CN104195369B - A kind of Zn-Ca system kirsite and preparation method and application - Google Patents
A kind of Zn-Ca system kirsite and preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of Zn Ca system kirsite and preparation method and application.Kirsite of the present invention includes Zn and Ca；By weight percentage, in described kirsite, the mass percent of Ca is 0～30%, but does not include 0.Also including trace element in described kirsite, described trace element is at least one in silicon, phosphorus, lithium, silver, stannum and rare earth element；In described kirsite, the weight/mass percentage composition of described trace element is 0～3%, but does not include 0.The mechanical property of Zn of the present invention Ca system kirsite meet the intensity of medical implant material and the requirement of toughness, nontoxic, possess good histocompatibility and blood compatibility, simultaneously the most again can degraded by body fluid, the metal ion of dissolution can be absorbed promotion osteogenesis by organism or metabolism is got rid of external, can be applicable to the preparation of medical implant.
Description
Technical field
The present invention relates to a kind of Zn-Ca system kirsite and preparation method and application, be specifically related to a kind of Zn-Ca system zinc
Alloy and preparation method thereof with preparation can application in degraded by body fluid medical implant, belong to medical metal material and prepare
Technical field.
Background technology
Be currently used for clinic bio-medical material mainly have biomedical metallic material, inorganic material, macromolecular material,
Composite and biomimetic material etc..Medical metal material, compared with macromolecular material and ceramic material, has higher strong
Degree, toughness and processing characteristics, be therefore most widely used.As: 316L, 317L, 304V rustless steel, Co-Cr-Mo
Alloy, pure titanium, Ti-6Al-4V, TiNi alloy etc..These materials non-degradable in human body, for permanent implanted,
When after implant the completing the term of service in human body, it is necessary to taken out by second operation, thus bring to patient unnecessary
Physiology misery and financial burden.
Along with medical science and the development of material science, the interim material being on active service is needed for some, such as stitching thread, fracture admittedly
Determining plate, intravascular stent, biliary tract rack etc., the material that it is desirable to implant simply plays the effect of temporarily replacement,
And along with tissue or the regeneration of organ gradually degraded and absorbed, reduce the material long-term shadow to body with maximum limit
Ring.Owing to Biodegradable material is easily gradually degraded with the medium interaction such as body fluid the most in vivo, it decomposes product
Thing with metabolism, and finally can excrete, it is not necessary to second operation takes out, thus is increasingly subject to people's attention,
Become forward position and the study hotspot of current international bio Material Field.
The most clinical conventional Biodegradable material is mainly biodegradable polymer and biodegradable pottery
Porcelain.Though biodegradable polymer can be absorbed by the body completely, but intensity is low, is difficult to provide structure to support
Function；The shortcoming of biodegradable ceramic is poor toughness, it is impossible to compatible deformation.
In recent years, degradable biological medical magnesium alloy material becomes one of study hotspot, develops a series of biological doctor
With degradable magnesium alloy, such as AZ31, WE43, Mg-Ca etc., although magnesium alloy has tempting as biomaterial
Application prospect, but research finds magnesium alloy, and to there is corrosion rate too fast, before histoorgan the most fully heals,
Implant the most quickly can lose its mechanical integrity, thus is necessary that developing novel degradable alloy has met clinical need
Ask.
Identical with magnesium and magnesium alloy, metallic zinc and alloy thereof are used frequently as corruption owing to chemical property is active, be prone to corrosion
The anode material being sacrificed in erosion protection.But compared with magnesium, metallic zinc and alloy thereof have higher corrosion potential, because of
And compare metallic zinc and alloy corrosion speed thereof for magnesium alloy and slow down, thus more conform to clinical demand, it is expected to development
Become new bio medical degradable embedded material and device.
Human normal zinc content is 2-3 gram.Zinc is the main component of internal tens of kinds of enzymes.Zinc is distributed in overwhelming majority device
Official is with tissue, and wherein liver, muscle and bone content are higher.Though zinc is trace element in human body, but effect
The most very large.There is the title of " spark of life plug ".(1) zinc is relevant with various bone matrix synzyme, and it can be joined
With bone formation and bone remoulding.When zinc deficiency, the activity decrease of multiple zinc enzyme in bone, the growth of bone is suppressed；
(2) zinc is biomembranous key components, and it is maintaining more than 2000 kind of transcription factor and the structure of more than 300 kind of enzyme
With function has important function；(3) zinc can quickly enter endotheliocyte, maintains the integrity of endotheliocyte, fall
Low blood vessel is to atherosclerotic susceptibility；(4) zinc can with protecting myocardial cell avoid Acute oxidative stress and the heart
The inflammatory reaction that muscle injury causes；(5) zinc can play an active part in nucleic acid-protein synthesis, accelerated wound healing；(6) this
Outward, zinc is also closely related with internal various cellular metabolism effects, such as carbohydrate metabolism, lipid metabolism with anti-ageing wait for a long time.Zinc lacks
Weary meeting cause arteriosclerosis, arrhythmia and exhaustion, brain function deformity, hypoimmunity, dysentery, inappetence,
Growth slows down, alopecia, nyctalopia, prostate hyperplasia, male reproductive function go down, anemia etc..Adult often supplements day by day
15-25mg zinc.
Calcium is a kind of essential element, is also the highest metallic element of content in human body.In the case of Zheng Chang in adult body
Calcium content is about 1000-1250g, and the most about 99% is present in skeleton and tooth, mainly with the shape of hydroxyapatite crystal
Formula exists, and maintains bone and tooth to have hard structure and support.The calcium of the most about 1% is often with free or combine
Ionic condition is present in the outer liquid of soft tissue cells and blood, for miscible calcium pool.Miscible calcium pool maintains with the calcium in skeleton
Dynamic equilibrium, i.e. calcium in bone constantly discharges entrance miscible calcium pool from osteoclast, it is ensured that calcium plasma concentration
Maintain constant；And the calcium in miscible calcium pool is constantly deposited in bone, so that the calcium in skeleton is constantly supplemented
Update, be bone and update.Calcium plays an important role in the various physiology of body and biochemical process.(1) cell is maintained
Normal physiological condition.Intracellular calcium ion is that cell is to stimulating aitiogenic medium.Calcium and receptor calcium etc. are adjusted jointly
The many important physiological functions of joint body, movable including skeletal muscle and the contraction of cardiac muscle, smooth muscle and nonmuscle cells and
The maintenance of neural excitation.The conduction of neural, the excitement of muscle and neural impulse is played an important role by calcium ion.During calcium deficiency
Human body there will be the symptom such as nerve block and dystonia.Calcium ion is to the adhesion of cell, cell membrane function
Maintenance plays an important role.Cell membrane is the barrier of cellular content, and the most various required nutrient substance and oxygen enter
The carrier of cell.The calcium ion of normal contents can guarantee that cell membrane successfully arrives nutrient substance " pump " intracellular.(2)
Reduce blood capillary and membrane passage, prevent from oozing out, control inflammation and edema；(3) blood clotting process is participated in,
Labile factor I is i.e. Ca2+, during calcium deficiency, blood clotting generation obstacle, human body there will be gingival hemorrhage, subcutaneous hemorrhage point,
The symptoms such as Irregular uterine bleeding, menorrhagia, hematuria, hematemesis；(4) internal many enzyme systems are participated in (such as: ATP
Enzyme, succinic acid deaminase, lipase and protease etc.) activation；(5) to the macromole participating in cellular metabolism
Synthesis, the enzyme changed have regulation effect；(6) calcium ion has decisive role to the secretion of human endocrine glandular hormone,
To maintain circulate, breathe, digest, urinary system, nerve, endocrine, the system organ such as reproduction function most important.
(7) functions such as body fluid acid-base balance are maintained.Calcium deficiency can cause osteoporosis, osteomalacia, neuroleptic, twitches, solidifying
The diseases such as blood mechanism is poor, waist and leg ache.Adult's daily requirement supplements 600-1000mg calcium.
Also there is no at present both at home and abroad document and the synthesis of patent report Zn-Ca system alloy and performance, and propose Zn-Ca
It is that alloy is used as degradable biological medical materials'use.
Summary of the invention
It is an object of the invention to provide a kind of Zn-Ca system kirsite and preparation method and application, be specifically related to one
Zn-Ca system kirsite and preparation method thereof can application in degraded by body fluid medical implant with in preparation.Prepared by the present invention
Kirsite excellent in mechanical performance, it is possible to permanently effective support force is provided in vivo, have excellence cell compatibility,
Blood compatibility and tissue, the organ compatibility, can be used for the preparation that bio-medical is implanted.
The Zn-Ca system kirsite that the present invention provides, including Zn and Ca；
By weight percentage, in described kirsite, the mass percent of Ca is 0～30%, but does not include 0.
Also including trace element in above-mentioned kirsite, described trace element is silicon, phosphorus, lithium, silver, stannum and rare earth element
In at least one；
In described kirsite, the weight/mass percentage composition of described trace element is 0～3%, but does not include 0.
The surface of above-mentioned kirsite also can be coated with degradable macromolecule coating, ceramic coating or medication coat；
The thickness of described degradable macromolecule coating, described ceramic coating and described medication coat can be all 0.01～5mm.
The material of preparing of described degradable macromolecule coating can be following 1) and 2) at least one:
1) polycaprolactone (PCL), polylactic acid (PLA), polyglycolic acid (PGA), PLLA (PLLA),
Polybutylcyanoacrylate (PACA), condensing model, poly phosphazene, poly-para-dioxane ketone, poly-butyric ester and
In poly-hydroxyl valerate any one；
2) polylactic acid (PLA), polycaprolactone (PCL), polyglycolic acid (PGA), PLLA (PLLA),
Two or more copolymer any in polybutylcyanoacrylate (PACA) and poly-para-dioxane ketone；
The material of preparing of described ceramic coating can be at least in hydroxyapatite, tricalcium phosphate or phosphoric acid oxygen four calcium
Kind；
Described medication coat can be rapamycin and derivant coating, paclitaxel coating, everolimus coating, western sieve
Do not take charge of at least one in coating, mitomycin coating and antimicrobial coating.
The present invention provide Zn-Ca system kirsite be specially following 1)-5) and in any one, be weight percentage:
1) it is made up of the Ca of 95～the Zn of 99% and 1%～5%；
2) it is made up of the Zn of 99% and the Ca of 1%；
3) it is made up of the Zn of 95% and the Ca of 5%；
4) it is made up of the Li of the Zn of 98.5%, the Ca of 1% and 0.5%；
5) it is made up of the Y of the Zn of 98.5%, the Ca of 1% and 0.5%.
Zn-Ca system kirsite prepared by the present invention is compact texture or loose structure, possesses good histocompatibility,
It it is a kind of biological and medicinal implant material reliably.
Invention further provides the preparation method of above-mentioned kirsite, comprise the steps:
By described Zn, described Ca and described trace element according to following 1) and 2) in any one mode mix
Obtain mixture；
1) Zn and Ca；
2) Zn, Ca and trace element；
Described kirsite is i.e. obtained according to following step a) or b)；
A) at CO2And SF6Under atmosphere protection, described mixture is carried out melting, the most i.e. obtains described kirsite；
B) at CO2And SF6Under atmosphere protection, described mixture is carried out melting, can drop described in coating after cooling
Solve polymeric coating layer, described ceramic coating or described medication coat and i.e. obtain described kirsite.
In said method, the temperature of described melting can be 700～850 DEG C, concretely 800 DEG C.
Said method also includes the step that described kirsite carries out machining；
Described machining can be at least one in rolling, forging, rapid solidification and extruding.
Described rolling includes carrying out successively hot rolling and finish rolling, and described hot rolling can be carried out at 200～300 DEG C, described finish rolling
Can carry out at 150～250 DEG C, the thickness after the rolling of described kirsite can be 1～2mm；Described hot rolling specifically can be
Carrying out at 250 DEG C, described finish rolling specifically can be carried out at 250 DEG C, and the thickness after the rolling of described kirsite is concretely
1.5mm。
Described forging includes carrying out described kirsite under conditions of 150～200 DEG C being incubated and at 200～300 DEG C
Under the conditions of carry out the step forged, the time of described insulation is 3～50 hours, and the speed of described forging is not less than
350mm/s。
The temperature of described extruding can be 150～250 DEG C, concretely 200；Extrusion ratio can be 10～70, concretely
20。
Described rapid solidification comprises the steps: under Ar gas shielded, uses fine vacuum fast quenching system to prepare fast rapid hardening
Gu strip, then described strip is broken into powder, finally under conditions of 200～350 DEG C, vacuum hotpressing 1～24
h。
Described fine vacuum fast quenching system be provided that feeding quantity 2～8g, induction heating power be 3～7kW, nozzle
With roller spacing be 0.80mm, expulsion pressure be 0.05～0.2MPa, roller speed is 500～3000r/min and nozzle is narrow
Stitch a size of 1film × 8mm × 6mm.
Present invention also offers the preparation method of a kind of kirsite, comprise the steps: described Zn, described Ca and
Described trace element is according to following 1) and 2) in any one mode carry out being mixed to get mixture；
1) Zn and Ca；
2) Zn, Ca and trace element；
Described kirsite is i.e. obtained according to following step a) or b)；
A) at CO2And SF6Under atmosphere protection, described mixture is sintered, the most i.e. obtains described kirsite；
B) at CO2And SF6Under atmosphere protection, described mixture is sintered, can drop described in coating after cooling
Solve polymeric coating layer, described ceramic coating or described medication coat and i.e. obtain described kirsite；
Described it is sintered to any one method following: element powders mixed-sintering method, prealloy powder sintering process and self-propagating are high
Temperature synthetic method.
Described element powders mixed-sintering method is by the described raw material mix homogeneously preparing loose structure Zn-Ca system alloy,
Be pressed into base, then in vacuum sintering furnace, with 2～4 DEG C/min be warming up at a slow speed 100～200 DEG C followed by with
30 DEG C/min is rapidly heated to 200～300 DEG C of sintering, then lowers the temperature, and obtains into the Zn-Ca system alloy of loose structure；
Described prealloy powder sintering process is to carry out high energy after the described raw material mixing preparing loose structure Zn-Ca system alloy
Ball milling, is then pressed into type, carries out heat treatment 10～20 hours at 250～350 DEG C, obtains the Zn-Ca of loose structure
It it is alloy；
Described self-propagating high-temperature synthesis is to be pressed into base after preparing the raw material mixing of loose structure Zn-Ca system alloy,
Under inert gas shielding, pressure is 1 × 103～1 × 105Pa, temperature is at 250～350 DEG C, then Zn-Ca system is closed
Gold blank is lighted and is carried out SHS process, obtains the Zn-Ca system alloy of loose structure.
For adapting to different clinical demand, above two is prepared the method for kirsite and is also included the step of applying coating.
The method of described coating Biodegradable high-molecular coating is that described kirsite is carried out pickling, then by it in institute
The material of preparing stating Biodegradable high molecular coating is dissolved in colloid prepared by trichloroethane dip-coating 10～after 30 minutes, even
Speed pull-out is centrifuged processing the kirsite obtaining being coated with Biodegradable high-molecular coating；
The method of described coated ceramic coating can be to appoint in plasma spraying, electrophoretic deposition, anodic oxidation and Hydrothermal Synthesis
A kind of；
The main gas of plasma gas used by described plasma spray coating is Ar, and flow is 30～100scfh, plasma gas
Secondary gas is H2, flow is 5～20scfh, and spraying current is 400～800A, and spray voltage is 40～80V, spray distance
It is 100～500mm；
The method of described electro-deposition degradable ceramic coating be with kirsite for negative electrode calcic, microcosmic salt electrolyte in,
Electric current density is 2～10mA/cm2, after processing 10～60min, cleaning-drying obtains described kirsite；
The method that described anodic oxidation and Hydrothermal Synthesis combine is containing 0.01～0.5mol/L β-sweet by described kirsite
In the electrolyte of oleophosphoric acid sodium and 0.1～2mol/L calcium acetate, under 200～500V, aoxidize 10～30min, then by institute
State kirsite at 200～400 DEG C, process 1～4h.
The method of described coated medicament coating is physics and chemical method；
Described physical method coating process mainly uses immersion, spraying method；Described chemical method mainly uses electrochemistry
Principle is electroplated；
Described immersion process is for being configured to solution, specifically by active medicine with controlled release carrier (or individually active medicine)
Concentration can be different because solution viscosity is different with required drug dose, are then soaked in solution by described medical implant,
It is then passed through the last handling process of necessity, such as steps such as crosslinking, dry, solidifications, makes medication coat；
Described spraying method is for being configured to solution, then by active medicine with controlled release carrier (or individually active medicine)
By sprinkling instrument or special spraying equipment solution is spread evenly across described medical embedded surface, drying, solid
Medication coat is i.e. made after the post-processing steps such as change；
Described chemical method is to utilize active medicine and (or) controlled release carrier on the electrode by described medical embedded making
There is electro-redox reaction, make described medical embedded surface be formed stable by the medication coat being chemically bonded.
The present invention utilizes Zn and Zn alloy to be prone to the feature of corrosion, have selected Zn-Ca system alloy as degradability material
It is applied to medical implant.The mechanical property of the Zn-Ca system alloy of the present invention meet medical implant material intensity and
The requirement of toughness, simultaneously the most again can vivo degradation, medical macromolecular materials intensity i.e. can be overcome low and 316L rustless steel,
The nondegradable weakness of conventional medical metal material such as titanium or titanium alloy, can overcome again magnesium and magnesium alloy degradation rate mistake
The defect that the mechanical property that causes soon implanting is lost, accomplishes with " can biological corrosion degradation characteristic " and " suitably
Corrosion rate ensure to provide permanently effective mechanical support " double grading.
The Zn-Ca system kirsite that the present invention provides can be used for preparing following medical implant: support, bone are implanted in treatment
Repair apparatus, gear division repairs apparatus；
It can be intravascular stent, esophageal stents appear, intestinal stent, trachea bracket, biliary tract rack that support is implanted in described treatment
Or urethra rack；
Described Bone Defect Repari apparatus can be bone tissue restoration support, bone fracture device, fixing line, fixed screw, fixing rivet,
Fixing pin, splenial bone plate, intramedullary needle or synthetism set；
It can be dental pulp pin or tooth filler that described gear division repairs apparatus.
Present invention have the advantage that
(1) mechanical property of the Zn-Ca system alloy that prepared by the present invention meets intensity and the toughness of medical implant material
Requirement, simultaneously the most again can vivo degradation, there is " can biological corrosion degradation characteristic " and " suitable corrosion rate guarantee
Permanently effective mechanical support is provided " double grading.
(2) Zn-Ca system of the present invention alloy is when degradable medical implant, can send out in implanting a period of time
Wave the high intensity feature of its metal material, complete the function of implant (as induction new bone tissue is formed or supports narrow
Blood vessel), again can human lesion position carry out self repair while as " allosome " gradually by human body corrosion degradation,
Quantity and volume gradually decrease, and the metal ion of dissolution can be absorbed promotion osteogenesis by organism or body is got rid of in metabolism
Outward, the finally degradable disappearance of metal material implant when human body terminates self to repair.
(3) present invention provide can the medical implant of degraded by body fluid nontoxic, possess good histocompatibility and blood
Liquid phase capacitive.
Accompanying drawing explanation
Fig. 1 is the photo of the Zn-Ca alloy cast ingot of embodiment 1 preparation.
Fig. 2 is the photo of the Zn-Ca sheet alloy of embodiment 2 preparation.
Fig. 3 is the photo of the Zn-Ca alloy bar material of embodiment 3 preparation.
Fig. 4 is the photo of the Zn-Ca system alloy tensile sample prepared according to testing standard.
Fig. 5 is the stress strain curve of Zn-Ca-Li alloy.
Fig. 6 is that after Zn-Ca alloy soaks 2 weeks in simulated body fluid, the SEM photograph (a) under different amplification is low
Times；(b) high power.
Fig. 7 is Zn-Ca alloy electrochemical corrosion curve in simulated body fluid.
Fig. 8 is Zn-Ca alloy platelet adhesion SEM photograph.
Fig. 9 is Zn-Ca alloy light microscopic photo (a) matched group to cytosis；(b) Zn-Ca alloy.
Figure 10 be Zn-Ca alloy to the cell after cytosis different time relative to the rate of increase (* p < 0.05,
**p<0.01)。
Figure 11 is that Zn-Ca alloy implants the X-ray of different time in Mice Body and corresponding comparison figure.
Figure 12 is mico-CT figure and the comparison figure that different time in Mice Body implanted by Zn-Ca alloy.
Figure 13 is histology's fluorescence staining photo that Zn-Ca alloy implants in Mice Body after 2 months.
Detailed description of the invention
Experimental technique used in following embodiment if no special instructions, is conventional method.
Material used in following embodiment, reagent etc., if no special instructions, the most commercially obtain.
Percentage composition used in following embodiment, if no special instructions, is weight/mass percentage composition.
Embodiment 1, preparation as cast condition Zn-Ca system alloy
With pure Zn (99.99wt.%), pure Ca (99.95wt.%) (purchased from Beijing Chinese incense cedar woods non-ferrous metal technological development
Center) as raw material, mix by different mass ratioes (mass ratio of Zn with Ca is respectively 99:1 and 95:5),
At CO2+SF6Under atmosphere protection, 800 DEG C of meltings, after raw material fully melts, after insulation 10min, recirculated water is fast
Quickly cooling but, prepares Zn-Ca system alloy pig (photo is as shown in Figure 1), and wherein, Zn-1Ca represents the matter of Zn Yu Ca
Amount represents that than for 99:1, Zn-5Ca the mass ratio of Zn Yu Ca is 95:5.
State Zn-Ca system alloy is rolled in embodiment 2, preparation
The step being first according in embodiment 1 prepares the Zn-Ca system alloy pig of as cast condition；Then obtain above-mentioned
Zn-Ca system alloy pig carries out hot rolling, first preheats ingot casting at 250 DEG C, then uses hot rolling mode, at reciprocation type milling train
Middle repeat-rolling, hot-rolled temperature is at 250 DEG C, finally in finishing mill, is rolled down to 1.5mm at 250 DEG C.
Fig. 2 is the photo rolling state Zn-Ca system alloy (Zn-1Ca) that the present embodiment obtains.
Embodiment 3, prepare As-extruded Zn-Ca system alloy
According to following 1) or 2) step be prepared:
1) step being first according in embodiment 1 prepares Zn-Ca system alloy pig (Zn-1Ca) of as cast condition, uses
The mode of extruding prepares Zn-Ca system alloy bar material (Zn-1Ca), uses radial compression, and extrusion temperature is 200 DEG C, squeezes
Pressure ratio is 20, prepares Zn-Ca system alloy bar material (Zn-1Ca) of a diameter of 10mm.
2) step being first according in embodiment 1 prepares the Zn-Ca system alloy cast ingot of as cast condition, uses fine vacuum fast
The system of quenching prepares rapid solidification Zn-Ca alloy thin band, and concrete grammar is: use height in described ratio after being mixed by raw material
Vacuum quick quenching system prepares rapid solidification Zn-Ca system strip, parameter be feeding quantity 2～8g, induction heating power 3～7kW,
Nozzle and roller spacing 0.80mm, expulsion pressure 0.1MPa, roller speed 2000r/mln and nozzle slot size 1film
×8mm×6mm.Then being pressed into base after being pulverized by strip, hot pressing condition is 200～350 DEG C, vacuum hotpressing 1～24h.
The mode using extruding prepares Zn-Ca system alloy bar material, uses radial compression, and extrusion temperature is 200 DEG C, extrusion ratio
It is 20, prepares Zn-Ca system alloy bar material (Zn-1Ca) (photo is as shown in Figure 3) of a diameter of 10mm.
Embodiment 4, the alloy mechanical property test of Zn-Ca system
The Zn-Ca system alloy will prepared according to the method for embodiment 1-3, respectively according to ASTM-E8-04 extension test
Standard prepares drawn samples (as shown in Figure 4), successively through 400#, 800#, 1200# and 2000#SiC sand paper series
Sanding and polishing.In acetone, dehydrated alcohol and deionized water after difference ultrasonic cleaning 15min, use universal material power
Learning testing machine and at room temperature carry out tension test, draw speed is 1mm/min.
Fig. 5 is Zn-Ca system alloy (as cast condition Zn-1Ca-0.5Li, its preparation method and embodiment 1 prepared by the present invention
The preparation method of middle as cast condition Zn-Ca system alloy is identical, and wherein the mass ratio of Zn, Ca and Li is 98.5:1:0.5)
Stress strain curve, it can be seen that the tensile strength of as cast condition Zn-1Ca-0.5Li alloy is 168.37MPa, surrender is strong
Degree is 95.85MPa, and elongation percentage is 1.372%.
The room temperature tensile properties of each sample of Zn-Ca system alloy is as shown in table 1, wherein, and the preparation method of Zn-1Ca-0.5Y
Identical with the preparation method rolling state Zn-Ca system alloy in embodiment 2, the mass ratio of Zn, Ca and Y is 98.5:1:
0.5.As shown in Table 1, with the increase of Ca content, alloy becomes fragile, and intensity and elongation percentage are decreased obviously.Relative to casting
State alloy, rolls state alloy and the yield strength of As-extruded alloy and hot strength is all significantly improved, meanwhile,
Elongation percentage is increased considerably, and shows that material mechanical property after process of deformation is optimized further.
Table 1.Zn-Ca alloy tensile experimental result
| Specimen coding | Tensile strength/MPa | Yield strength/MPa | Elongation percentage/% |
| Zn-1Ca ingot casting | 162.42 | 122.35 | 1.835 |
| Zn-5Ca ingot casting | 60.35 | 43.26 | 0.463 |
| Zn-1Ca-0.5Y rolls plate | 172.83 | 128.47 | 1.407 |
| Zn-1Ca rolls plate | 264.13 | 210.42 | 13.727 |
| Zn-1Ca bar | 254.53 | 200.27 | 7.404 |
Embodiment 5, Zn-Ca alloy corrosion performance are tested
By in embodiment 2 through rolling Zn-Ca alloy, by line cut preparation 10 × 10 × 1.5mm Zn-Ca alloy
Coupons, successively through 400#, 800#, 1200# and 2000#SiC sand paper series sanding and polishing.In acetone, anhydrous second
In alcohol and deionized water after difference ultrasonic cleaning 15min, it is dried at 25 DEG C.It is immersed in Hank ' s simulated body fluid afterwards
(NaCl 8.0g,CaCl20.14g,KCl 0.4g,NaHCO30.35g, glucose 1.0g, MgCl2·6H2O 0.1g,
Na2HPO4·2H2O 0.06g,KH2PO40.06g,MgSO4·7H2O 0.06g is dissolved in 1L deionized water) in,
Taking out after soaking different time interval, observe sample surfaces, Fig. 6 is that Zn-Ca alloy (Zn-1Ca) is at Hank ' s
Stereoscan photograph under different amplification after soaking in simulated body fluid two weeks, (a) is low power, and (b) is high power.
Result shows that Zn-Ca alloy surface keeps complete and deposition great amount of hydroxy group apatite mineral, shows that Zn-Ca alloy is in fall
The deposition of bone mineral can be induced while solution, thus the reparation of osseous tissue can be promoted in vivo.
Fig. 7 is the Zn-Ca alloy (Zn-1Ca) electrochemical corrosion polarization curve in Hank ' s solution, from Fig. 7
In can obtain, the corrosion rate of Zn-1Ca alloy is 0.16mm/.
Embodiment 6, Zn-Ca alloy blood compatibility are tested
By embodiment 2 through the Zn-Ca alloy of rolling, cut preparation 10 × 10 × 1.5mm Zn-Ca alloy sample by line
Sheet, through 400#, 800#, 1200# and 2000#SiC sand paper series sanding and polishing.Acetone, dehydrated alcohol and go from
In sub-water after difference ultrasonic cleaning 15min, it is dried at 25 DEG C.Gather fresh blood with healthy volunteer, in being placed in
Preserve as the anticoagulant tube of anticoagulant containing 3.8wt.% sodium citrate.The dilution proportion of 4:5 is pressed with 0.9% normal saline
Make dilute blood sample.Sample is immersed in 10mL normal saline, 37 ± 0.5 DEG C of insulation 30min, adds 0.2mL
Dilute blood sample, 37 ± 0.5 DEG C of insulation 60min.10mL normal saline is used to go as negative control group, 10mL
Ionized water is as positive controls.It is centrifuged 5 minutes through 3000rpm, takes supernatant Unic-7200 UV, visible light and divide
Light photometer 545nm measures absorbance OD value, arranges three groups of Duplicate Samples to carry out statistical analysis.
Hemolysis rate is calculated by below equation:
Hemolysis rate=(experimental group OD value-feminine gender group OD value)/(positive group OD value-feminine gender group OD value) × 100%.
After collecting whole blood, 1000rpm is centrifuged 10min and prepares platelet rich plasma.Platelet rich plasma is dripped in sample
Surface, 37 ± 0.5 DEG C of insulation 60min, often 3 Duplicate Samples of group.Take out sample, PBS (pH value is 7.2)
Rinse 3 times and do not stick platelet to remove.Fix blood platelet method is: it is 2.5% that every hole adds 500 μ L concentration
Glutaraldehyde fixative, fixes 60 minutes under room temperature, then by fixative sucking-off, use PBS 3 times, use
Concentration is 50%, 60%, 70%, 80%, 90%, 95%, and 100% ethanol carries out serial dehydration, each concentration ladder
Degree dehydration 10 minutes, uses scanning electron microscope (S-4800, Hitachi, Japan) to observe platelet after vacuum drying
Sticking quantity and form, each sample randomly chooses 6 regions and carries out platelet count and statistical analysis.
Test result indicate that, the hemolysis rate of Zn-Ca alloy (Zn-1Ca) is 0.3%, is far smaller than Clinical practice requirement
Secure threshold 5%, show good erythrocyte and the hemoglobin compatibility.
Fig. 8 is the platelet pattern photo of Zn-Ca alloy (Zn-1Ca) surface adhesion, it can be seen that Zn-Ca
The platelet counts that alloy surface adheres to is rare, and in smooth spherical shape, does not has tail to flicker and pseudopodium stretches out, not
It is activated, shows the anticoagulation function of excellence.
Embodiment 7, can the preparation of degraded by body fluid medical Zn-Ca implant and cell compatibility experiment thereof
Prepare Zn-Ca alloy by the method for embodiment 1-3,6 pieces of length and widths, thickness are respectively 10,10,1.5mm
The Zn-Ca alloy block (Zn-1Ca, as cast condition and roll state) of above-mentioned preparation through gamma-rays sterilization, be placed in aseptic training
Supporting in bottle, long-pending by specimen surface and MEM cell culture medium volume ratio is 125cm2The ratio of/mL adds MEM
Cell culture medium, be placed in 37 DEG C, 95% relative humidity, 5%CO272h in incubator, obtains the extraction of Zn-Ca alloy
Liquid stock solution, seals, and 4 DEG C of Refrigerator stores are standby.
Lixiviating solution is observed with cell inoculated and cultured and result: by MG63 cell (the Guangzhou limited public affairs of Ji Niou biotechnology
Department) recover, pass on after, be suspended in MEM cell culture medium, be inoculated on 96 well culture plates, negative control group
Adding MEM cell culture medium, Zn-Ca alloy lixiviating solution stock solution group adds Zn-Ca alloy lixiviating solution obtained above
Stock solution, making final cell concentration is 5 × 104/mL.It is placed in 37 DEG C, 5%CO2Incubator is cultivated, takes out after 5 days
Culture plate, observes the form (as shown in Figure 9) of living cells under inverted phase contrast microscope.Result shows: right with feminine gender
Comparing according to group, cell quantity is in the same order of magnitude, and pattern is rendered as the fusiformis convergence growth of healthy stretching, extension, explanation
Zn-Ca alloy has the cell compatibility of excellence.
Figure 10 be MG63 osteocyte cultivate after different time in Zn-Ca system alloy (Zn-1Ca) lixiviating solution thin
Born of the same parents are relative to rate of increase experimental result, it can be seen from fig. 10 that add calcium constituent can be effectively improved the increasing of osteocyte
Grow activity, promote bone cell proliferation.
Embodiment 8, can the preparation of degraded by body fluid medical Zn-Ca implant and zoopery thereof
By lathe process Zn-Ca alloy intramedullary needle, the intramedullary needle dimensional parameters of preparation is: length: 5mm；Diameter:
1mm.Take the Zn-Ca alloy implantation intramedullary needle 10 that said method prepares, implant respectively in 10 mouse femurs.
Carrying out X-ray observation (Figure 11) behind art one week after, two weeks, three weeks, surrounding, six weeks and eight weeks, micro-CT observes
(Figure 12) with tissue slice Fluirescence observation (Figure 13), result shows, operation one week after, two weeks, surrounding and eight weeks,
10 mices the most do not find that implant causes the foreign body reactions such as surrounding tissue inflammation, and intramedullary needle keeps intact form, plants
After entering two weeks, it was observed that freshman bone tissue's (shown in arrow) around implant, and freshman bone tissue is thick around implant
Degree, more than matched group, shows that Zn-Ca alloy medical implant can promote the generation of osseous tissue, shortens the wounds such as fracture
Repair time.
Claims (11)
1. a Zn-Ca system kirsite, it is characterised in that: described Zn-Ca system kirsite is following 1)-2) and in appoint
One, by weight percentage:
1) it is made up of the Li of the Zn of 98.5%, the Ca of 1% and 0.5%；
2) it is made up of the Y of the Zn of 98.5%, the Ca of 1% and 0.5%.
Kirsite the most according to claim 1, it is characterised in that: the surface-coated of described kirsite has degradable
Polymeric coating layer, ceramic coating or medication coat；
The thickness of described degradable macromolecule coating, described ceramic coating and described medication coat is 0.01～5mm.
3. a preparation method for kirsite described in claim 1, comprises the steps: the group in claim 1
Divide and carry out being mixed to get mixture；
The most i.e. obtain described kirsite；
A) at CO2And SF6Under atmosphere protection, described mixture is carried out melting, the most i.e. obtains described kirsite；
The temperature of described melting is 700～850 DEG C.
4. a preparation method for kirsite described in claim 2, comprises the steps: the group in claim 1
Divide and carry out being mixed to get mixture；
The most i.e. obtain described kirsite；
B) at CO2And SF6Under atmosphere protection, described mixture is carried out melting, coats described degradable after cooling
Polymeric coating layer, described ceramic coating or described medication coat i.e. obtain described kirsite；
The temperature of described melting is 700～850 DEG C.
5. according to the preparation method of kirsite described in claim 3 or 4, it is characterised in that: described method also include by
Described kirsite carries out the step of machining；
Described machining is at least one in rolling, forging, rapid solidification and extruding.
The preparation method of kirsite the most according to claim 5, it is characterised in that:
Described rolling includes carrying out successively hot rolling and finish rolling, and described hot rolling is carried out at 200～300 DEG C, and described finish rolling exists
Carrying out at 150～250 DEG C, described kirsite is rolled 1～3mm；
Described forging includes carrying out described kirsite under conditions of 150～200 DEG C being incubated and at 200～300 DEG C
Under the conditions of carry out the step forged, the time of described insulation is 3～50 hours, and the speed of described forging is not less than
350mm/s；
The temperature of described extruding is 150～250 DEG C, and extrusion ratio is 10～70；
Described rapid solidification comprises the steps: under Ar gas shielded, uses fine vacuum fast quenching system to prepare rapid solidification
Strip, is then broken into powder by described strip, finally under conditions of 200～350 DEG C, and vacuum hotpressing 1～24h.
7. a preparation method for kirsite described in claim 1, comprises the steps: the component of claim 1
Carry out being mixed to get mixture；
The most i.e. obtain described kirsite；
A) at CO2And SF6Under atmosphere protection, described mixture is sintered, the most i.e. obtains described kirsite；
Described it is sintered to any one method following: element powders mixed-sintering method, prealloy powder sintering process and self-propagating are high
Temperature synthetic method.
8. a preparation method for kirsite described in claim 2, comprises the steps: the component of claim 1
Carry out being mixed to get mixture；
The most i.e. obtain described kirsite；
B) at CO2And SF6Under atmosphere protection, described mixture is sintered, coats described degradable after cooling
Polymeric coating layer, described ceramic coating or described medication coat i.e. obtain described kirsite；
Described it is sintered to any one method following: element powders mixed-sintering method, prealloy powder sintering process and self-propagating are high
Temperature synthetic method.
9. kirsite described in claim 1 can application in degraded by body fluid medical implant in preparation.
Application the most according to claim 9, it is characterised in that: described application shows as following 1)-4) in
Any one:
1) described kirsite promotes the reparation of osseous tissue；
2) anticoagulation function of described kirsite；
3) cell compatibility of described kirsite；
4) described kirsite promotes the generation of osseous tissue.
11. 1 kinds can degraded by body fluid medical implant, it is prepared by kirsite described in claim 1.
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| DE102015101264A1 (en) * | 2015-01-28 | 2016-07-28 | Limedion GmbH | Biodegradable alloy and its production and use, in particular for the production of stents and other implants |
| CN104651665B (en) * | 2015-03-13 | 2017-11-03 | 西安爱德万思医疗科技有限公司 | A kind of tough Zn-Fe-Li systems kirsite of the degradable corrosion-proof and high-strength of human body and its application |
| CN104689369B (en) * | 2015-03-13 | 2017-06-30 | 西安爱德万思医疗科技有限公司 | A kind of tough Zn-Fe systems kirsite of the degradable corrosion-proof and high-strength of human body and its application |
| CN104689378B (en) * | 2015-03-13 | 2017-04-05 | 西安爱德万思医疗科技有限公司 | A kind of tough Zn-Fe-X systems kirsite of the degradable corrosion-proof and high-strength of human body and its application |
| CN106236235A (en) * | 2015-05-03 | 2016-12-21 | 刘乐 | A kind of medical apparatus and instruments Minimally Invasive Surgery blade plate |
| CN106609327B (en) * | 2015-10-21 | 2018-05-18 | 北京大学 | A kind of Zn-HAP systems kirsite and preparation method and application |
| CN105838924B (en) * | 2016-04-07 | 2018-04-06 | 南京云开合金有限公司 | A kind of hot dip zinc calcium intermediate alloy, its preparation method and its application |
| CN107456610B (en) * | 2016-06-02 | 2020-02-14 | 北京大学 | Zn-Ag series zinc alloy and preparation method and application thereof |
| CN106319287A (en) * | 2016-08-25 | 2017-01-11 | 上海交通大学 | Biodegradable medical Zn-Li-X series alloy material and preparation method and application |
| CN109200342A (en) * | 2017-07-06 | 2019-01-15 | 先健科技(深圳)有限公司 | Implantable device |
| CN109966563B (en) * | 2017-12-28 | 2021-08-03 | 元心科技(深圳)有限公司 | Implanted medicine carrying device |
| CN110512117B (en) * | 2019-09-27 | 2022-05-13 | 石家庄新日锌业有限公司 | Medical zinc alloy material and preparation method thereof |
| CN111331128A (en) * | 2020-04-16 | 2020-06-26 | 长沙镁捷新材料科技有限公司 | Method for preparing zinc alloy degradable material by sintering metal powder |
| CN111676390B (en) * | 2020-08-03 | 2022-03-11 | 北京科技大学 | Zn-Ga alloy, preparation method and application thereof |
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