourth ball milling tank, putting agate balls into the fourth ball milling tank, and sealing the fourth ball milling tank at a ball-to-material ratio of 3: 1; the whole process of weighing and filling the powder is carried out in a vacuum hand-filling box with the vacuum degree of 7 Pa;
(2) ball mill
Putting the ball milling tank in the step (1) on a planetary ball mill for mixing powder, performing ball milling at the ball milling rotation speed of 400r/min for 5 hours, wherein the ball milling tank rotates forwards for 25 minutes, stops for 10 minutes, rotates backwards for 25 minutes, and obtains Zn-10Mg powder, Zn-30Mg powder, Zn-60Mg powder and Zn-90Mg powder after ball milling;
(3) ball grinding ball
Opening the ball milling tank after ball milling in a vacuum hand-packed box, and taking out agate balls with the vacuum degree of 7 Pa;
(4) moulding
The mould is made of graphite blocks, the mould cavity is cylindrical, the size of the mould cavity is phi 50mm multiplied by 7mm, and the roughness of the inner surface of the mould cavity is Ra less than or equal to 0.08 mu m;
(5) die filling
Firstly, vertically placing a graphite mould on a steel flat plate and fixing the graphite mould by a fixed seat; placing a graphite cushion block at the bottom of a mold cavity, placing graphite paper on the upper part of the graphite cushion block, weighing 51.91g +/-0.001 g of ball-milled Zn-10Mg powder, placing the powder on the upper part of the graphite paper, and pre-pressing by using a press;
secondly, 43.32g +/-0.001 g of ball-milled Zn-30Mg powder is weighed and placed on the upper part of the Zn-10Mg powder in the step I, and a press machine is used for prepressing;
thirdly, 30.61g +/-0.001 g of ball-milled Zn-60Mg powder is weighed and placed on the upper part of the Zn-30Mg powder in the second step, and a press machine is used for prepressing;
fourthly, placing the ball-milled Zn-90Mg powder on the upper part of the Zn-60Mg powder in the third step, and prepressing by a press;
fifthly, placing the rest 30.61g +/-0.001 g of ball-milled Zn-60Mg powder on the upper part of the Zn-90Mg powder in the step IV, and prepressing by using a press;
sixthly, putting the rest 43.32g +/-0.001 g of Zn-30Mg powder subjected to ball milling on the upper part of the Zn-60Mg powder in the fifth step, and prepressing by using a press;
seventhly, placing the remaining 51.91g +/-0.001 g of ball-milled Zn-10Mg powder on the upper part of the Zn-30Mg powder in the step sixthly, and prepressing by using a press;
eighthly, covering another piece of graphite paper on the upper part after the steps are finished, and placing another piece of graphite pressing block on the upper part of the graphite paper for pressing firmly; powder is sequentially and uniformly spread layer by layer according to the steps, so that uniform transition of different chemical components is ensured, and the comprehensive mechanical property is improved;
(6) preparation of zinc-magnesium gradient block
The whole preparation process is carried out in a vacuum discharge plasma sintering furnace, and the preparation process specifically comprises the following steps:
opening an external water circulating cooling valve of the discharge plasma sintering furnace to carry out external water circulating cooling;
opening the discharge plasma sintering furnace, translating the graphite mold with the mold to a workbench in the sintering furnace, ensuring the mold to be vertical, and firmly pressing the mold by an upper pressing block and a lower pressing block again;
thirdly, closing the door of the discharge plasma sintering furnace, and sealing;
starting a vacuum pump of the discharge plasma sintering furnace, and extracting air in the furnace to enable the pressure in the furnace chamber to reach 4 Pa;
opening the gas feeding valve of the argon bottle, inputting argon into the furnace chamber at the argon input speed of 160cm3Min, keeping the pressure in the furnace chamber constant at one atmosphere;
sixthly, starting a discharge plasma temperature rising switch, quickly rising the temperature to 300 ℃ at a temperature rising speed of 65 ℃/min, then slowly rising the temperature to 370 +/-1 ℃ at a temperature rising speed of 35 ℃/min, and keeping the temperature constant;
seventhly, starting a pressure motor, keeping the pressure of the pressure motor at 60MPa, keeping the temperature and pressurizing for 10min, then stopping heating and pressurizing, and cooling the die to room temperature along with the furnace;
opening the furnace, opening a discharge plasma sintering furnace door, taking out the mold, opening the mold, and taking out the zinc-magnesium gradient block;
(7) polishing
Polishing the block body by using abrasive paper, and cleaning the periphery and the surface of the block body;
(8) cleaning of
Cleaning the surface and periphery of the block body with absolute ethyl alcohol, and removing foreign matters to clean the surface of the block body;
(9) detection, analysis, characterization
Detecting, analyzing and representing the appearance, components and density of the prepared zinc-magnesium gradient block, the corrosion resistance and corrosion appearance, the compressive strength and the bending strength in SBF simulated body fluid;
observing the overall appearance and the corrosion appearance of the zinc-magnesium gradient material by using a scanning electron microscope;
detecting the compactness of the zinc-magnesium gradient material by an Archimedes method;
analyzing the element content of the zinc-magnesium gradient material by an energy spectrum analyzer;
and (5) representing the compressive strength and the bending strength of the gradient material by using a universal testing machine.
And (4) conclusion: the invention obtains a controllable degradation zinc-magnesium gradient material, the density of which is 3.58g/cm3, the density of which reaches 98.2%, the compressive strength of which is 261MPa, the bending strength of which is 114MPa, and the bending modulus of which is 7.1GPa, which is matched with the performance of human bone tissues, can effectively avoid the generation of stress shielding effect and meet the performance requirements of human hard tissue implants (cortical bone: compressive strength 160-240MPa, and elastic modulus of which is 3-23 GPa); the soaking corrosion shows that the average corrosion rate of the gradient material in the early stage (3 months) is only 1.188mm/a, the gradient material has good corrosion resistance, the appearance of the gradient material is not changed greatly, and the corrosion rate in the later stage (6 months) is obviously increased to 62.101 mm/a. Therefore, the controllable degradation zinc-magnesium gradient material prepared by the invention can realize the unique functional requirements of corrosion resistance of the outer layer material at the early stage of implantation, mechanical property guarantee and rapid degradation at the later stage of implantation.
(10) Packaging and storing
The prepared zinc-magnesium gradient material is vacuum-packaged by using a soft material, is stored in a cool and clean environment, and is required to be damp-proof, sun-proof and acid-base salt corrosion-proof, and the storage temperature is 20 ℃ and the relative humidity is less than or equal to 10%.
Advantageous effects
Compared with the prior art, the invention has obvious advancement, aims at the problem that a single homogeneous material is difficult to meet the application requirement of the diversity of degradable implant materials, and develops a controllable degradable zinc-magnesium gradient material combining different characteristics and functions by taking magnesium powder and zinc powder as raw materials and adopting the preparation technologies of powder preparation, ball milling and powder mixing, powder laying, pre-pressing and forming and discharge plasma sintering. The material has the density of 3.58g/cm3, the density of 98.2 percent, the compressive strength of 261MPa, the bending strength of 114MPa and the bending modulus of 7.1GPa, is matched with the performance of human bone tissues, can effectively avoid the stress shielding effect and meet the performance requirements of human hard tissue implants (cortical bone, the compressive strength of 160-240MPa and the elastic modulus of 3-23 GPa); the soaking corrosion shows that the gradient material has good corrosion resistance in the early stage, and the corrosion rate is obviously increased in the later stage. Therefore, the controllable degradation zinc-magnesium gradient material prepared by the invention can realize the unique functional requirements of corrosion resistance of the outer layer material at the early stage of implantation, mechanical property guarantee and rapid degradation at the later stage of implantation.
The preparation method has advanced process and accurate and detailed data, and is an advanced method for preparing the controllable degradation zinc-magnesium gradient material.
Drawings
FIG. 1 is a diagram of a zinc-magnesium gradient material sintering state by spark plasma;
FIG. 2 is an overall morphology diagram of a zinc-magnesium gradient material;
FIG. 3 is a diagram of the energy spectrum analysis of a zinc-magnesium gradient material;
FIG. 4 is a compressive stress-strain curve of a zinc-magnesium gradient material;
FIG. 5 is a graph of corrosion profile of a zinc-magnesium gradient material after 1 month;
FIG. 6 is a graph of corrosion profile of a zinc-magnesium gradient material after 3 months;
FIG. 7 is a graph showing the change of corrosion rate of a zinc-magnesium gradient material.
As shown in the figures, the list of reference numbers is as follows:
1. a vacuum sintering furnace, 2, a top seat, 3, a base, 4, a support, 5, an external water circulation cooling pipe, 6, a vacuum pump, 7, a vacuum pipe, 8, a cooling water tank, 9, a water pump, 10, a water outlet pipe, 11, a water return pipe, 12, a workbench, 13, an upper pressure head, 14, a graphite mold, 15, a graphite cushion block, 16, first graphite paper, 17, magnesium-zinc gradient mixed powder which is laid layer by layer, 18, second graphite paper, 19, a graphite pressing block, 20, a gas outlet pipe valve, 21, a pressure motor, 22, an argon gas bottle, 23, an argon gas valve, 24, an argon gas pipe, 25, argon gas, 26, an electric cabinet, 27, a display screen, 28, an indicator light, 29, a power switch, 30, a discharge plasma heating controller, 31, a pressure motor controller, 32, a vacuum pump controller, 33, a water pump controller, 34, a first lead, 35, a second lead, 36 and a third lead, 37. fourth wire, 38, fixing seat, 39, furnace chamber, 40, discharge plasma heater.
Detailed Description
The invention is further described below with reference to the accompanying drawings:
FIG. 1 shows the sintering state diagram of Mg-Zn gradient mixed powder discharge plasma, which needs to connect each part correctly and operate in sequence.
The amount of chemicals used in the preparation is determined in the preset range, and is measured in grams, milliliters, micrometers, moles/liter and centimeters3Is a unit of measurement.
Sintering the magnesium-zinc gradient mixed powder in a spark plasma sintering furnace protected by argon, wherein the sintering is completed in the process of heating the spark plasma;
the discharge plasma sintering furnace is vertical and comprises a vacuum sintering furnace 1, wherein the lower part of the vacuum sintering furnace 1 is provided with a base 3, the upper part of the vacuum sintering furnace 1 is provided with a top seat 2, and the inner part of the vacuum sintering furnace is provided with a furnace chamber 39; a support 4 is arranged at the upper part of the base 3, and a vacuum pump 6 and a water tank 8 are arranged in the support 4; the vacuum tube 7 is arranged at the upper part of the vacuum pump 6, and the upper part of the vacuum tube 7 extends into the furnace chamber 39; the upper part of the cooling water tank 8 is provided with a water pump 9, the upper part of the water pump 9 is connected with a water outlet pipe 10, the water outlet pipe 10 is connected with an external water circulating cooling pipe 5, the external water circulating cooling pipe 5 is connected with a water return pipe 11, and the water return pipe 11 is connected with the cooling water tank 8 to form external water circulating cooling; a workbench 12 is arranged at the bottom in a furnace chamber 39, a graphite die 14 is vertically arranged at the upper part of the workbench 12 and is fixed by a fixing base 38, a graphite cushion block 15 is arranged at the bottom in the graphite die 14, first graphite paper 16 is arranged at the upper part of the graphite cushion block 15, magnesium-zinc gradient mixed powder 17 is laid layer by layer at the upper part of the first graphite paper 16, second graphite paper 18 is arranged at the upper part of the magnesium-zinc gradient mixed powder 17 laid layer by layer, a graphite pressing block 19 is arranged at the upper part of the second graphite paper 18, an upper pressing head 13 is connected at the upper part of the graphite pressing block 19, and the upper part of the upper pressing head 13 is connected with a top seat 2 and a pressure motor 21; a discharge plasma heater 40 is arranged on the inner wall of the vacuum sintering furnace 1; an air outlet pipe valve 20 is arranged at the upper right part of the vacuum sintering furnace 1; an argon gas bottle 22 is arranged at the left part of the vacuum sintering furnace 1, an argon gas valve 23 and an argon gas pipe 24 are arranged at the upper part of the argon gas bottle 22, and argon gas 25 is input into the furnace chamber 39; an electric cabinet 26 is arranged at the right part of the vacuum sintering furnace 1, and a display screen 27, an indicator light 28, a power switch 29, a discharge plasma heating controller 30, a pressure motor controller 31, a vacuum pump controller 32 and a water pump controller 33 are arranged on the electric cabinet 26; the electric control box 26 is connected with the water pump 9 through a first lead 34, the vacuum pump 6 through a second lead 35, the discharge plasma heater 40 through a third lead 36 and the pressure motor 21 through a fourth lead 37.
FIG. 2 shows the overall morphology of the Zn-Mg gradient material, in which the Zn-Mg alloy powders of Zn-10Mg, Zn-30Mg, Zn-60Mg and Zn-90Mg laid layer by layer are uniformly combined together, the black color deepens the increase of the Mg content, the transition between layers is uniform and smooth, and the stress mismatch phenomenon caused by excessive component differences can not occur, so that the overall performance is not affected.
FIG. 3 is a graph showing the energy spectrum analysis of a Zn-Mg gradient material, and line scan elemental analysis is performed on a Zn-10Mg and Zn-30Mg bonding interface, a Zn-30Mg and Zn-60Mg bonding interface and a Zn-60Mg and Zn-90Mg bonding interface to find that the Zn-Mg alloy with each component has good fusion and no obvious component transition layer.
FIG. 4 shows the compressive stress-strain curve of the zinc-magnesium gradient material, the compressive strength is 261MPa, and the bending strength is 114 MPa.
FIG. 5 shows the corrosion morphology of the zinc-magnesium gradient material after 1 month, and it can be seen that only partial corrosion pits appear.
FIG. 6 shows the corrosion morphology of the Zn-Mg gradient material after 3 months, which shows that after 3 months of corrosion, large areas of corrosion pits appear on the Zn-Mg gradient material.
FIG. 7 is a graph showing the change of corrosion rate of the zinc-magnesium gradient material within 6 months, and it can be seen that the corrosion rate of the zinc-magnesium gradient material has a significant gradient increasing trend.
Claims (2)
1. A preparation method of a controllable degradation zinc-magnesium gradient material is characterized by comprising the following steps: the chemical materials used were: zinc powder, magnesium powder, deionized water, absolute ethyl alcohol, graphite blocks, graphite cushion blocks, graphite pressing blocks, graphite paper and sand paper, wherein the combined preparation dosage is as follows: measured in units of millimeter, gram, milliliter and micron
Zinc powder: 238.48g + -0.001 g Zn with purity of 99.9% and particle size of 5-10 μm
Magnesium powder: 10.1g of Mg +/-0.001 g of 99.8% purity and 100-150 μm of particle diameter
Anhydrous ethanol: c2H6O600 mL +/-10 mL, purity 99.7%
Deionized water: h2O3000 mL +/-10 mL, purity 99%
Graphite paper: phi 50mm is multiplied by 1mm, 2 pieces;
the preparation method comprises the following steps:
(1) weighing and filling the powder
Weighing 101.2g +/-0.001 g of zinc powder and 2.62g +/-0.001 g of magnesium powder according to the volume percentage of 90% of Zn and 10% of Mg, filling the zinc powder and the magnesium powder into a first ball milling tank, putting agate balls into the first ball milling tank, and sealing the first ball milling tank at a ball-to-material ratio of 3: 1;
secondly, 78.46g +/-0.001 g of zinc powder and 8.18g +/-0.001 g of magnesium powder are respectively weighed according to the volume percentage of 70 percent of Zn and 30 percent of Mg, the weighed zinc powder and the magnesium powder are put into a second ball milling tank, agate balls are put into the second ball milling tank, the ball-to-material ratio is 3:1, and the second ball milling tank is sealed;
thirdly, according to the volume percentage of 40 percent of Zn and 60 percent of Mg, respectively weighing 44.84g +/-0.001 g of zinc powder and 16.38g +/-0.001 g of magnesium powder, putting the zinc powder and the magnesium powder into a third ball-milling tank, putting agate balls into the third ball-milling tank, and sealing the third ball-milling tank at a ball-to-material ratio of 3: 1;
weighing 5.6g +/-0.001 g of zinc powder and 12.28g +/-0.001 g of magnesium powder according to the volume percentage of 10% of Zn and 90% of Mg, respectively, filling the zinc powder and the magnesium powder into a fourth ball milling tank, putting agate balls into the fourth ball milling tank, and sealing the fourth ball milling tank at a ball-to-material ratio of 3: 1; the whole process of weighing and filling powder is carried out in a vacuum glove box with the vacuum degree of 7 Pa;
(2) ball mill
Respectively placing the ball milling tanks in the step (1) on a planetary ball mill to mix powder, performing ball milling at the ball milling rotation speed of 400r/min for 5 hours, wherein the ball milling is performed for 25 minutes in a forward rotation mode, is stopped for 10 minutes, is performed for 25 minutes in a reverse rotation mode, and is performed to obtain Zn-10Mg powder, Zn-30Mg powder, Zn-60Mg powder and Zn-90Mg powder respectively after ball milling;
(3) ball grinding ball
Opening the ball milling tank after ball milling in a vacuum glove box, and taking out agate balls with the vacuum degree of 7 Pa;
(4) moulding
The mould is made of graphite blocks, the mould cavity is cylindrical, the size of the mould cavity is phi 50mm multiplied by 7mm, and the roughness of the inner surface of the mould cavity is Ra less than or equal to 0.08 mu m;
(5) die filling
Firstly, vertically placing a graphite mould on a steel flat plate and fixing the graphite mould by a fixed seat; placing a graphite cushion block at the bottom of a mold cavity, placing graphite paper on the upper part of the graphite cushion block, weighing 51.91g +/-0.001 g of ball-milled Zn-10Mg powder, placing the powder on the upper part of the graphite paper, and pre-pressing by using a press;
secondly, 43.32g +/-0.001 g of ball-milled Zn-30Mg powder is weighed and placed on the upper part of the Zn-10Mg powder in the step I, and a press machine is used for prepressing;
thirdly, 30.61g +/-0.001 g of ball-milled Zn-60Mg powder is weighed and placed on the upper part of the Zn-30Mg powder in the second step, and a press machine is used for prepressing;
fourthly, placing the ball-milled Zn-90Mg powder on the upper part of the Zn-60Mg powder in the third step, and prepressing by a press;
fifthly, placing the rest 30.61g +/-0.001 g of ball-milled Zn-60Mg powder on the upper part of the Zn-90Mg powder in the step IV, and prepressing by using a press;
sixthly, putting the rest 43.32g +/-0.001 g of Zn-30Mg powder subjected to ball milling on the upper part of the Zn-60Mg powder in the fifth step, and prepressing by using a press;
seventhly, placing the remaining 51.91g +/-0.001 g of ball-milled Zn-10Mg powder on the upper part of the Zn-30Mg powder in the step sixthly, and prepressing by using a press;
eighthly, covering another piece of graphite paper on the upper part after the steps are finished, and placing a graphite pressing block on the upper part of the graphite paper for pressing firmly;
(6) preparation of zinc-magnesium gradient block
The whole preparation process is carried out in a vacuum discharge plasma sintering furnace, and the preparation process specifically comprises the following steps:
opening an external water circulating cooling valve of the discharge plasma sintering furnace to carry out external water circulating cooling;
opening the discharge plasma sintering furnace, translating the graphite mold with the mold to a workbench in the sintering furnace, ensuring the mold to be vertical, and firmly pressing the graphite mold again by a graphite pressing block;
thirdly, closing the door of the discharge plasma sintering furnace, and sealing;
starting a vacuum pump of the discharge plasma sintering furnace, and extracting air in the furnace to enable the pressure in the furnace chamber to reach 4 Pa;
opening the gas feeding valve of the argon bottle, inputting argon into the furnace chamber at the argon input speed of 160cm3Min, keeping the pressure in the furnace chamber constant at one atmosphere;
sixthly, starting a discharge plasma temperature rising switch, quickly rising the temperature to 300 ℃ at a temperature rising speed of 65 ℃/min, then slowly rising the temperature to 370 +/-1 ℃ at a temperature rising speed of 35 ℃/min, and keeping the temperature constant;
seventhly, starting a pressure motor, keeping the pressure of the pressure motor at 60MPa, keeping the temperature and pressurizing for 10min, then stopping heating and pressurizing, and cooling the die to room temperature along with the furnace;
opening the furnace, opening a discharge plasma sintering furnace door, taking out the mold, opening the mold, and taking out the zinc-magnesium gradient block;
(7) polishing
Polishing the block body by using abrasive paper, and cleaning the periphery and the surface of the block body;
(8) cleaning of
And (3) cleaning the surface and periphery of the block body by using absolute ethyl alcohol, and removing foreign matters to clean the surface of the block body.
2. The preparation method of the controllable degradation zinc-magnesium gradient material according to claim 1, characterized in that:
the sintering of the zinc-magnesium gradient material is carried out in a spark plasma sintering furnace and is finished in the processes of argon protection and spark plasma heating;
the discharge plasma sintering furnace is vertical and comprises a vacuum sintering furnace (1), wherein the lower part of the vacuum sintering furnace (1) is provided with a base (3), the upper part of the vacuum sintering furnace is provided with a top seat (2), and the interior of the vacuum sintering furnace is provided with a furnace chamber (39); a bracket (4) is arranged at the upper part of the base (3), and a vacuum pump (6) and a cooling water tank (8) are arranged in the bracket (4); a vacuum tube (7) is arranged at the upper part of the vacuum pump (6), and the upper part of the vacuum tube (7) extends into the furnace chamber (39); a water pump (9) is arranged at the upper part of the water tank (8), the upper part of the water pump (9) is connected with a water outlet pipe (10), the water outlet pipe (10) is connected with an external water circulating cooling pipe (5), the external water circulating cooling pipe (5) is connected with a water return pipe (11), and the water return pipe (11) is connected with the cooling water tank (8) to form external water circulating cooling; a workbench (12) is arranged at the bottom in a furnace chamber (39), a graphite mold (14) is vertically placed on the upper portion of the workbench (12) and fixed by a fixing base (38), a graphite cushion block (15) is arranged at the bottom in the graphite mold (14), first graphite paper (16) is arranged on the upper portion of the graphite cushion block (15), magnesium-zinc gradient mixed powder (17) laid layer by layer is arranged on the upper portion of the first graphite paper (16), second graphite paper (18) is arranged on the upper portion of the magnesium-zinc gradient mixed powder (17) laid layer by layer, a graphite pressing block (19) is arranged on the upper portion of the second graphite paper (18), an upper pressing head (13) is connected on the upper portion of the graphite pressing block (19), and the upper portion of the upper pressing head (13) is connected with a top seat (2) and is connected with a pressure motor (21); a discharge plasma heater (40) is arranged on the inner wall of the vacuum sintering furnace (1); an air outlet pipe valve (20) is arranged at the right upper part of the vacuum sintering furnace (1); an argon bottle (22) is arranged at the left part of the vacuum sintering furnace (1), an argon valve (23) and an argon pipe (24) are arranged at the upper part of the argon bottle (22), and argon (25) is input into the furnace chamber (39); an electric cabinet (26) is arranged at the right part of the vacuum sintering furnace (1), and a display screen (27), an indicator light (28), a power switch (29), a discharge plasma heating controller (30), a pressure motor controller (31), a vacuum pump controller (32) and a water pump controller (33) are arranged on the electric cabinet (26); the electric cabinet (26) is connected with the water pump (9) through a first lead (34), connected with the vacuum pump (6) through a second lead (35), connected with the discharge plasma heater (40) through a third lead (36) and connected with the pressure motor (21) through a fourth lead (37).
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| JPH0633104A (en) * | 1992-07-16 | 1994-02-08 | Nippon Tungsten Co Ltd | Distortionless alloy body having graded composition and production thereof |
| CN104911554A (en) * | 2015-04-10 | 2015-09-16 | 中国钢研科技集团有限公司 | Industrialized whole continuous PVD production process of zinc magnesium alloy coating steel strip |
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