CN106191597A - A kind of novel biodegradable Mg Zn Y antibacterial magnesium alloy of Nd Ag and preparation method thereof - Google Patents

A kind of novel biodegradable Mg Zn Y antibacterial magnesium alloy of Nd Ag and preparation method thereof Download PDF

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CN106191597A
CN106191597A CN201610820508.5A CN201610820508A CN106191597A CN 106191597 A CN106191597 A CN 106191597A CN 201610820508 A CN201610820508 A CN 201610820508A CN 106191597 A CN106191597 A CN 106191597A
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magnesium alloy
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antibacterial
magnesium
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关绍康
李爽
朱世杰
任晨星
常蕾
王俊
王利国
张其美
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Zhengzhou University
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Abstract

A kind of novel biodegradable Mg Zn Y antibacterial magnesium alloy of Nd Ag and preparation method thereof, belong to magnesium alloy bio-medical material preparation field, the described Mg Zn Y antibacterial magnesium alloy of Nd Ag consists of the following components in percentage by weight: Zn:1% 3%, Y:0.2% 1%, Nd:0.2% 1%, Ag:0.05% 1.5%, surplus is Mg.This alloy in this alloy can produce Trace Ag in degradation process+, the infection around implant can be suppressed, reduce postoperative infection rate, reduce the use of antibiotic, reduce medical treatment cost.The Mg Zn Y Nd Ag alloy of the present invention has good mechanical property and decay resistance, is provided simultaneously with the antibacterial functions of excellence.This alloy has good biocompatibility, can meet the demand of different implant, can be used for the bone implant materials such as intravascular stent, hone lamella and nail.

Description

A kind of antibacterial magnesium alloy of novel biodegradable Mg-Zn-Y-Nd-Ag and preparation thereof Method
Technical field
The invention belongs to magnesium alloy bio-medical material preparation field, be specifically related to a kind of novel biodegradable Mg-Zn- Antibacterial magnesium alloy of Y-Nd-Ag and preparation method thereof.
Background technology
Along with the mankind enter the quickening of aging paces, the increasing of wound, the increase of difficult diseases patient and new and high technology Development, the development of bio-medical material seems more and more important.At present, the bio-medical material being applied to clinic is main Including: metal class bio-medical material, organic polymer class bio-medical material, inorganic non-metallic class bio-medical material, with And bio-medical composition prepared by above-mentioned different materials.In all biological and medicinal implant materials, metal material is applied Early, the application and in clinic is the most extensive.
Magnesium is one of material needed for mankind's metabolism, and the content in human body is only second to potassium, sodium, calcium, internal magnesium In the tissues such as 50%～60% is distributed in osseous tissue, and about 25% is distributed in skeletal muscle, and remaining is distributed in liver, heart, one The adult human body of individual quality 70kg is contained within the magnesium of about 1mol.All of metabolic processes in magnesium almost participant's body, it The content of Blood Cholesterol can be reduced, prevent arteriosclerosis, hypertension and myocardial infarction, improve cardiovascular antiviral energy Power.In human body, the magnesium of half is to be stored in osseous tissue with the form of biological magnesium, and magnesium ion can promote the deposition of calcium, is that bone is raw Long indispensable element, the shortage of magnesium can stop bone growth, reduce osteoblast and the activity of osteoclast, and cause sclerotin Fragile.
Magnesium alloy has low-density, high specific strength, high specific stiffness, high elastic modulus, also has excellent machinability Energy.The density of Mg is the least, is 1.74 g/cm3, minimum at all of structural material Midst density, close with the density of human bone. The fracture toughness of magnesium is higher than ceramic biomaterial hydroxyapatite, and its elastic modelling quantity and compressive yield strength are then than other gold Genus embedded material, closer to human bone, after implanting human body as bone fishplate bar, can effectively reduce " stress-shielding effect ".
It is titanium alloy owing to medical equipment and embedded material being applied more, but does not possess because of embedded material anti-every year Bacterium performance and caused high infection rate and mortality rate." the nosocomial infection's preventing and treating promulgated according to World Health Organization (WHO) (WHO) Application manual " in relevant data, the whole world had more than 14,000,000 people and suffered infected misery every day, wherein 60% thin Bacterium infects relevant with the medical apparatus and instruments used.The generation that implant infects is mainly among operative site and operation process.Gold Staphylococcus aureus and staphylococcus epidermidis are the main bacteria causing orthopaedics implantation instrument to infect, and account for 34% and 32% respectively, Other coccus accounts for 13%.
Staphylococcuses etc. can enter in osteoblast, produces " internalization " effect, makes antibiotic be difficult to play a role, and resist A large amount of uses of raw element can make antibacterial produce drug resistance.Therefore, a kind of medical degradable magnesium alloy possessing antibacterial functions is developed Embedded material has great importance.
Research finds, silver is the inorganic antiseptic of a kind of safety non-toxic, has biological safety height, has a broad antifungal spectrum, lasting Property good, do not produce the features such as drug resistance, in all metal ions, the antibiotic property of silver ion is the strongest, the trace release of silver, favorably Bacterial inflammation around suppression implant.Mg-Ag alloy can kill two kinds of encountered pathogenic bacteria staphylococcus aureuses With staphylococcus epidermidis, sterilizing rate is up to more than 90%.
Silver solid solubility in magnesium is up to 15.5%, has higher solution strengthening effect, and silver can be with Refining Mg Alloy Crystal grain, increases substantially the mechanical property of magnesium alloy, and the interpolation of Ag can also significantly improve the age-hardening effect of Mg-Zn alloy Really, Mg-Al-Zn alloy adds the Ag of 0.20% ~ 0.35%, heavy alloyed property indices can be carried.Ag can be complete Entirely it is solid-solubilized in α-Mg, carries heavy alloyed corrosion potential, it is not easy to form the second phase, thus carry heavy alloyed degradation property.
Summary of the invention
The purpose of the present invention aims to the problem that the metal implant material infection rate of current Clinical practice is higher, it is provided that one Plant the antibacterial magnesium alloy of novel biodegradable Mg-Zn-Y-Nd-Ag, provide the preparation method of this alloy simultaneously.
Based on above-mentioned purpose, the present invention adopts the following technical scheme that:
A kind of antibacterial magnesium alloy of novel biodegradable Mg-Zn-Y-Nd-Ag, the antibacterial magnesium alloy of described Mg-Zn-Y-Nd-Ag by with The component composition of lower percentage by weight: Zn:1%-3%, Y (yttrium): 0.2%-1%, Nd (neodymium): 0.2%-1%, Ag:0.05%-1.5%, remaining Amount is Mg.
A kind of method preparing the above-mentioned antibacterial magnesium alloy of novel biodegradable Mg-Zn-Y-Nd-Ag, with high-purity magnesium ingot, height Pure zinc ingot, Mg-Y intermediate alloy, Mg-Nd intermediate alloy and high-purity filamentary silver are that furnace charge melting is made as cast condition Mg-Zn-Y-Nd-Ag and pressed down Bacterium magnesium alloy, Zn in furnace charge, the consumption of Y, Nd is its in the antibacterial magnesium alloy of Mg-Zn-Y-Nd-Ag 1.2-1.3 times of content, Ag Consumption be its in the antibacterial magnesium alloy of Mg-Zn-Y-Nd-Ag 1.1-1.2 times of content.
Preferably, Mg-Y intermediate alloy is Mg-30wt%Y intermediate alloy, and Mg-Nd intermediate alloy is in the middle of Mg-30wt%Nd Alloy, high-purity magnesium ingot, high-purity zinc ingot metal and purity >=99.9% of high-purity filamentary silver.
Concretely comprising the following steps of the above-mentioned antibacterial magnesium alloy preparation method of novel biodegradable Mg-Zn-Y-Nd-Ag: by high-purity Magnesium ingot heats under the protection of protective gas, after high-purity magnesium ingot is completely melt, adds high-purity filamentary silver, temperature is risen to 740 DEG C- 800 DEG C, it is incubated 30min-50min, is subsequently adding Mg-Y intermediate alloy, Mg-Nd intermediate alloy, after insulation 15min-30min, adds Enter high-purity zinc ingot metal, cool the temperature to 680 DEG C-730 DEG C, be incubated 15min-20min, then stir 3min-5min, then take off Slag, casting, the demoulding i.e. prepares the antibacterial magnesium alloy of as cast condition Mg-Zn-Y-Nd-Ag.
Further, protective gas is CO2And SF6Gaseous mixture, wherein, CO2And SF6Volume ratio is 99 1.
Yet further, antibacterial for as cast condition Mg-Zn-Y-Nd-Ag magnesium alloy is carried out Homogenization Treatments, after Homogenization Treatments Alloy make the corresponding antibacterial magnesium alloy of As-extruded Mg-Zn-Y-Nd-Ag by extrusion process.
Preferably, Homogenization Treatments temperature is 350 DEG C-450 DEG C, and the time is 24h-120h.
Preferably, the technological parameter that extrusion process is implemented is: extrusion temperature 300 DEG C-450 DEG C, extrusion ratio 15-50, extruding Speed 1m/min-4m/min.
Compared with existing degradable magnesium alloy, present invention have the advantage that
1, compared with existing degradable blood vessel bracket magnesium alloy, alloying element in the Mg-Zn-Y-Nd-Ag alloy of the present invention Content is relatively low, makes alloy have the biocompatibility of excellence, and Mg, Zn are the necessary trace element of human body, Mg2+Can stimulate The generation of fracture end os osseum crust, induced osteogenesis, promote union of fracture, and stimulate Chondrogenesis, the rich magnesium environment of local can sting Swash osteogenesis, improve osteoblast adhesion rate, suppression osteoclast activity, produced during degradable magnesium alloy material degradation High local concentrations magnesium ion can promote the combination of bone and material interface, not only contribute to bone and fix, it is also possible to promote that bone is more Close；Zn is indispensable in multiple enzyme and function of receptors regulate, and also can affect neural 26S Proteasome Structure and Function.Additionally, In alloy, Element segregation is less, and corrosion rate reduces, and corrosion is more uniform.
2, this alloy can produce Trace Ag in degradation process+, the infection around implant can be suppressed, reduce Post operation Infection rate, reduce antibiotic use, reduce medical treatment cost.
The Mg-Zn-Y-Nd-Ag alloy of the present invention has good mechanical property and decay resistance, is provided simultaneously with excellence Antibacterial functions.This alloy has good biocompatibility, can meet the demand of different implant, can be used for blood vessel and prop up The bone implant materials such as frame, hone lamella and nail.
Accompanying drawing explanation
Fig. 1 is the microscopic structure of embodiment 1 gained As-extruded Mg-2Zn-0.5Y-0.5Nd-0.2Ag alloy；
Fig. 2 is the corrosive nature test result of As-extruded Mg-2Zn-0.5Y-0.5Nd-0.2Ag alloy；
Fig. 3 is that As-extruded Mg-2Zn-0.5Y-0.5Nd-0.2Ag alloy soaks 72 h post-etching pattern SEM and EDS in SBF.
Detailed description of the invention
Below in conjunction with specific embodiment technical scheme done and be discussed in detail into a ground, but the protection model of the present invention Enclose and be not limited thereto.
Embodiment 1
Prepare As-extruded Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.2 wt%Ag magnesium alloy
The preparation of first step as cast condition Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.2wt%Ag magnesium alloy, comprises the following steps:
(1) raw material is prepared:
The quality of each alloying element needed for calculating melting, wherein, Zn in furnace charge, the weight of Y, Nd is its content in the magnesium alloy 1.2-1.3 times, the weight of Ag is 1.1-1.2 times of its content in the magnesium alloy.
Needed for this Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.2wt%Ag magnesium alloy of melting 1kg, quality of furnace charge is as follows:
High-purity magnesium ingot: 941.2g；
High-purity zinc ingot metal: 25g；
Mg-30wt%Y intermediate alloy: 20.8g；
Mg-30wt%Nd intermediate alloy: 20.8g；
High-purity filamentary silver: 2.2g；
High-purity magnesium ingot, high-purity zinc ingot metal and purity >=99.9% of high-purity filamentary silver.
(2) as cast condition Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.2wt%Ag magnesium alloy is prepared:
A, by crucible, Slag Tool, stirring rod and mould heat 150 DEG C, the coating that brush last layer is the veryyest thin, be then placed in Drying baker is dried, dries furnace charge simultaneously；
B, crucible is put in resistance furnace, when temperature is risen to 400 DEG C, be passed through CO2And SF6Mixed gas as protection gas Body, wherein CO2And SF6Flow-rate ratio be 99 1；
C, be passed through protective gas 12 minutes after add high-purity magnesium ingot, under the protection of protective gas 400 DEG C preheating 15min, then Temperature is risen to 700 DEG C, is incubated 20min；
D, after high-purity magnesium ingot is completely melt, add high-purity filamentary silver, temperature risen to 750 DEG C, be incubated 30min；
E, it is subsequently adding Mg-Y intermediate alloy, Mg-Nd intermediate alloy, is incubated 20min；
F, it is eventually adding high-purity zinc ingot metal, cools the temperature to 700 DEG C simultaneously, be incubated 15min；It particularly to be noted that, add stove (volume flow ratio of carbon dioxide and sulfur hexafluoride is to be connected with protection gas during material the most incessantly in resistance furnace 99 1)；
G, stirring, mixing speed is wanted uniformly, counterclockwise, after stirring 5 minutes, to skim, stand 20 minutes；
Before h, casting, mould is passed through above-mentioned CO2And SF6Mixed gas 2min, cast gate at funnel, held stationary；
I, cast complete after, at once residual alloys liquid is poured out, crucible is naturally cooled to about 100 DEG C, pour into boiled water leaching Bubble about 10min, clears up crucible, and melting i.e. ends；
As cast condition Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.2wt%Ag magnesium alloy is i.e. prepared after j, the demoulding.
(3) As-extruded Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.2wt%Ag magnesium alloy is prepared:
The as cast condition Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.2wt%Ag magnesium alloy of preparation in step (2) is carried out homogenization Annealing, annealing temperature 430 DEG C, annealing time 24h.Alloy is processed into the cylinder of diameter 20mm, by clean for surface polishing, uses Conventional extrusion technique as well known to those skilled in the art carries out extruding prepared As-extruded Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd- 0.2wt%Ag magnesium alloy, the parameter of extrusion process process is set to: extrusion temperature 320 DEG C, extrusion ratio: 25, extruding rate: 1m/ min。
Embodiment 2
Prepare As-extruded Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.4wt%Ag magnesium alloy
The preparation of first step as cast condition Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.4wt%Ag magnesium alloy, comprises the following steps:
(1) raw material is prepared:
The quality of each alloying element needed for calculating melting, wherein, Zn in furnace charge, the consumption of Y, Nd is its content in the magnesium alloy 1.2-1.3 times, the consumption of Ag is in its magnesium alloy 1.1-1.2 times of content.
Needed for this Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.4wt%Ag magnesium alloy of melting 1.1kg, quality of furnace charge is as follows:
High-purity magnesium ingot: 1210g
High-purity zinc ingot metal: 32.2g
Mg-30wt%Y intermediate alloy: 26.8g
Mg-30wt%Nd intermediate alloy: 26.8g
High-purity filamentary silver: 5.7g
High-purity magnesium ingot, high-purity zinc ingot metal and purity >=99.9% of high-purity filamentary silver.
(2) as cast condition Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.4wt%Ag magnesium alloy is prepared:
A, crucible, Slag Tool, stirring rod and mould are heated to 180 DEG C, the coating that brush last layer is the veryyest thin, then put Enter in drying baker and dry, dry furnace charge simultaneously；
B, crucible is put in resistance furnace, temperature is risen to 450 DEG C, when temperature reaches, is passed through CO2And SF6Mixed gas As protective gas, wherein CO2And SF6Flow-rate ratio be 99 1；
C, it is passed through above-mentioned protective gas and adds high-purity magnesium ingot after 15 minutes, 450 DEG C of preheating 20min under the protection of protective gas, Then temperature is risen to 720 DEG C, be incubated 20min；
D, after high-purity magnesium ingot is completely melt, add high-purity filamentary silver, temperature risen to 750 DEG C, be incubated 30min；
E, it is subsequently adding Mg-Y intermediate alloy, Mg-Nd intermediate alloy, is incubated 20min；
F, it is eventually adding high-purity zinc ingot metal, simultaneously by temperature to 720 DEG C, is incubated 15min；It particularly to be noted that, add furnace charge During in resistance furnace, be connected with protective gas the most incessantly (volume flow ratio of carbon dioxide and sulfur hexafluoride be 99 1)；
G, stirring, mixing speed is wanted uniformly, counterclockwise, after stirring 5 minutes, to skim, stand 30 minutes；
Before h, casting, mould is passed through above-mentioned CO2And SF6Mixed gas 3min, cast gate at funnel, held stationary；
I, cast complete after, at once residual alloys liquid is poured out, crucible is naturally cooled to about 100 DEG C, pour into boiled water leaching Bubble about 15min, clears up crucible, and melting i.e. ends；
As cast condition Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.4wt%Ag magnesium alloy is i.e. prepared after j, the demoulding.
(3) As-extruded Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.4wt%Ag magnesium alloy is prepared:
The as cast condition Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.4wt%Ag magnesium alloy of preparation in step (2) is carried out homogenization Annealing, annealing temperature 430 DEG C, annealing time 36h.Alloy is processed into the cylinder of diameter 20mm, by clean for surface polishing, uses Conventional extrusion technique as well known to those skilled in the art carries out extruding prepared As-extruded Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd- 0.4wt%Ag magnesium alloy, the parameter of extrusion process process is set to: extrusion temperature 320 DEG C, extrusion ratio: 25, extruding rate: 2m/ min。
Embodiment 3
Prepare As-extruded Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.6wt%Ag magnesium alloy
The preparation of first step as cast condition Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.6wt%Ag magnesium alloy, comprises the following steps:
(1) raw material is prepared:
The quality of each alloying element needed for calculating melting, wherein, Zn in furnace charge, the consumption of Y, Nd is its content in the magnesium alloy 1.2-1.3 times, the consumption of Ag is 1.1-1.2 times of its content in the magnesium alloy.
Needed for this Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.6wt%Ag magnesium alloy of melting 1.3kg, quality of furnace charge is as follows:
High-purity magnesium ingot: 1020g
High-purity zinc ingot metal: 27.2g
Mg-30wt%Y intermediate alloy: 22.8g
Mg-30wt%Nd intermediate alloy: 22.8g
High-purity filamentary silver: 7.3g
High-purity magnesium ingot, high-purity zinc ingot metal and purity >=99.9% of high-purity filamentary silver.
(2) as cast condition Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.6wt%Ag magnesium alloy is prepared:
A, crucible, Slag Tool, stirring rod and mould are heated to 180 DEG C, the coating that brush last layer is the veryyest thin, then put Enter in drying baker and dry, dry furnace charge simultaneously；
B, crucible is put in resistance furnace, temperature is risen to 450 DEG C, when temperature reaches, is passed through CO2And SF6Mixed gas As protective gas, wherein CO2And SF6Flow-rate ratio be 99:1；
C, it is passed through above-mentioned protective gas and adds high-purity magnesium ingot after 15 minutes, 450 DEG C of preheating 20min under the protection of protective gas, Then temperature is risen to 730 DEG C, be incubated 20min；
D, after high-purity magnesium ingot is completely melt, add high-purity filamentary silver, temperature risen to 770 DEG C, be incubated 40min；
E, it is subsequently adding Mg-Y intermediate alloy, Mg-Nd intermediate alloy, is incubated 30min；
F, it is eventually adding high-purity zinc ingot metal, cools the temperature to 730 DEG C simultaneously, be incubated 20min；It particularly to be noted that, add stove (volume flow ratio of carbon dioxide and sulfur hexafluoride is to be connected with protective gas during material the most incessantly in resistance furnace 99 1)；
G, stirring, mixing speed is wanted uniformly, counterclockwise, after stirring 5 minutes, to skim, stand 30 minutes；
Before h, casting, mould is passed through above-mentioned CO2And SF6Mixed gas 3min, cast gate at funnel, held stationary；
I, cast complete after, at once residual alloys liquid is poured out, crucible is naturally cooled to about 100 DEG C, pour into boiled water leaching Bubble about 15min, clears up crucible, and melting i.e. ends；
As cast condition Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.6wt%Ag magnesium alloy is i.e. prepared after j, the demoulding.
(3) As-extruded Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.6wt%Ag magnesium alloy is prepared:
The as cast condition Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.6wt%Ag magnesium alloy of preparation in step (2) is carried out homogenization Annealing, annealing temperature 430 DEG C, annealing time 72h.Alloy is processed into the cylinder of diameter 20mm, by clean for surface polishing, uses Conventional extrusion technique as well known to those skilled in the art carries out extruding prepared As-extruded Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd- 0.6wt%Ag magnesium alloy, the parameter of extrusion process process is set to: extrusion temperature 350 DEG C, extrusion ratio: 25, extruding rate: 2m/ min。
Embodiment 4
Prepare As-extruded Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.8wt%Ag magnesium alloy
The preparation of first step as cast condition Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.8wt%Ag magnesium alloy, comprises the following steps:
(1) raw material is prepared:
The quality of each alloying element needed for calculating melting, wherein, Zn in furnace charge, the consumption of Y, Nd is its content in the magnesium alloy 1.2-1.3 times, the consumption of Ag is 1.1-1.2 times of its content in the magnesium alloy.
Needed for this Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.8wt%Ag magnesium alloy of melting 1.3kg, quality of furnace charge is as follows:
High-purity magnesium ingot: 1245g
High-purity zinc ingot metal: 33.3g
Mg-30wt%Y intermediate alloy: 27.7g
Mg-30wt%Nd intermediate alloy: 27.7g
High-purity filamentary silver: 11.8g
High-purity magnesium ingot, high-purity zinc ingot metal and purity >=99.9% of high-purity filamentary silver.
(2) as cast condition Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.8wt%Ag magnesium alloy is prepared:
A, crucible, Slag Tool, stirring rod and mould are heated to 180 DEG C, the coating that brush last layer is the veryyest thin, then put Enter in drying baker and dry, dry furnace charge simultaneously；
B, crucible is put in resistance furnace, temperature is risen to 450 DEG C, when temperature reaches, is passed through CO2And SF6Mixed gas As protective gas, wherein CO2And SF6Flow-rate ratio be 99 1；
C, be passed through hybrid protection gas 20 minutes after add high-purity magnesium ingot, under the protection of protective gas 450 DEG C preheating 20min, so After temperature is risen to 750 DEG C, be incubated 30min；
D, after high-purity magnesium ingot is completely melt, add high-purity filamentary silver, temperature risen to 800 DEG C, be incubated 40min；
E, it is subsequently adding Mg-Y intermediate alloy, Mg-Nd intermediate alloy, is incubated 30min；
F, it is eventually adding high-purity zinc ingot metal, cools the temperature to 750 DEG C simultaneously, be incubated 25min；It particularly to be noted that, add stove (volume flow ratio of carbon dioxide and sulfur hexafluoride is to be connected with protective gas during material the most incessantly in resistance furnace 99 1)
G, stirring, mixing speed is wanted uniformly, counterclockwise, after stirring 5 minutes, to skim, stand 40 minutes；
Before h, casting, mould is passed through above-mentioned CO2And SF6Mixed gas 3min, cast gate at funnel, held stationary；
I, cast complete after, at once residual alloys liquid is poured out, crucible is naturally cooled to about 100 DEG C, pour into boiled water leaching Bubble about 15min, clears up crucible, and melting i.e. ends；
As cast condition Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.8wt%Ag magnesium alloy is i.e. prepared after j, the demoulding.
(3) As-extruded Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.8wt%Ag magnesium alloy is prepared:
The as cast condition Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.8wt%Ag magnesium alloy of preparation in step (2) is carried out homogenization Annealing, annealing temperature 430 DEG C, annealing time 120h.Alloy is processed into the cylinder of diameter 20mm, by clean for surface polishing, adopts Carry out extruding prepared As-extruded Mg-2wt%Zn-0.5wt%Y-0.5wt% with conventional extrusion technique as well known to those skilled in the art Nd-0.8wt%Ag magnesium alloy, the parameter of extrusion process process is set to: extrusion temperature 360 DEG C, extrusion ratio: 25, extruding rate: 2m/min。
The As-extruded Mg-2wt%Zn-0.5 wt%Y-0.5 wt%Nd-0.2 wt%Ag magnesium of embodiment 1 preparation closes after testing Gold, the As-extruded Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.4wt%Ag magnesium alloy of embodiment 2 preparation, embodiment 3 preparation As-extruded Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.6wt%Ag magnesium alloy, and the As-extruded Mg-2wt% of embodiment 4 preparation The room temperature tensile intensity of Zn-0.5wt%Y-0.5wt%Nd-0.8wt%Ag magnesium alloy respectively reaches 286MPa, 292MPa, 310MPa And 277MPa, yield strength is respectively 98MPa, 101MPa, 101MPa, 114MPa.
Bacteriostatic experiment shows, implements 1 to 4 magnesium alloy prepared equal to the killing rate of escherichia coli and staphylococcus aureus Reach more than 99.9%.
Micro-group of embodiment 1 gained As-extruded Mg-2wt%Zn-0.5 wt%Y-0.5 wt%Nd-0.2wt%Ag magnesium alloy Knitting as it is shown in figure 1, as can be seen from Figure 1 this alloy even tissue after extrusion process, crystal grain is tiny, average grain size Being 13 μm, the second phase is evenly distributed and disperse.
The corrosivity of embodiment 1 gained As-extruded Mg-2wt%Zn-0.5 wt%Y-0.5 wt%Nd-0.2 wt%Ag magnesium alloy As in figure 2 it is shown, as can be drawn from Figure 2, the corrosion potential of this alloy is-1.60V to energy test result, and corrosion electric current density is 1.38×10-4A•cm-2, its corrosive nature meets biological medical magnesium alloy requirement.
Embodiment 1 gained As-extruded Mg-2wt%Zn-0.5 wt%Y-0.5 wt%Nd-0.2 wt%Ag magnesium alloy is in SBF Soak 72 h post-etching pattern SEM and EDS as it is shown on figure 3, from figure 3, it can be seen that alloy through corrosion after primarily formed with Magnesium hydroxide and Ca-P salt are main corrosion product, detect the existence of substantial amounts of Ag element, this explanation in the drawings in A point Ag in alloy is to separate out with the form of Ag ion.

Claims (8)

1. the antibacterial magnesium alloy of novel biodegradable Mg-Zn-Y-Nd-Ag, it is characterised in that described Mg-Zn-Y-Nd-Ag Antibacterial magnesium alloy consists of the following components in percentage by weight: Zn:1%-3%, Y:0.2%-1%, Nd:0.2%-1%, Ag:0.05%- 1.5%, surplus is Mg.
2. the method preparing the antibacterial magnesium alloy of novel biodegradable Mg-Zn-Y-Nd-Ag as claimed in claim 1, its It is characterised by, with high-purity magnesium ingot, high-purity zinc ingot metal, Mg-Y intermediate alloy, Mg-Nd intermediate alloy and high-purity filamentary silver for furnace charge melting system Becoming the antibacterial magnesium alloy of as cast condition Mg-Zn-Y-Nd-Ag, Zn in furnace charge, the consumption of Y, Nd is that it closes at the antibacterial magnesium of Mg-Zn-Y-Nd-Ag In gold 1.2-1.3 times of content, the consumption of Ag is its in the antibacterial magnesium alloy of Mg-Zn-Y-Nd-Ag 1.1-1.2 times of content.
3. the preparation method of the antibacterial magnesium alloy of novel biodegradable Mg-Zn-Y-Nd-Ag as claimed in claim 2, its feature Being, Mg-Y intermediate alloy is Mg-30wt%Y intermediate alloy, and Mg-Nd intermediate alloy is Mg-30wt%Nd intermediate alloy, high purity magnesium Ingot, high-purity zinc ingot metal and purity >=99.9% of high-purity filamentary silver.
4. the preparation method of the antibacterial magnesium alloy of novel biodegradable Mg-Zn-Y-Nd-Ag as claimed in claim 2 or claim 3, its It is characterised by, high-purity magnesium ingot is heated under the protection of protective gas, after high-purity magnesium ingot is completely melt, add high-purity filamentary silver, Temperature is risen to 740 DEG C-800 DEG C, is incubated 30min-50min, is subsequently adding Mg-Y intermediate alloy, Mg-Nd intermediate alloy, insulation After 15min-30min, add high-purity zinc ingot metal, cool the temperature to 680 DEG C-730 DEG C, be incubated 15min-20min, then stir 3min-5min, then skim, casting, the demoulding i.e. prepares the antibacterial magnesium alloy of as cast condition Mg-Zn-Y-Nd-Ag.
5. the preparation method of the antibacterial magnesium alloy of novel biodegradable Mg-Zn-Y-Nd-Ag as claimed in claim 4, its feature Being, protective gas is CO2And SF6Gaseous mixture, wherein, CO2And SF6Volume ratio is 99 1.
6. the preparation method of the antibacterial magnesium alloy of novel biodegradable Mg-Zn-Y-Nd-Ag as claimed in claim 2, its feature It is, antibacterial for as cast condition Mg-Zn-Y-Nd-Ag magnesium alloy is carried out Homogenization Treatments, to the alloy after Homogenization Treatments by extruding work Skill makes the corresponding antibacterial magnesium alloy of As-extruded Mg-Zn-Y-Nd-Ag.
7. the preparation method of the antibacterial magnesium alloy of novel biodegradable Mg-Zn-Y-Nd-Ag as claimed in claim 6, its feature It is that the technological parameter that Homogenization Treatments is implemented is: Homogenization Treatments temperature is 350 DEG C-450 DEG C, and the time is 24h-120h.
8. the preparation method of the antibacterial magnesium alloy of novel biodegradable Mg-Zn-Y-Nd-Ag as claimed in claim 6, it is special Levying and be, the technological parameter that extrusion process is implemented is: extrusion temperature 300 DEG C-450 DEG C, extrusion ratio 15-50, extruding rate 1m/ min -4m/min。
CN201610820508.5A 2016-09-13 2016-09-13 A kind of novel biodegradable Mg Zn Y antibacterial magnesium alloy of Nd Ag and preparation method thereof Pending CN106191597A (en)

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CN107653410A (en) * 2017-09-15 2018-02-02 中国兵器科学研究院宁波分院 Magnesium alloy that biological medical degradable absorbs and its preparation method and application
CN108285987A (en) * 2018-02-01 2018-07-17 山东建筑大学 The preparation method of copper oxide-vanadium carbide particle enhancing antibacterial medical magnesium alloy materials

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Application publication date: 20161207