CN110449579A - A kind of preparation method of controlled degradation zinc-magnesium functionally gradient material (FGM) - Google Patents
A kind of preparation method of controlled degradation zinc-magnesium functionally gradient material (FGM) Download PDFInfo
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- CN110449579A CN110449579A CN201910647972.2A CN201910647972A CN110449579A CN 110449579 A CN110449579 A CN 110449579A CN 201910647972 A CN201910647972 A CN 201910647972A CN 110449579 A CN110449579 A CN 110449579A
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- graphite
- fgm
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- 239000000463 material Substances 0.000 title claims abstract description 82
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 24
- 230000015556 catabolic process Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 55
- 238000005245 sintering Methods 0.000 claims abstract description 35
- 230000007797 corrosion Effects 0.000 claims abstract description 28
- 238000005260 corrosion Methods 0.000 claims abstract description 28
- 238000000498 ball milling Methods 0.000 claims abstract description 27
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 18
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000005452 bending Methods 0.000 claims abstract description 11
- 230000006835 compression Effects 0.000 claims abstract description 10
- 238000007906 compression Methods 0.000 claims abstract description 10
- 238000000465 moulding Methods 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 54
- 229910002804 graphite Inorganic materials 0.000 claims description 54
- 239000010439 graphite Substances 0.000 claims description 54
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 229910001868 water Inorganic materials 0.000 claims description 27
- 229910052786 argon Inorganic materials 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 15
- 239000011777 magnesium Substances 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 238000004458 analytical method Methods 0.000 claims description 7
- 238000012512 characterization method Methods 0.000 claims description 6
- 230000003628 erosive effect Effects 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 5
- 238000004826 seaming Methods 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000000498 cooling water Substances 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- 238000007088 Archimedes method Methods 0.000 claims description 2
- 244000137852 Petrea volubilis Species 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 238000005054 agglomeration Methods 0.000 claims description 2
- 230000002776 aggregation Effects 0.000 claims description 2
- 150000001447 alkali salts Chemical class 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 238000005336 cracking Methods 0.000 claims description 2
- 230000003001 depressive effect Effects 0.000 claims description 2
- 238000001514 detection method Methods 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 239000012890 simulated body fluid Substances 0.000 claims description 2
- 239000007779 soft material Substances 0.000 claims description 2
- 238000004611 spectroscopical analysis Methods 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims 1
- 238000007710 freezing Methods 0.000 claims 1
- 230000008014 freezing Effects 0.000 claims 1
- 238000004806 packaging method and process Methods 0.000 claims 1
- 238000002513 implantation Methods 0.000 abstract description 12
- 210000000988 bone and bone Anatomy 0.000 abstract description 10
- 210000001519 tissue Anatomy 0.000 abstract description 7
- 239000012620 biological material Substances 0.000 abstract description 4
- 238000005253 cladding Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000002791 soaking Methods 0.000 abstract 1
- 238000010586 diagram Methods 0.000 description 4
- 239000007943 implant Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000008439 repair process Effects 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
- 229910052725 zinc Inorganic materials 0.000 description 2
- 208000010392 Bone Fractures Diseases 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 241000973495 Odax pullus Species 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 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
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000007281 self degradation Effects 0.000 description 1
- 239000004575 stone Substances 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
- 230000001225 therapeutic effect Effects 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- 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
-
- 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
-
- 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
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- 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
- 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
-
- 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
- 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
-
- 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
-
- 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
- C22C1/0483—Alloys based on the low melting point metals Zn, Pb, Sn, Cd, In or Ga
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
-
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
-
- 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
- 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
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
Abstract
The present invention relates to a kind of preparation methods of controlled degradation zinc-magnesium functionally gradient material (FGM), belong to the technical field of preparation and the application of biomaterial for medical purpose, aiming at the problem that single homogeneous material is difficult to meet degradable implantation material multifarious application requirement, using magnesium powder and zinc powder as raw material, by mixing the technology of preparing of powder, powder laying, pre-molding, discharge plasma sintering with powder, ball milling, a kind of combination controlled degradation zinc-magnesium functionally gradient material (FGM) is developed.The density of material is 3.58g/cm3, consistency reaches 98.2%, and compression strength is about 261MPa, and bending strength 114MPa, bending modulus 7.1GPa match with body bone tissue performance, can effectively avoid the generation of stress shielding effect, meets the performance requirement of human body hard tissue implantation material；Meanwhile the soaking corrosion of functionally gradient material (FGM), good corrosion resistance is shown in early period, and the characteristics of later period corrosion rate obviously increases, be able to achieve corrosion-resistant in implantation initial stage cladding material, guaranteed mechanical property, be implanted into the unique functional requirements of later period fast degradation.
Description
Technical field
The present invention relates to a kind of preparation method of controlled degradation zinc-magnesium functionally gradient material (FGM), belong to biomaterial for medical purpose preparation and
The technical field of application.
Background technique
Sclerous tissues' structure repair backing material is a kind of relatively early development, technology maturation, studies more deep biomaterial.Its
The defect part that body bone tissue is rebuild usually as filling material of bone, to the physiological function for restoring lesion and wound bone defect
It is highly effective.Traditional sclerous tissues' structure repair backing material is with titanium alloy, stainless steel, cobalt-base alloys and pure metal (tantalum, niobium)
Main, they all have good corrosion resistance, but many adverse effects can also be generated in human body by being chronically implanted.Titanium alloy
It is much higher than human body nature bone with the elasticity modulus of stainless steel, will cause serious " stress shielding ".Fixed frame is answered with green bone tissue
Power mismatches, and there are risk of bone fracture, lead to operative failure.Cobalt-base alloys and pure metal are implanted into human body, after knitting, need secondary
It takes out, increases sufferer pain.
At this stage, biodegradable medical metal material is due to having the characteristics that unique self-degradation by as sclerous tissues' structure
Backing material is repaired to study and apply extensively.Wherein, zinc-magnesium is with good biocompatibility and biodegradable spy
Point becomes research hotspot.But magnesium leads to a large amount of plasma diffusing W,Mos, not only influences biofacies because degradation rate in human body is too fast
Capacitive, but also material mechanical performance can be made to be deteriorated；When zinc is implanted into as implant, though degradation rate is slow, mechanical property is tight
Weight is insufficient.Ideal degradable biomaterial meets mechanical property and corrosion rate, and the phase slowly reduces before the treatment, after the treatment the phase
Fast degradation and the characteristics of corrosion product is not accumulated around implant.Working environment of the bio-medical material in inside of human body
In, it will be in contact and react with tissue and body fluid, this requires materials to possess good biocompatibility and corrosion resistance
Energy；Meanwhile implant also needs to be subjected to external force repeatedly in environment in vivo for a long time, in degradation process, still keeps uniform
Mechanical property, avoid " stress shielding ".
Single homogeneous material is difficult to meet the multifarious application requirement of degradable implantation material, corrosion resistance, mechanics
Performance and biocompatibility cannot enhance simultaneously.Thus, the controlled degradation zinc of a kind of combination different characteristics and function need to be developed
Magnesium functionally gradient material (FGM), making material integrally has good biocompatibility, corrosion resisting property and suitable mechanical property, to improve the life
The therapeutic effect of object material.
Summary of the invention
Goal of the invention
The purpose of the present invention is be difficult to meet asking for the degradable implantation multifarious application requirement of material for single homogeneous material
Topic, develops the controlled degradation zinc-magnesium functionally gradient material (FGM) of a kind of combination different characteristics and function.The material may be implemented in implantation initial stage
Cladding material is corrosion-resistant, guarantees overall mechanical properties, after the implantation the unique functional requirements of phase fast degradation.Specifically with magnesium powder and
Zinc powder is raw material, by mixing powder, powder laying, pre-molding, discharge plasma sintering with powder, ball milling and being made.
Technical solution
The chemical substance material that the present invention uses are as follows: zinc powder, magnesium powder, deionized water, dehydrated alcohol, graphite block, graphite cushion block, stone
Black briquetting, graphite paper, sand paper, it is as follows that a combination thereof prepares dosage: with millimeter, gram, milliliter, micron, centimetre3For measurement unit
Zinc powder: 5 ~ 10 μm of 99.9% partial size of Zn 238.48g ± 0.001g purity
Magnesium powder: 100 ~ 150 μm of 99.8% partial size of Mg 10.1g ± 0.001g purity
Dehydrated alcohol: C2H6O 600mL ± 10mL purity 99.7%
Deionized water: H2O 3000mL ± 10mL purity 99%
Graphite paper: Φ 50mm × 1mm, 2；
The preparation method is as follows:
(1) claim powder, dress powder
1. being 90% by Zn, the percent by volume that Mg is 10%, zinc powder 101.2g ± 0.001g is weighed respectively, magnesium powder 2.62g ±
0.001g is packed into first ball grinder, is put into agate ball, ratio of grinding media to material 3:1, sealing；
2. being 70% by Zn, the percent by volume that Mg is 30%, zinc powder 78.46g ± 0.001g is weighed respectively, magnesium powder 8.18g ±
0.001g is packed into second ball grinder, is put into agate ball, ratio of grinding media to material 3:1, sealing；
3. being 40% by Zn, the percent by volume that Mg is 60%, zinc powder 44.84g ± 0.001g is weighed respectively, magnesium powder 16.38g ±
0.001g is packed into third ball grinder, is put into agate ball, ratio of grinding media to material 3:1, sealing；
4. being 10% by Zn, the percent by volume that Mg is 90%, zinc powder 5.6g ± 0.001g is weighed respectively, magnesium powder 12.28g ±
0.001g is packed into the 4th ball grinder, is put into agate ball, ratio of grinding media to material 3:1, sealing；Claim powder, dress powder whole process in vacuum degree
It is carried out in the vacuum hand vanning of 7Pa；
(2) ball milling
Ball grinder in (1) is placed on planetary ball mill and mixes powder, rotational speed of ball-mill 400r/min carries out ball milling and mixes powder 5 hours,
Middle rotating forward 25min, stops 10min, then invert 25min, respectively obtained after ball milling Zn-10Mg powder, Zn-30Mg powder, Zn-60Mg powder,
Zn-90Mg powder；
(3) ball milling ball is taken out
The ball grinder after ball milling is opened in the vanning of vacuum hand, takes out agate ball, vacuum degree 7Pa；
(4) molding
Mold is manufactured using graphite block body, mold cavity be it is cylindric, cavity dimension is φ 50mm × 7mm, and type inner cavity surface is thick
Rugosity is Ra≤0.08 μm；
(5) die-filling
1. graphite jig is vertically arranged on steel plate, and is fixed by fixing seat；One block of graphite is put in mold cavity bottom
Cushion block, and graphite paper is put on graphite cushion block top, weighing 51.91g ± 0.001g ball milling, good Zn-10Mg powder is placed on graphite paper
Portion, with press machine precompressed；
2. weighing 43.32g ± 0.001g ball milling, good Zn-30Mg powder is placed in step 1. middle Zn-10Mg powder top, pre- with press machine
Pressure；
3. weighing 30.61g ± 0.001g ball milling, good Zn-60Mg powder is placed in step 2. middle Zn-30Mg powder top, pre- with press machine
Pressure；
4. the good Zn-90Mg powder of ball milling is placed in step 3. middle Zn-60Mg powder top, with press machine precompressed；
5. the good Zn-60Mg powder of remaining 30.61g ± 0.001g ball milling is placed in step 4. middle Zn-90Mg powder top, press machine is used
Precompressed；
6. the good Zn-30Mg powder of remaining 43.32g ± 0.001g ball milling is placed in step 5. middle Zn-60Mg powder top, press machine is used
Precompressed；
7. the good Zn-10Mg powder of remaining 51.91g ± 0.001g ball milling is placed in step 6. middle Zn-30Mg powder top, press machine is used
Precompressed；
8. covering another graphite paper after completing above step on top, putting another piece of graphite briquetting pressure on graphite paper top
Jail；Successively by above-mentioned steps, successively uniform powdering, guarantee different chemical composition even transition promote comprehensive mechanical property；
(6) zinc-magnesium gradient block is prepared
Whole preparation process carries out in vacuum discharge plasma agglomeration furnace, and preparation process is specific as follows:
1. opening the outer water circulating cooling valve of discharge plasma sintering furnace, outer water circulating cooling is carried out；
2. opening discharge plasma sintering furnace, die-filling graphite jig is moved on the workbench in sintering furnace, guarantees mold
Vertically, it is fastened again by upper lower lock block；
3. closing discharge plasma sintering furnace door, and seal closed；
4. opening the vacuum pump of discharge plasma sintering furnace, furnace air is extracted, pressure in furnace chamber is made to reach 4Pa；
The valve 5. unlatching argon bottle is supplied gas, argon gas, argon gas input speed 160cm are inputted into furnace chamber3/ min, constant furnace chamber internal pressure
By force at one atm；
6. opening plasma discharging heating switch, first it is rapidly heated with the heating rate of 65 DEG C/min to 300 DEG C, then with 35
DEG C/heating rate of min is slowly increased to 370 DEG C ± 1 DEG C, steady temperature；
7. then cracking pressure motor, pressure motor pressure 60MPa, constant temperature pressing time 10min stop heating, pressurization, mold
Cool to room temperature with the furnace；
8. blow-on, discharge plasma sintering furnace door is opened in die sinking, takes out mold, opens mold, takes out zinc-magnesium gradient block；
(7) it polishes
With sandpaper block body, block periphery and surface are cleaned；
(8) it cleans
With washes of absolute alcohol block surface and periphery, foreign matter is removed, keeps block surface clean；
(9) test, analysis and characterization
Corrosion resistance and corrosion shape to zinc-magnesium gradient block pattern, ingredient and the consistency of preparation, in SBF simulated body fluid
The test, analysis and characterization of looks, compression strength and bending strength；
With the whole pattern and erosion profile of scanning electron microscopic observation zinc-magnesium functionally gradient material (FGM)；
With the compactness of Archimedes method detection zinc-magnesium functionally gradient material (FGM)；
Constituent content analysis is carried out to zinc-magnesium functionally gradient material (FGM) with energy depressive spectroscopy；
Compression strength, the characterization of bending strength are carried out to functionally gradient material (FGM) with universal testing machine machine.
Conclusion: the present invention obtains a kind of controlled degradation zinc-magnesium functionally gradient material (FGM), density 3.58g/cm3, and consistency reaches
98.2%, compression strength is about 261MPa, bending strength 114MPa, bending modulus 7.1GPa, with body bone tissue performance phase
Matching, can effectively avoid the generation of stress shielding effect, meets the performance requirement (cortex bone: resistance to compression of human body hard tissue implantation material
Intensity 160-240MPa, elasticity modulus 3-23GPa)；It is found by immersion corrosion, functionally gradient material (FGM) is in (3 months) early period of average corruption
Losing rate is only 1.188mm/a, has good corrosion resistance, and the variation of functionally gradient material (FGM) pattern is little, and in later period (6 months)
Corrosion rate obviously increases, and reaches 62.101mm/a.Thus, controlled degradation zinc-magnesium functionally gradient material (FGM) prepared by the present invention is able to achieve
Implantation initial stage cladding material is corrosion-resistant, guarantees mechanical property, is implanted into the unique functional requirements of later period fast degradation.
(10) it packs, store
The zinc-magnesium functionally gradient material (FGM) of preparation is vacuum-packed with soft material, is stored in shady and cool clean environment, moisture-proof, sun-proof, acid-proof
Alkali salt corrodes, and 20 DEG C of storage temperature, relative humidity≤10%.
Beneficial effect
There is apparent advance compared with the background technology, the present invention, be to be difficult to meet degradable implantation for single homogeneous material
The problem of material multifarious application requirement, using magnesium powder and zinc powder as raw material, by mixing powder, powder laying, precompressed with powder, ball milling
It forms, the technology of preparing of discharge plasma sintering, develops the controlled degradation zinc-magnesium gradient of a kind of combination different characteristics and function
Material.The density of material is 3.58g/cm3, and consistency reaches 98.2%, and compression strength is about 261MPa, and bending strength is
114MPa, bending modulus 7.1GPa match with body bone tissue performance, can effectively avoid the generation of stress shielding effect,
Meet the performance requirement (cortex bone: compression strength 160-240MPa, elasticity modulus 3-23GPa) of human body hard tissue implantation material；It is logical
Immersion corrosion discovery is crossed, functionally gradient material (FGM) has good corrosion resistance in early period, and obviously increases in later period corrosion rate.Cause
And controlled degradation zinc-magnesium functionally gradient material (FGM) prepared by the present invention is able to achieve, guarantee mechanical property corrosion-resistant in implantation initial stage cladding material
Can, it is implanted into the unique functional requirements of later period fast degradation.
This preparation method technique is advanced, and data are accurately full and accurate, is the advanced side for preparing controlled degradation zinc-magnesium functionally gradient material (FGM)
Method.
Detailed description of the invention
Fig. 1 is the discharge plasma sintering state diagram of zinc-magnesium functionally gradient material (FGM)；
Fig. 2 is the whole shape appearance figure of zinc-magnesium functionally gradient material (FGM)；
Fig. 3 is the energy spectrum analysis figure of zinc-magnesium functionally gradient material (FGM)；
Fig. 4 is the compressive stress strain curve of zinc-magnesium functionally gradient material (FGM)；
Fig. 5 is erosion profile figure of the zinc-magnesium functionally gradient material (FGM) after 1 month；
Fig. 6 is erosion profile figure of the zinc-magnesium functionally gradient material (FGM) after 3 months；
Fig. 7 is zinc-magnesium functionally gradient material (FGM) corrosion rate variation diagram.
As shown in the figure, list of numerals is as follows:
1, vacuum sintering furnace, 2, footstock, 3, pedestal, 4, support, 5, outer water circulating cooling pipe, 6, vacuum pump, 7, vacuum tube, 8, cold
But water tank, 9, water pump, 10, outlet pipe, 11, return pipe, 12, workbench, 13, seaming chuck, 14, graphite jig, 15, graphite pads
Block, the 16, first graphite paper, 17, the magnesium zinc gradient mixed-powder successively laid, the 18, second graphite paper, 19, graphite briquetting, 20,
Outlet pipe valve, 21, pressure motor, 22, argon bottle, 23, argon gas valve, 24, tunger tube, 25, argon gas, 26, electric cabinet, 27, display
Screen, 28, indicator light, 29, power switch, 30, plasma discharging heating controller, 31, pressure electric machine controller, 32, vacuum pump
Controller, 33, water pump controller, the 34, first conducting wire, the 35, second conducting wire, 36, privates, 37, privates, 38, fixation
Seat, 39, furnace chamber, 40, plasma discharging heater.
Specific embodiment
The present invention will be further described below with reference to the accompanying drawings:
Shown in Fig. 1, it is the mixed-powder discharge plasma sintering state diagram of magnesium zinc gradient, need to correctly connects each section, sequentially grasp
Make.
The amount of the chemicals used when preparation by pre-set range determine, with gram, milliliter, micron, mol/L,
Centimetre3For measurement unit.
The sintering of magnesium zinc gradient mixed-powder carries out in the discharge plasma sintering furnace that argon gas is protected, be electric discharge etc. from
It is completed in sub- temperature-rise period；
Discharge plasma sintering furnace is vertical, including vacuum sintering furnace 1, and 1 lower part of vacuum sintering furnace is pedestal 3, top is footstock
2, inside is furnace chamber 39；Portion is equipped with bracket 4 on the base 3, and vacuum pump 6, water tank 8 are equipped in bracket 4；6 top of vacuum pump is set
There is vacuum tube 7,7 top of vacuum tube is protruded into furnace chamber 39；8 top of cooling water tank is equipped with water pump 9, and 9 top of water pump connects outlet pipe
10, outlet pipe 10 connects outer water circulating cooling pipe 5, and outer water circulating cooling pipe 5 connects return pipe 11, and return pipe 11 connects cooling water
Case 8 forms outer water circulating cooling；Bottom is equipped with workbench 12 in furnace chamber 39, and portion is disposed vertically graphite mo(u)ld on table 12
Tool 14, and fixed by firm banking 38, bottom is graphite cushion block 15 in graphite jig 14, is first on 15 top of graphite cushion block
Graphite paper 16 is the magnesium zinc gradient mixed-powder 17 successively laid, the magnesium zinc gradient successively laid on 16 top of the first graphite paper
17 top of mixed-powder is the second graphite paper 18, and 18 top of the second graphite paper is graphite briquetting 19, the connection of 19 top of graphite briquetting
Seaming chuck 13,13 top of seaming chuck connects footstock 2, and connects pressure motor 21；Electric discharge is equipped on the inner wall of vacuum sintering furnace 1
Plasma heater 40；Outlet pipe valve 20 is equipped in the upper right quarter of vacuum sintering furnace 1；The left part of vacuum sintering furnace 1 is equipped with argon gas
Bottle 22,22 top of argon bottle are equipped with argon gas valve 23, tunger tube 24, and argon gas 25 is inputted into furnace chamber 39；In vacuum sintering furnace 1
Right part is equipped with electric cabinet 26, and display screen 27, indicator light 28, power switch 29, plasma discharging heating are equipped on electric cabinet 26
Controller 30, pressure electric machine controller 31, controller for vacuum pump 32, water pump controller 33；Electric cabinet 26 passes through the first conducting wire 34
Connection water pump 9 connects vacuum pump 6 by the second conducting wire 35, plasma discharging heater 40 is connected by privates 36, is passed through
Privates 37 connect pressure motor 21.
Shown in Fig. 2, the whole shape appearance figure of zinc-magnesium functionally gradient material (FGM), it can be seen that Zn-10Mg, the Zn-30Mg successively laid,
The zinc magnesium alloy powder of Zn-60Mg, Zn-90Mg are incorporated evenly among together, black deepen content of magnesium increase, layer by layer between transition
Uniform smooth, be not in because ingredient difference it is excessive caused by stress mismatch phenomenon, to influence overall performance.
It is the energy spectrum analysis figure of zinc-magnesium functionally gradient material (FGM) shown in Fig. 3, by Zn-10Mg and Zn-30Mg combination interface,
Zn-30Mg and Zn-60Mg combination interface and Zn-60Mg and Zn-90Mg combination interface carry out the analysis of line scan element, find it is each at
Divide zinc magnesium alloy that there is good fusion, occurs without apparent ingredient transition zone.
It is the compressive stress strain curve of zinc-magnesium functionally gradient material (FGM), compression strength 261MPa, bending strength shown in Fig. 4
For 114MPa.
It is erosion profile figure of the zinc-magnesium functionally gradient material (FGM) after 1 month, it can be seen that only partial corrosion pitting shown in Fig. 5
Occur.
It is erosion profile figure of the zinc-magnesium functionally gradient material (FGM) after 3 months, it can be seen that zinc-magnesium functionally gradient material (FGM) is through 3 shown in Fig. 6
After the corrosion of the moon, there is the etch pit of large area to occur.
It is 6 months internal corrosion rate variation diagrams of zinc-magnesium functionally gradient material (FGM), it can be seen that zinc-magnesium functionally gradient material (FGM) shown in Fig. 7
Corrosion rate is in obvious gradient growth trend.
Claims (4)
1. a kind of preparation method of controlled degradation zinc-magnesium functionally gradient material (FGM), it is characterised in that: the chemical substance material used are as follows: zinc
Powder, magnesium powder, deionized water, dehydrated alcohol, graphite block, graphite cushion block, graphite briquetting, graphite paper, sand paper, a combination thereof prepare dosage
It is as follows: with millimeter, gram, milliliter, micron, centimetre3For measurement unit
Zinc powder: 5 ~ 10 μm of Zn partial size
Magnesium powder: 100 ~ 150 μm of Mg partial size
Dehydrated alcohol: C2H6O purity 99.7%
Deionized water: H2O purity 99%
Graphite paper: 2；
The preparation method is as follows:
(1) claim powder, dress powder
1. being 90% by Zn, the percent by volume that Mg is 10%, zinc powder 101.2g ± 0.001g is weighed respectively, magnesium powder 2.62g ±
0.001g is packed into first ball grinder, is put into agate ball, ratio of grinding media to material 3:1, sealing；
2. being 70% by Zn, the percent by volume that Mg is 30%, zinc powder 78.46g ± 0.001g is weighed respectively, magnesium powder 8.18g ±
0.001g is packed into second ball grinder, is put into agate ball, ratio of grinding media to material 3:1, sealing；
3. being 40% by Zn, the percent by volume that Mg is 60%, zinc powder 44.84g ± 0.001g is weighed respectively, magnesium powder 16.38g ±
0.001g is packed into third ball grinder, is put into agate ball, ratio of grinding media to material 3:1, sealing；
4. being 10% by Zn, the percent by volume that Mg is 90%, zinc powder 5.6g ± 0.001g is weighed respectively, magnesium powder 12.28g ±
0.001g is packed into the 4th ball grinder, is put into agate ball, ratio of grinding media to material 3:1, sealing；Claim powder, dress powder whole process in vacuum degree
It is carried out in the vacuum hand vanning of 7Pa；
(2) ball milling
Ball grinder in (1) is respectively placed on planetary ball mill and mixes powder, it is small to carry out the mixed powder 5 of ball milling by rotational speed of ball-mill 400r/min
When, wherein rotating forward 25min, stop 10min, then invert 25min, Zn-10Mg powder, Zn-30Mg powder, Zn- are respectively obtained after ball milling
60Mg powder, Zn-90Mg powder；
(3) ball milling ball is taken out
The ball grinder after ball milling is opened in the vanning of vacuum hand, takes out agate ball, vacuum degree 7Pa；
(4) molding
Mold is manufactured using graphite block body, mold cavity be it is cylindric, cavity dimension is φ 50mm × 7mm, and type inner cavity surface is thick
Rugosity is Ra≤0.08 μm；
(5) die-filling
1. graphite jig is vertically arranged on steel plate, and is fixed by fixing seat；One block of graphite is put in mold cavity bottom
Cushion block, and graphite paper is put on graphite cushion block top, weighing 51.91g ± 0.001g ball milling, good Zn-10Mg powder is placed on graphite paper
Portion, with press machine precompressed；
2. weighing 43.32g ± 0.001g ball milling, good Zn-30Mg powder is placed in step 1. middle Zn-10Mg powder top, pre- with press machine
Pressure；
3. weighing 30.61g ± 0.001g ball milling, good Zn-60Mg powder is placed in step 2. middle Zn-30Mg powder top, pre- with press machine
Pressure；
4. the good Zn-90Mg powder of ball milling is placed in step 3. middle Zn-60Mg powder top, with press machine precompressed；
5. the good Zn-60Mg powder of remaining 30.61g ± 0.001g ball milling is placed in step 4. middle Zn-90Mg powder top, press machine is used
Precompressed；
6. the good Zn-30Mg powder of remaining 43.32g ± 0.001g ball milling is placed in step 5. middle Zn-60Mg powder top, press machine is used
Precompressed；
7. the good Zn-10Mg powder of remaining 51.91g ± 0.001g ball milling is placed in step 6. middle Zn-30Mg powder top, press machine is used
Precompressed；
8. covering another graphite paper on top after completing above step, one piece of graphite briquetting is put on graphite paper top and is fastened；
(6) zinc-magnesium gradient block is prepared
Whole preparation process carries out in vacuum discharge plasma agglomeration furnace, and preparation process is specific as follows:
1. opening the outer water circulating cooling valve of discharge plasma sintering furnace, outer water circulating cooling is carried out；
2. opening discharge plasma sintering furnace, die-filling graphite jig is moved on the workbench in sintering furnace, guarantees mold
Vertically, it is fastened again by upper lower lock block；
3. closing discharge plasma sintering furnace door, and seal closed；
4. opening the vacuum pump of discharge plasma sintering furnace, furnace air is extracted, pressure in furnace chamber is made to reach 4Pa；
The valve 5. unlatching argon bottle is supplied gas, argon gas, argon gas input speed 160cm are inputted into furnace chamber3/ min, constant furnace chamber internal pressure
By force at one atm；
6. opening plasma discharging heating switch, first it is rapidly heated with the heating rate of 65 DEG C/min to 300 DEG C, then with 35
DEG C/heating rate of min is slowly increased to 370 DEG C ± 1 DEG C, steady temperature；
7. then cracking pressure motor, pressure motor pressure 60MPa, constant temperature pressing time 10min stop heating, pressurization, mold
Cool to room temperature with the furnace；
8. blow-on, discharge plasma sintering furnace door is opened in die sinking, takes out mold, opens mold, takes out zinc-magnesium gradient block；
(7) it polishes
With sandpaper block body, block periphery and surface are cleaned；
(8) it cleans
With washes of absolute alcohol block surface and periphery, foreign matter is removed, keeps block surface clean.
2. a kind of preparation method of controlled degradation zinc-magnesium functionally gradient material (FGM) according to claim 1, it is characterised in that: further include
Step (9) test, analysis and characterization
Corrosion resistance and corrosion shape to zinc-magnesium gradient block pattern, ingredient and the consistency of preparation, in SBF simulated body fluid
The test, analysis and characterization of looks, compression strength and bending strength；
With the whole pattern and erosion profile of scanning electron microscopic observation zinc-magnesium functionally gradient material (FGM)；
With the compactness of Archimedes method detection zinc-magnesium functionally gradient material (FGM)；
Constituent content analysis is carried out to zinc-magnesium functionally gradient material (FGM) with energy depressive spectroscopy；
Compression strength, the characterization of bending strength are carried out to functionally gradient material (FGM) with universal testing machine machine.
3. a kind of preparation method of controlled degradation zinc-magnesium functionally gradient material (FGM) according to claim 2, it is characterised in that: further include
Step (10) packaging, storage
The zinc-magnesium functionally gradient material (FGM) of preparation is vacuum-packed with soft material, is stored in shady and cool clean environment, moisture-proof, sun-proof, acid-proof
Alkali salt corrodes, and 20 DEG C of storage temperature, relative humidity≤10%.
4. a kind of preparation method of described in any item controlled degradation zinc-magnesium functionally gradient material (FGM)s, feature exist according to claim 1 ~ 3
In:
The sintering of zinc-magnesium functionally gradient material (FGM) is carried out in discharge plasma sintering furnace, is added in argon gas protection, plasma discharging
It is completed in thermal process；
Discharge plasma sintering furnace is vertical, including vacuum sintering furnace (1), vacuum sintering furnace (1) lower part are pedestal (3), top
For footstock (2), inside is furnace chamber (39)；Bracket (4) are equipped on pedestal (3) top, are equipped in the bracket (4) vacuum pump (6), cold
But water tank (8)；Vacuum pump (6) top is equipped with vacuum tube (7), and vacuum tube (7) top is protruded into furnace chamber (39)；Water tank (8) top
Equipped with water pump (9), water pump (9) top connects outlet pipe (10), and outlet pipe (10) connects outer water circulating cooling pipe (5), and outer water follows
Ring cooling tube (5) connects return pipe (11), and return pipe (11) connects cooling water tank (8), forms outer water circulating cooling；In furnace chamber
(39) interior bottom is equipped with workbench (12), places graphite jig (14) in workbench (12) upper vertical, and by firm banking
(38) fixed, it is graphite cushion block (15) in graphite jig (14) interior bottom, is the first graphite paper on graphite cushion block (15) top
It (16), is the magnesium zinc gradient mixed-powder (17) successively laid, the magnesium zinc gradient successively laid on the first graphite paper (16) top
Mixed-powder (17) top is the second graphite paper (18), and the second graphite paper (18) top is graphite briquetting (19), graphite briquetting
(19) top connection seaming chuck (13), seaming chuck (13) top connects footstock (2), and connects pressure motor (21)；It is burnt in vacuum
The inner wall of freezing of a furnace (1) is equipped with plasma discharging heater (40)；Outlet pipe valve is equipped in the upper right quarter of vacuum sintering furnace (1)
(20)；The left part of vacuum sintering furnace (1) is equipped with argon bottle (22), and argon bottle (22) top is equipped with argon gas valve (23), tunger tube
(24), argon gas (25) and into furnace chamber (39) are inputted；Electric cabinet (26) are equipped in the right part of vacuum sintering furnace (1), in electric cabinet
(26) display screen (27), indicator light (28), power switch (29), plasma discharging heating controller (30), pressure electricity are equipped with
Machine controller (31), controller for vacuum pump (32), water pump controller (33)；Electric cabinet (26) connects water by the first conducting wire (34)
Pump (9), plasma discharging heater (40) are connected by the second conducting wire (35) connection vacuum pump (6), by privates (36),
Pressure motor (21) are connected by privates (37).
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| CN112620630A (en) * | 2020-12-15 | 2021-04-09 | 昆明理工大学 | Preparation method of zinc-magnesium/hydroxyapatite porous composite material |
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| 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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