CN108677074A - A kind of medical degradable corrosion-resistant magnesium alloy bracket and preparation method thereof of implantation heart - Google Patents
A kind of medical degradable corrosion-resistant magnesium alloy bracket and preparation method thereof of implantation heart Download PDFInfo
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
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Abstract
The invention discloses a kind of medical degradable corrosion-resistant magnesium alloy brackets of implantation heart, it is characterised in that：It is made of the element of following mass percent：Zn 12.5 13, Nd 3.6 3.8, Ca 3.2 3.8, Mn 1.1 1.3, Y 0.5 0.8, Zr 0.2 0.4, Sn 0.5 0.7, Gd 0.4 0.5, Sr 0.2 0.3, Nd/Y 4.55 7, Gd/Zr 1.1 2.4, remaining is Mg and inevitable impurity element, and the component and each component weight percent of the inevitable impurity element are：Fe 0.002 0.005%, Ni 0.005 0.008%, Si 0.015 0.05%, Mg in metallographic structure3Nd precipitate grain sizes are 0.10 0.15 μm, Mg3Y2Zn3Precipitate grain size is 0.15 0.20 μm, Ca in metallographic structure2Mg6Zn3Precipitate grain size is 0.3 0.5 μm, and magnesium alloy crystal grain is 50 60 μm, 300 380MPa of tensile strength, 180 250MPa of yield strength, elongation 20 35%.
Description
Technical field
The invention belongs to medical alloy field, more particularly to a kind of medical degradable corrosion-resistant magnesium alloy branch of implantation heart
Frame.
Background technology
Relative to traditional implantation material, it is connected to each other with skeleton in specific strength and Young's modulus etc. magnesium alloy
Closely, and magnesium ion is conducive to the formation of osteocyte, not only reduces the stress shielding between implantable material and bone in this way
Effect, avoid osteoporosis, and promote the regrowth of skeleton.Therefore, magnesium alloy is counted as very promising
Implantable biomaterial.From another point of view, magnesium elements can degrade in human body, patient be avoided so secondary
Operation slows down the pain that operation is brought, and reduces medical expense.Therefore, degradable biological magnesium alloy is extensive
Applied to fields such as orthopaedics, angiocarpy, departments of general surgery.
Magnesium and magnesium alloy, which are used as this new bio metal material, has unrivaled advantage.First, magnesium be human body only
Inferior to the intracellular cation of potassium, it participates in a series of metabolic processes in vivo, and daily required amount of magnesium is more than in adult body
350mg, the magnesium alloy materials to implant not will produce toxic side effect；Secondly, magnesium and magnesium alloy are several all or several after the implantation
It can be by the degradable absorption of human body, at the beginning of this has conformed exactly to the design of the materials such as intravascular stent, bone plate " urgently needed, interim " after month
Inner feelings.Therefore, magnesium and magnesium alloy, which are used as bio-medical material, has huge development potentiality, causes the pass of more and more people
Note and research.But that there are intensity is low, plasticity is poor, contains the deficiencies of toxic element (Al, Zn etc.) for traditional magnesium and magnesium alloy, limitation
Their applications in bio-medical field.
One of the key factor for determining holder comprehensive performance quality is the suitable vascular stent material of selection.At present
There are many different types of bio-medical materials to be used to make intravascular stent, sums up, these bio-medical materials are main
Including two major classes：Biological medical polymer material and biomedical metallic material.Wherein, biomedical metallic material is broadly divided into
Two classes：Non-degradable biomedical metallic material and degradable biological medical metal material.Non-degradable intravascular stent is placed in people
After body, even if the blood vessel blocked has been dredged, holder can also be left permanently in internal blood vessel.Non-degradable metallic support is as outer
Carry out foreign matter to stay in human body, stimulation can be generated to vascular wall, so that the endometrial hyperplasia probability of blood vessel is had obvious increase, be easy
Cause the narrow again of blood vessel.It is (general in the given time after biodegradable stent is placed according to specified path at vascular lesion
4 months or so) complete dredge block blood vessel effect after, will degrade and finish, catabolite with it is normal metabolism and
Slowly absorbed by human body.In this way, after blocking blood vessel dredging, internal blood vessel will not again there are foreign matter, reangiostenosis it is several
Rate is also reduced.Therefore, in recent years, degradable blood vessel bracket material be increasingly becoming scientists from all over the world research hot spot it
One, it is increasingly becoming the later development trend of vascular stent material.
Invention content
The present invention develops a kind of implantation heart on the basis of conventional medical magnesium alloy, by composition adjustment and process modification
Dirty medical degradable corrosion-resistant magnesium alloy bracket and preparation method thereof, the alloy have excellent mechanical property and corrosion resistance
Can, and the damage to health is avoided, there are important social and economic implications.
The present invention specifically provides a kind of medical degradable corrosion-resistant magnesium alloy bracket of implantation heart, it is characterised in that：
It is made of the element of following mass percent：Zn 12.5-13、Nd 3.6-3.8、Ca 3.2-3.8、Mn 1.1-1.3、Y 0.5-
0.8, Zr 0.2-0.4, Sn 0.5-0.7, Gd 0.4-0.5, Sr 0.2-0.3, Nd/Y 4.55-7, Gd/Zr 1.1-2.4,
Remaining is Mg and inevitable impurity element, and the component and each component weight percent of the inevitable impurity element are：
Fe0.002-0.005%, Ni 0.005-0.008%, Si 0.015-0.05%, Mg in metallographic structure3Nd precipitate grain sizes are
0.10-0.15 μm, Mg3Y2Zn3Precipitate grain size is 0.15-0.20 μm, Ca in metallographic structure2Mg6Zn3Precipitate grain size is 0.3-
0.5 μm, magnesium alloy crystal grain is 50-60 μm, tensile strength 300-380MPa, yield strength 180-250MPa, elongation 20-
35%.
Preferably a kind of medical degradable corrosion-resistant magnesium alloy bracket of implantation heart, it is characterised in that：By following matter
Measure the element composition of percentage：Zn 12.6-12.8、Nd 3.65-3.75、Ca 3.3-3.7、Mn 1.15-1.25、Y 0.55-
0.75, Zr 0.25-0.35, Sn 0.55-0.65, Gd 0.42-0.48, Sr 0.22-0.28, Nd/Y 4.55-7, Gd/Zr
1.1-2.4, remaining is Mg and inevitable impurity element, the component and each component weight of the inevitable impurity element
Percentage is：Fe 0.002-0.005%, Ni 0.005-0.008%, Si 0.015-0.05%.
Preferably a kind of medical degradable corrosion-resistant magnesium alloy bracket of implantation heart, it is characterised in that：By following matter
Measure the element composition of percentage：Zn 12.5、Nd 3.6、Ca 3.2、Mn 1.1、Y 0.52、Zr 0.2、Sn 0.5、Gd 0.4、
Sr 0.25, Nd/Y 6.92, Gd/Zr 2, remaining is Mg and inevitable impurity element.
Preferably a kind of medical degradable corrosion-resistant magnesium alloy bracket of implantation heart, it is characterised in that：By following matter
Measure the element composition of percentage：Zn 12.6、Nd 3.65、Ca 3.3、Mn 1.15、Y 0.55、Zr 0.25、Sn 0.55、Gd
0.42,0.22 Sr, Nd/Y 6.63, Gd/Zr 1.68, remaining is Mg and inevitable impurity element.
Preferably a kind of medical degradable corrosion-resistant magnesium alloy bracket of implantation heart, it is characterised in that：By following matter
Measure the element composition of percentage：Zn 12.8、Nd 3.75、Ca 3.7、Mn 1.25、Y 0.75、Zr 0.35、Sn 0.65、Gd
0.48,0.28 Sr, Nd/Y 5, Gd/Zr 1.37, remaining is Mg and inevitable impurity element.
Preferably a kind of medical degradable corrosion-resistant magnesium alloy bracket of implantation heart, it is characterised in that：By following matter
Measure the element composition of percentage：Zn 13、Nd 3.8、Ca 3.8、Mn 1.3、Y 0.8、Zr 0.35、Sn 0.7、Gd 0.5、Sr
0.3, Nd/Y 4.75, Gd/Zr 1.43, remaining is Mg and inevitable impurity element.
The preparation method of the medical degradable corrosion-resistant magnesium alloy bracket of above-mentioned implantation heart, it is characterised in that：
(1) raw material is chosen
Purity be 99.99% Mg ingots, purity be 99.99% Zn ingots, Zn mass ratioes account for 53wt% Mg-Zn intermediate alloys,
Nd mass ratioes account for the Mg-Nd intermediate alloys of 18wt%, Gd mass ratioes account for 25% Mg-Gd intermediate alloys, Y mass ratioes account in Mg-Y
Between alloy, Zr mass ratioes account for 30% Mg-Zr intermediate alloys, other required elements are in the form of intermediate alloy or simple substance according to mesh
Mark magnesium alloy ingredient is stocked up；
(2) alloy melting
Alloy melting carries out in gas shield resistance furnace, and the fused salt for being first 2: 1 with KCl: NaCl weight ratio cleans plant crucible,
Then crucible is put into resistance furnace and is preheated to 530-550 DEG C, be packed into Mg ingots and be warming up to 700 DEG C, after Mg ingots all fusing
It is warming up to 750-800 DEG C, sequentially adds Zn ingots and Mg-Zn intermediate alloys, Mg-Nd intermediate alloys, Mg-Gd intermediate alloys, Mg-Y
Intermediate alloy, Mg-Zr intermediate alloys and remaining raw material are sufficiently stirred fusing and stand 20-30min, and melting whole process is passed through guarantor
Gas is protected, protection gas group becomes：CO2 volume ratios are that 50%, SF6 volume ratios are 1-2%, and surplus is argon gas；What fusion process was added
Refining agent accounts for the 1.2-1.5% of alloy solution weight, and refining agent ingredient is that magnesium chloride accounts for 65wt%, potassium chloride accounts for 15wt%, chlorine
Barium accounts for 15wt%, gadolinium chloride accounts for 5wt% for change, and after alloy is cooled to 720 DEG C, slagging-off is cast in is preheated to clean diameter in advance
In the mold of 30mm, to wait for that temperature reaches room temperature, casting rod is taken out, hot extrusion technique processing is ready for；
(3) hot extrusion
Homogenizing annealing is first carried out, under the conditions of 450 DEG C, 12 hours is kept the temperature, eliminates the microsegregation formed in casting process, so
Water cooling afterwards forms supersaturated solid solution；Before extrusion, using the oxide skin on coarse sandpaper removal raw material surface, it is placed on heat preservation
In stove, 30min is kept the temperature under the conditions of 200 DEG C, the temperature of extruding is set to 350 DEG C, while by mold and extrusion cylinder respectively in extruder
On holding furnace in kept the temperature, the temperature of heat preservation is identical as temperature is squeezed, and the lubricating oil used squeezes fast for vegetable lhybricant
Degree is 40-50mm/s, extrusion ratio 16:1, obtain medical degradable corrosion-resistant magnesium alloy；
(4) subsequent processing
Medical degradable corrosion-resistant magnesium alloy prepared by step (3), which carries out laser engraving, becomes holder, is then polished, and throws
It is cleaned with the acid solution of 10-15wt% after light and uses ultrasonic cleaning again, ultrasonic frequency 50-60khz is cleaned 3 times repeatedly, single
Secondary scavenging period is 10 minutes；Drug-carried coat processing is carried out by spraying collagen to the holder later, coating layer thickness is
0.1-0.2mm。
The preparation method of the medical degradable corrosion-resistant magnesium alloy bracket of the preferably described implantation heart, feature exist
In：Step (3) first carries out homogenizing annealing, under the conditions of 450 DEG C, keeps the temperature 12 hours, is formed in elimination casting process transgranular
Segregation, then water cooling, forms supersaturated solid solution；Before extrusion, it using the oxide skin on coarse sandpaper removal raw material surface, puts
In holding furnace, 30min is kept the temperature under the conditions of 200 DEG C, the temperature of extruding is set to 350 DEG C, while mold and extrusion cylinder being existed respectively
Kept the temperature in holding furnace on extruder, the temperature of heat preservation is identical as temperature is squeezed, the lubricating oil used for vegetable lhybricant,
Extrusion speed is 45mm/s, extrusion ratio 16:1, obtain medical degradable corrosion-resistant magnesium alloy.
The preparation method of the medical degradable corrosion-resistant magnesium alloy bracket of the preferably described implantation heart, feature exist
In：The medical degradable corrosion-resistant magnesium alloy that step (4) prepares step (3), which carries out laser engraving, becomes holder, then carries out
Polishing is cleaned with the acid solution of 12.5wt% after polishing and ultrasonic cleaning, ultrasonic frequency 55khz is used to clean 3 repeatedly again
Secondary, single scavenging period is 10 minutes；Drug-carried coat processing is carried out by spraying collagen to the holder later, applies thickness
Degree is 0.15mm.
The effect of each element is as follows in magnesium alloy provided by the present invention：
Zn is indispensable trace element in human body, all extremely important to the formation of protein and collagen, participates in human body
Energetic supersession, and play the role of antibacterial anti-inflammatory, cell development is influenced, is the necessary micronutrient element of human body.Zn's adds
Enter the intensity of alloy can be improved, while effectively facilitating the generation of the non-basal slip of magnesium alloy at room temperature, improves the plasticity of magnesium alloy
Working ability.Zn increases fluidity of molten, is a kind of weak grain refiner.The second phases of MgZn2 can be formed in Mg alloys, had
There is stronger dispersion-strengthened effect, improves the mechanical property of alloy；Zn elements can generate passivation, improve the spot corrosion electricity of alloy
Position, drops low-alloyed corrosion degradation speed, improves the corrosion resisting property of alloy.The content of Zn is 12.5-13% in the present invention, preferably
Zn12.6-12.8%.
Nd belongs to a kind of light rare earth elements, has preferable biological safety, is different from this kind of toxic element of La, Ce, Er.Nd's
Addition can ensure that magnesium alloy has the effect of good Precipitation reinforcing and solution strengthening, while the addition of Nd can be significantly
The electrode potential of magnesium alloy substrate is improved, the potential difference of matrix and the galvanic corrosion of the second phase is reduced, is closed to significantly improve magnesium
The corrosion resisting property of gold.Moreover it is possible to which crystalline substance can effectively be refined by playing the role of purification, removal of impurities, and Nd during magnesium alloy smelting
Grain improves mechanical property and corrosion resistance；Nd can improve room-temperature mechanical property with uniform formation.Rare earth element can enter
In the corrosive film of magnesium alloy, the aquation of corrosive film is reduced, improves the compactness of corrosive film.The content of Nd is in the present invention
3.6-3.8%, preferably Nd 3.65-3.75%.
Ca is that the macroelement in human body is also known as inorganic salts element, is the basic element for constituting tissue, is to maintain acid in vivo
Soda balance, the important element for adjusting various physiological functions, are one of main components of human body hard tissue bone, can promote
Bone growth；Ca can improve the creep-resistant property of magnesium alloy；Magnesium alloy burning point can be improved in fusion process, prevent melt
Oxidation；Simultaneously Ca can crystal grain thinning, formed the second phases of Ca2Mg6Zn3, have stronger dispersion-strengthened effect, improve alloy
Mechanical property；Ca is the alloying element for influencing anodic process, and micro Ca can become the loose MgO membrane of alloy surface more
The skin covering of the surface of fine and close MgO/CaO, improves the corrosion resisting property of alloy.The content of Ca is 3.2-3.8% in the present invention, preferably
3.3-3.7%.Mn is nutriment necessary to the metabolism of bon e formation, lipid, amino acid and carbohydrate, is mainly passed through
The intermetallic compound that relative harmless is generated with iron and the effect of other heavy metal elements, to make the corrosion resistance of magnesium alloy be carried
It is high.Has the function of crystal grain thinning；The content of Mn is 1.1-1.3%, preferably Mn 1.15-1.25% in the present invention.
Y is rare earth element, has anticoagulation, anti-inflammatory, bactericidal effect in human body, prevents or delay the formation of atherosclerosis,
Melt, crystal grain thinning can also be purified by participating in immunologic process.Y can not only play purification during magnesium alloy smelting, removal of impurities is made
With, and Y it is similar with Nd can crystal grain thinning, improve mechanical property and corrosion resistance；Rare earth element can enter magnesium alloy
In corrosive film, the aquation of corrosive film is reduced, improves the compactness of corrosive film.When Zn/Y mass percents are >=5 in alloy
When, it can promote the generation of Mg3YZn6 Icosahedral phases, Mg3YZn6 Icosahedral phases that there is symbiosis and epibiosis with Mg matrixes, strong original can be formed
Sub-key combines, and prevents the generation of basal slip and interface crackle, significantly improves the mechanical property of alloy；Mg3YZn6 Icosahedral phases
Activity is relatively low, can improve alloy corrosion resistance energy.The content of Y is 0.5-0.8%, preferably 0.55-0.75% in the present invention.
Zr human body good biocompatibility it is verified that, bio-toxicity is relatively low.Core of the Zr elements as heterogeneous forming core
Significantly refining alloy crystal grain, purification melt it can further increase obdurability, the corrosion resistance of alloy.Zn, Y can be with shapes in Mg
At the second phase of Mg3Y2Zn3, Mg3YZn6, Mg24Y5, there is stronger dispersion-strengthened effect, improve the mechanical property of alloy.Zn、
Ca can form the second phases of Ca2Mg6Zn3 in Mg, have stronger dispersion-strengthened effect, improve the mechanical property of alloy.This
The content of Zr is 0.2-0.4%, preferably 0.25-0.35% in invention.
Sn is conducive to the growth and development of body, can promote the healing of wound, participates in the function of influencing hemoglobin, meanwhile, Sn
The mechanical property and corrosion resistance of magnesium alloy can be improved with crystal grain thinning by being added in magnesium alloy.The content of Sn in the present invention
For 0.5-0.7%, preferably 0.55-0.65%.
Alloy elements of the Gd as magnesium can form high melting compound with harmful elements such as iron ambrose alloys and be precipitated and purify and close
Gold；Have the function of crystal grain thinning, is not only able to improve the corrosion resistance of alloy, the mechanical property of alloy can also be improved；
It can enter in the corrosive film of magnesium alloy, reduce the aquation of corrosive film, improve the compactness of corrosive film.Gd in the present invention
Content be 0.4-0.5%, preferably Gd 0.42-0.48%.
Sr is the necessary trace element of the element and organism that are had a major impact to cell development, and drug containing strontium has
Promote bone tissue to be formed, the effect of inhibition bone information, is clinically used for treatment osteoporosis.There is scholar to promote bone tissue to give birth to using strontium
Long feature prepares coating containing strontium, for improving the effect of its Integrated implant on medical metal surface.Sr is that one of magnesium alloy is important
There is alloy element Grain Refinement Effect, the appropriate Sr that adds can improve the intensity of magnesium alloy and the corrosion resistance of alloy.
The content of Sr is 0.2-0.3%, preferably 0.22-0.28% in the present invention.
Medical magnesium alloy is currently, there are individually or the case where add Nd, Y simultaneously, researcher of the present invention passes through a large amount of real
It tests, finds, as Nd/Y 4.55-7, the mechanical property of medical magnesium alloy can be significantly improved, slightly improve corrosion resistance in addition
Energy.
Medical magnesium alloy is currently, there are individually or the case where add Gd, Zr simultaneously, researcher of the present invention passes through a large amount of real
It tests, finds, as Gd/Zr 1.1-2.4, the corrosion resistance of medical magnesium alloy can be significantly improved, slightly improve mechanics in addition
Performance.
The advantage of the invention is that：
(1) medical degradable corrosion-resistant magnesium alloy of the present invention, by selecting human essential elements and part hypotoxicity member
Plain and stringent control element additive amount to reduce the bio-toxicity of medical degradable corrosion-resistant magnesium alloy, while also ensuring wound
The nutrition of oral area position, contributes to wound healing.
(2) method of the invention realizes regulation and control by the cooperation of composition design and preparation process, especially heat treatment, crimp
Medical degradable corrosion-resistant magnesium alloy, obtained alloy material can meet field of stents to material corrosion resistance, mechanical property and
The requirement of biological safety.
(3) medical degradable corrosion-resistant magnesium alloy of the present invention, although it is added to more alloying element, but in life
Object compatibility, corrosion resistance, mechanical property achieve significant raising, achieve good social benefit.
(4) medical degradable corrosion-resistant magnesium alloy of the present invention, by choosing suitable raw material, control intermediate alloy is added
Sequentially, reach being uniformly distributed for the second phase, reduce the scaling loss in fusion process.
(5) medical degradable corrosion-resistant magnesium alloy of the present invention, Mg in metallographic structure3Nd precipitate grain sizes are 0.10-0.15
μm, Mg3Y2Zn3Precipitate grain size is 0.15-0.20 μm, Ca in metallographic structure2Mg6Zn3Precipitate grain size is 0.3-0.5 μm, magnesium
Alloy grain is 50-60 μm, tensile strength 300-380MPa, yield strength 180-250MPa, elongation 20-35%.
Specific implementation mode
It elaborates to technical solution of the present invention below with reference to example embodiment.However, example embodiment can
Implement in a variety of forms, and is not understood as limited to embodiment set forth herein；On the contrary, thesing embodiments are provided so that
The design of example embodiment more comprehensively and completely, and is comprehensively communicated to those skilled in the art by the present invention.
Embodiment 1
A kind of medical degradable corrosion-resistant magnesium alloy bracket of implantation heart, it is characterised in that：By the member of following mass percent
Element composition：Zn 12.5, Nd 3.6, Ca 3.2, Mn 1.1, Y 0.52, Zr 0.2, Sn 0.5, Gd 0.4, Sr 0.25, Nd/Y
6.92, Gd/Zr 2, remaining is Mg and inevitable impurity element, the component and each group of the inevitable impurity element
Point weight percent is：Fe 0.002-0.005%, Ni 0.005-0.008%, Si 0.015-0.05%.
The preparation method of the medical degradable corrosion-resistant magnesium alloy bracket of the implantation heart, it is characterised in that：
(1) raw material is chosen
Purity be 99.99% Mg ingots, purity be 99.99% Zn ingots, Zn mass ratioes account for 53wt% Mg-Zn intermediate alloys,
Nd mass ratioes account for the Mg-Nd intermediate alloys of 18wt%, Gd mass ratioes account for 25% Mg-Gd intermediate alloys, Y mass ratioes account in Mg-Y
Between alloy, Zr mass ratioes account for 30% Mg-Zr intermediate alloys, other required elements are in the form of intermediate alloy or simple substance according to mesh
Mark magnesium alloy ingredient is stocked up；
(2) alloy melting
Alloy melting carries out in gas shield resistance furnace, and the fused salt for being first 2: 1 with KCl: NaCl weight ratio cleans plant crucible,
Then crucible is put into resistance furnace and is preheated to 530-550 DEG C, be packed into Mg ingots and be warming up to 700 DEG C, after Mg ingots all fusing
It is warming up to 750-800 DEG C, sequentially adds Zn ingots and Mg-Zn intermediate alloys, Mg-Nd intermediate alloys, Mg-Gd intermediate alloys, Mg-Y
Intermediate alloy, Mg-Zr intermediate alloys and remaining raw material are sufficiently stirred fusing and stand 20-30min, and melting whole process is passed through guarantor
Gas is protected, protection gas group becomes：CO2 volume ratios are that 50%, SF6 volume ratios are 1-2%, and surplus is argon gas；What fusion process was added
Refining agent accounts for the 1.2-1.5% of alloy solution weight, and refining agent ingredient is that magnesium chloride accounts for 65wt%, potassium chloride accounts for 15wt%, chlorine
Barium accounts for 15wt%, gadolinium chloride accounts for 5wt% for change, and after alloy is cooled to 720 DEG C, slagging-off is cast in is preheated to clean diameter in advance
In the mold of 30mm, to wait for that temperature reaches room temperature, casting rod is taken out, hot extrusion technique processing is ready for；
(3) hot extrusion
Homogenizing annealing is first carried out, under the conditions of 450 DEG C, 12 hours is kept the temperature, eliminates the microsegregation formed in casting process, so
Water cooling afterwards forms supersaturated solid solution；Before extrusion, using the oxide skin on coarse sandpaper removal raw material surface, it is placed on heat preservation
In stove, 30min is kept the temperature under the conditions of 200 DEG C, the temperature of extruding is set to 350 DEG C, while by mold and extrusion cylinder respectively in extruder
On holding furnace in kept the temperature, the temperature of heat preservation is identical as temperature is squeezed, and the lubricating oil used squeezes fast for vegetable lhybricant
Degree is 40-50mm/s, extrusion ratio 16:1, obtain medical degradable corrosion-resistant magnesium alloy；
(4) subsequent processing
Medical degradable corrosion-resistant magnesium alloy prepared by step (3), which carries out laser engraving, becomes holder, is then polished, and throws
It is cleaned with the acid solution of 10-15wt% after light and uses ultrasonic cleaning again, ultrasonic frequency 50-60khz is cleaned 3 times repeatedly, single
Secondary scavenging period is 10 minutes；Drug-carried coat processing is carried out by spraying collagen to the holder later, coating layer thickness is
0.1-0.2mm。
Embodiment 2
A kind of medical degradable corrosion-resistant magnesium alloy bracket of implantation heart, it is characterised in that：By the member of following mass percent
Element composition：Zn 12.6, Nd 3.65, Ca 3.3, Mn 1.15, Y 0.55, Zr 0.25, Sn 0.55, Gd 0.42, Sr 0.22,
Nd/Y6.63, Gd/Zr 1.68, remaining is Mg and inevitable impurity element, the component of the inevitable impurity element
And each component weight percent is：Fe 0.002-0.005%, Ni 0.005-0.008%, Si 0.015-0.05%.
The preparation method of the medical degradable corrosion-resistant magnesium alloy bracket of the implantation heart, it is characterised in that：
(1) raw material is chosen
Purity be 99.99% Mg ingots, purity be 99.99% Zn ingots, Zn mass ratioes account for 53wt% Mg-Zn intermediate alloys,
Nd mass ratioes account for the Mg-Nd intermediate alloys of 18wt%, Gd mass ratioes account for 25% Mg-Gd intermediate alloys, Y mass ratioes account in Mg-Y
Between alloy, Zr mass ratioes account for 30% Mg-Zr intermediate alloys, other required elements are in the form of intermediate alloy or simple substance according to mesh
Mark magnesium alloy ingredient is stocked up；
(2) alloy melting
Alloy melting carries out in gas shield resistance furnace, and the fused salt for being first 2: 1 with KCl: NaCl weight ratio cleans plant crucible,
Then crucible is put into resistance furnace and is preheated to 530-550 DEG C, be packed into Mg ingots and be warming up to 700 DEG C, after Mg ingots all fusing
It is warming up to 750-800 DEG C, sequentially adds Zn ingots and Mg-Zn intermediate alloys, Mg-Nd intermediate alloys, Mg-Gd intermediate alloys, Mg-Y
Intermediate alloy, Mg-Zr intermediate alloys and remaining raw material are sufficiently stirred fusing and stand 20-30min, and melting whole process is passed through guarantor
Gas is protected, protection gas group becomes：CO2 volume ratios are that 50%, SF6 volume ratios are 1-2%, and surplus is argon gas；What fusion process was added
Refining agent accounts for the 1.2-1.5% of alloy solution weight, and refining agent ingredient is that magnesium chloride accounts for 65wt%, potassium chloride accounts for 15wt%, chlorine
Barium accounts for 15wt%, gadolinium chloride accounts for 5wt% for change, and after alloy is cooled to 720 DEG C, slagging-off is cast in is preheated to clean diameter in advance
In the mold of 30mm, to wait for that temperature reaches room temperature, casting rod is taken out, hot extrusion technique processing is ready for；
(3) hot extrusion
Homogenizing annealing is first carried out, under the conditions of 450 DEG C, 12 hours is kept the temperature, eliminates the microsegregation formed in casting process, so
Water cooling afterwards forms supersaturated solid solution；Before extrusion, using the oxide skin on coarse sandpaper removal raw material surface, it is placed on heat preservation
In stove, 30min is kept the temperature under the conditions of 200 DEG C, the temperature of extruding is set to 350 DEG C, while by mold and extrusion cylinder respectively in extruder
On holding furnace in kept the temperature, the temperature of heat preservation is identical as temperature is squeezed, and the lubricating oil used squeezes fast for vegetable lhybricant
Degree is 40-50mm/s, extrusion ratio 16:1, obtain medical degradable corrosion-resistant magnesium alloy；
(4) subsequent processing
Medical degradable corrosion-resistant magnesium alloy prepared by step (3), which carries out laser engraving, becomes holder, is then polished, and throws
It is cleaned with the acid solution of 10-15wt% after light and uses ultrasonic cleaning again, ultrasonic frequency 50-60khz is cleaned 3 times repeatedly, single
Secondary scavenging period is 10 minutes；Drug-carried coat processing is carried out by spraying collagen to the holder later, coating layer thickness is
0.1-0.2mm。
Embodiment 3
A kind of medical degradable corrosion-resistant magnesium alloy bracket of implantation heart, it is characterised in that：By the member of following mass percent
Element composition：Zn 12.8, Nd 3.75, Ca 3.7, Mn 1.25, Y 0.75, Zr 0.35, Sn 0.65, Gd 0.48, Sr 0.28,
Nd/Y5, Gd/Zr 1.37, remaining be Mg and inevitable impurity element, the component of the inevitable impurity element and
Each component weight percent is：Fe 0.002-0.005%, Ni 0.005-0.008%, Si 0.015-0.05%.
The preparation method of the medical degradable corrosion-resistant magnesium alloy bracket of the implantation heart, it is characterised in that：
(1) raw material is chosen
Purity be 99.99% Mg ingots, purity be 99.99% Zn ingots, Zn mass ratioes account for 53wt% Mg-Zn intermediate alloys,
Nd mass ratioes account for the Mg-Nd intermediate alloys of 18wt%, Gd mass ratioes account for 25% Mg-Gd intermediate alloys, Y mass ratioes account in Mg-Y
Between alloy, Zr mass ratioes account for 30% Mg-Zr intermediate alloys, other required elements are in the form of intermediate alloy or simple substance according to mesh
Mark magnesium alloy ingredient is stocked up；
(2) alloy melting
Alloy melting carries out in gas shield resistance furnace, and the fused salt for being first 2: 1 with KCl: NaCl weight ratio cleans plant crucible,
Then crucible is put into resistance furnace and is preheated to 530-550 DEG C, be packed into Mg ingots and be warming up to 700 DEG C, after Mg ingots all fusing
It is warming up to 750-800 DEG C, sequentially adds Zn ingots and Mg-Zn intermediate alloys, Mg-Nd intermediate alloys, Mg-Gd intermediate alloys, Mg-Y
Intermediate alloy, Mg-Zr intermediate alloys and remaining raw material are sufficiently stirred fusing and stand 20-30min, and melting whole process is passed through guarantor
Gas is protected, protection gas group becomes：CO2 volume ratios are that 50%, SF6 volume ratios are 1-2%, and surplus is argon gas；What fusion process was added
Refining agent accounts for the 1.2-1.5% of alloy solution weight, and refining agent ingredient is that magnesium chloride accounts for 65wt%, potassium chloride accounts for 15wt%, chlorine
Barium accounts for 15wt%, gadolinium chloride accounts for 5wt% for change, and after alloy is cooled to 720 DEG C, slagging-off is cast in is preheated to clean diameter in advance
In the mold of 30mm, to wait for that temperature reaches room temperature, casting rod is taken out, hot extrusion technique processing is ready for；
(3) hot extrusion
Homogenizing annealing is first carried out, under the conditions of 450 DEG C, 12 hours is kept the temperature, eliminates the microsegregation formed in casting process, so
Water cooling afterwards forms supersaturated solid solution；Before extrusion, using the oxide skin on coarse sandpaper removal raw material surface, it is placed on heat preservation
In stove, 30min is kept the temperature under the conditions of 200 DEG C, the temperature of extruding is set to 350 DEG C, while by mold and extrusion cylinder respectively in extruder
On holding furnace in kept the temperature, the temperature of heat preservation is identical as temperature is squeezed, and the lubricating oil used squeezes fast for vegetable lhybricant
Degree is 40-50mm/s, extrusion ratio 16:1, obtain medical degradable corrosion-resistant magnesium alloy；
(4) subsequent processing
Medical degradable corrosion-resistant magnesium alloy prepared by step (3), which carries out laser engraving, becomes holder, is then polished, and throws
It is cleaned with the acid solution of 10-15wt% after light and uses ultrasonic cleaning again, ultrasonic frequency 50-60khz is cleaned 3 times repeatedly, single
Secondary scavenging period is 10 minutes；Drug-carried coat processing is carried out by spraying collagen to the holder later, coating layer thickness is
0.1-0.2mm。
Embodiment 4
A kind of medical degradable corrosion-resistant magnesium alloy bracket of implantation heart, it is characterised in that：By the member of following mass percent
Element composition：Zn 13, Nd 3.8, Ca 3.8, Mn 1.3, Y 0.8, Zr 0.35, Sn 0.7, Gd 0.5, Sr 0.3, Nd/Y
4.75, Gd/Zr 1.43, remaining is Mg and inevitable impurity element, the component of the inevitable impurity element and each
Weight percentages of components is：Fe 0.002-0.005%, Ni 0.005-0.008%, Si 0.015-0.05%.
The preparation method of the medical degradable corrosion-resistant magnesium alloy bracket of the implantation heart, it is characterised in that：
(1) raw material is chosen
Purity be 99.99% Mg ingots, purity be 99.99% Zn ingots, Zn mass ratioes account for 53wt% Mg-Zn intermediate alloys,
Nd mass ratioes account for the Mg-Nd intermediate alloys of 18wt%, Gd mass ratioes account for 25% Mg-Gd intermediate alloys, Y mass ratioes account in Mg-Y
Between alloy, Zr mass ratioes account for 30% Mg-Zr intermediate alloys, other required elements are in the form of intermediate alloy or simple substance according to mesh
Mark magnesium alloy ingredient is stocked up；
(2) alloy melting
Alloy melting carries out in gas shield resistance furnace, and the fused salt for being first 2: 1 with KCl: NaCl weight ratio cleans plant crucible,
Then crucible is put into resistance furnace and is preheated to 530-550 DEG C, be packed into Mg ingots and be warming up to 700 DEG C, after Mg ingots all fusing
It is warming up to 750-800 DEG C, sequentially adds Zn ingots and Mg-Zn intermediate alloys, Mg-Nd intermediate alloys, Mg-Gd intermediate alloys, Mg-Y
Intermediate alloy, Mg-Zr intermediate alloys and remaining raw material are sufficiently stirred fusing and stand 20-30min, and melting whole process is passed through guarantor
Gas is protected, protection gas group becomes：CO2 volume ratios are that 50%, SF6 volume ratios are 1-2%, and surplus is argon gas；What fusion process was added
Refining agent accounts for the 1.2-1.5% of alloy solution weight, and refining agent ingredient is that magnesium chloride accounts for 65wt%, potassium chloride accounts for 15wt%, chlorine
Barium accounts for 15wt%, gadolinium chloride accounts for 5wt% for change, and after alloy is cooled to 720 DEG C, slagging-off is cast in is preheated to clean diameter in advance
In the mold of 30mm, to wait for that temperature reaches room temperature, casting rod is taken out, hot extrusion technique processing is ready for；
(3) hot extrusion
Homogenizing annealing is first carried out, under the conditions of 450 DEG C, 12 hours is kept the temperature, eliminates the microsegregation formed in casting process, so
Water cooling afterwards forms supersaturated solid solution；Before extrusion, using the oxide skin on coarse sandpaper removal raw material surface, it is placed on heat preservation
In stove, 30min is kept the temperature under the conditions of 200 DEG C, the temperature of extruding is set to 350 DEG C, while by mold and extrusion cylinder respectively in extruder
On holding furnace in kept the temperature, the temperature of heat preservation is identical as temperature is squeezed, and the lubricating oil used squeezes fast for vegetable lhybricant
Degree is 40-50mm/s, extrusion ratio 16:1, obtain medical degradable corrosion-resistant magnesium alloy；
(4) subsequent processing
Medical degradable corrosion-resistant magnesium alloy prepared by step (3), which carries out laser engraving, becomes holder, is then polished, and throws
It is cleaned with the acid solution of 10-15wt% after light and uses ultrasonic cleaning again, ultrasonic frequency 50-60khz is cleaned 3 times repeatedly, single
Secondary scavenging period is 10 minutes；Drug-carried coat processing is carried out by spraying collagen to the holder later, coating layer thickness is
0.1-0.2mm。
Comparative example 1
A kind of medical degradable corrosion-resistant magnesium alloy bracket of implantation heart, it is characterised in that：By the member of following mass percent
Element composition：Zn 12.5, Nd 2.288, Ca 3.2, Mn 1.1, Y 0.52, Zr 0.2, Sn 0.5, Gd 0.4, Sr 0.25, Nd/
Y 4.4, Gd/Zr 2, remaining is Mg and inevitable impurity element, the component and each group of the inevitable impurity element
Point weight percent is：Fe 0.002-0.005%, Ni 0.005-0.008%, Si 0.015-0.05%.
It is manufactured according to the method that embodiment 1 is recorded.Nd/Y is less than 4.55 at this time.
Comparative example 2
A kind of medical degradable corrosion-resistant magnesium alloy bracket of implantation heart, it is characterised in that：By the member of following mass percent
Element composition：Zn 12.5, Nd 3.69, Ca 3.2, Mn 1.1, Y 0.52, Zr 0.2, Sn 0.5, Gd 0.4, Sr 0.25, Nd/Y
7.1, Gd/Zr 2, remaining is Mg and inevitable impurity element, the component and each component of the inevitable impurity element
Weight percent is：Fe 0.002-0.005%, Ni 0.005-0.008%, Si 0.015-0.05%.
It is manufactured according to the method that embodiment 1 is recorded.Nd/Y is more than 7 at this time.
Comparative example 3
A kind of medical degradable corrosion-resistant magnesium alloy bracket of implantation heart, it is characterised in that：By the member of following mass percent
Element composition：Zn 12.5, Nd 3.6, Ca 3.2, Mn 1.1, Y 0.82, Zr 0.2, Sn 0.5, Gd 0.4, Sr 0.25, Nd/Y
4.4, Gd/Zr 2, remaining is Mg and inevitable impurity element, the component and each component of the inevitable impurity element
Weight percent is：Fe 0.002-0.005%, Ni 0.005-0.008%, Si 0.015-0.05%.
It is manufactured according to the method that embodiment 1 is recorded.Nd/Y is less than 4.55 at this time.
Comparative example 3
A kind of medical degradable corrosion-resistant magnesium alloy bracket of implantation heart, it is characterised in that：By the member of following mass percent
Element composition：Zn 12.5, Nd 3.6, Ca 3.2, Mn 1.1, Y 0.51, Zr 0.2, Sn 0.5, Gd 0.4, Sr 0.25, Nd/Y
7.1, Gd/Zr 2, remaining is Mg and inevitable impurity element, the component and each component of the inevitable impurity element
Weight percent is：Fe 0.002-0.005%, Ni 0.005-0.008%, Si 0.015-0.05%.
It is manufactured according to the method that embodiment 1 is recorded.Nd/Y is more than 7 at this time.
Comparative example 5
A kind of medical degradable corrosion-resistant magnesium alloy bracket of implantation heart, it is characterised in that：By the member of following mass percent
Element composition：Zn 12.6, Nd 3.65, Ca 3.3, Mn 1.15, Y 0.55, Zr 0.25, Sn 0.55, Gd 0.25, Sr 0.22,
Nd/Y6.63, Gd/Zr 1, remaining be Mg and inevitable impurity element, the component of the inevitable impurity element and
Each component weight percent is：Fe 0.002-0.005%, Ni 0.005-0.008%, Si 0.015-0.05%.
It is manufactured according to the method that embodiment 1 is recorded.Gd/Zr is less than 1.1 at this time.
Comparative example 6
A kind of medical degradable corrosion-resistant magnesium alloy bracket of implantation heart, it is characterised in that：By the member of following mass percent
Element composition：Zn 12.6、Nd 3.65、Ca 3.3、Mn 1.15、Y 0.55、Zr 0.25、Sn 0.55、Gd 0.625、Sr
0.22, Nd/Y 6.63, Gd/Zr 2.5, remaining is Mg and inevitable impurity element, the inevitable impurity element
Component and each component weight percent be：Fe 0.002-0.005%, Ni 0.005-0.008%, Si 0.015-0.05%.
It is manufactured according to the method that embodiment 1 is recorded.Gd/Zr is more than 2.4 at this time.
Comparative example 7
A kind of medical degradable corrosion-resistant magnesium alloy bracket of implantation heart, it is characterised in that：By the member of following mass percent
Element composition：Zn 12.6, Nd 3.65, Ca 3.3, Mn 1.15, Y 0.55, Zr 0.42, Sn 0.55, Gd 0.42, Sr 0.22,
Nd/Y6.63, Gd/Zr 1, remaining be Mg and inevitable impurity element, the component of the inevitable impurity element and
Each component weight percent is：Fe 0.002-0.005%, Ni 0.005-0.008%, Si 0.015-0.05%.
It is manufactured according to the method that embodiment 1 is recorded.Gd/Zr is less than 1.1 at this time.
Comparative example 8
A kind of medical degradable corrosion-resistant magnesium alloy bracket of implantation heart, it is characterised in that：By the member of following mass percent
Element composition：Zn 12.6, Nd 3.65, Ca 3.3, Mn 1.15, Y 0.55, Zr 0.16, Sn 0.55, Gd 0.42, Sr 0.22,
Nd/Y6.63, Gd/Zr 2.5, remaining is Mg and inevitable impurity element, the component of the inevitable impurity element
And each component weight percent is：Fe 0.002-0.005%, Ni 0.005-0.008%, Si 0.015-0.05%.
It is manufactured according to the method that embodiment 1 is recorded.Gd/Zr is more than 2.4 at this time.
Comparative example 9
A kind of medical degradable corrosion-resistant magnesium alloy bracket of implantation heart, it is characterised in that：By the member of following mass percent
Element composition：Zn 10, Nd 3.75, Ca 2, Mn 0.8, Y 0.75, Zr 0.35, Sn 0.65, Gd 0.48, Sr 0.28, Nd/Y
5, Gd/Zr 1.37, remaining is Mg and inevitable impurity element, the component and each group of the inevitable impurity element
Point weight percent is：Fe 0.002-0.005%, Ni 0.005-0.008%, Si 0.015-0.05%.
The preparation method of the medical degradable corrosion-resistant magnesium alloy bracket of the implantation heart, it is characterised in that：
(1) raw material is chosen
Purity be 99.99% Mg ingots, purity be 99.99% Zn ingots, Zn mass ratioes account for 53wt% Mg-Zn intermediate alloys,
Nd mass ratioes account for the Mg-Nd intermediate alloys of 18wt%, Gd mass ratioes account for 25% Mg-Gd intermediate alloys, Y mass ratioes account in Mg-Y
Between alloy, Zr mass ratioes account for 30% Mg-Zr intermediate alloys, other required elements are in the form of intermediate alloy or simple substance according to mesh
Mark magnesium alloy ingredient is stocked up；
(2) alloy melting
Alloy melting carries out in gas shield resistance furnace, and the fused salt for being first 2: 1 with KCl: NaCl weight ratio cleans plant crucible,
Then crucible is put into resistance furnace and is preheated to 530-550 DEG C, be packed into Mg ingots and be warming up to 700 DEG C, after Mg ingots all fusing
It is warming up to 750-800 DEG C, sequentially adds Zn ingots and Mg-Zn intermediate alloys, Mg-Nd intermediate alloys, Mg-Gd intermediate alloys, Mg-Y
Intermediate alloy, Mg-Zr intermediate alloys and remaining raw material are sufficiently stirred fusing and stand 20-30min, and melting whole process is passed through guarantor
Gas is protected, protection gas group becomes：CO2 volume ratios are that 50%, SF6 volume ratios are 1-2%, and surplus is argon gas；What fusion process was added
Refining agent accounts for the 1.2-1.5% of alloy solution weight, and refining agent ingredient is that magnesium chloride accounts for 65wt%, potassium chloride accounts for 15wt%, chlorine
Barium accounts for 15wt%, gadolinium chloride accounts for 5wt% for change, and after alloy is cooled to 720 DEG C, slagging-off is cast in is preheated to clean diameter in advance
In the mold of 30mm, to wait for that temperature reaches room temperature, casting rod is taken out, hot extrusion technique processing is ready for；
(3) hot extrusion
Homogenizing annealing is first carried out, under the conditions of 450 DEG C, 12 hours is kept the temperature, eliminates the microsegregation formed in casting process, so
Water cooling afterwards forms supersaturated solid solution；Before extrusion, using the oxide skin on coarse sandpaper removal raw material surface, it is placed on heat preservation
In stove, 30min is kept the temperature under the conditions of 200 DEG C, the temperature of extruding is set to 350 DEG C, while by mold and extrusion cylinder respectively in extruder
On holding furnace in kept the temperature, the temperature of heat preservation is identical as temperature is squeezed, and the lubricating oil used squeezes fast for vegetable lhybricant
Degree is 40-50mm/s, extrusion ratio 16:1, obtain medical degradable corrosion-resistant magnesium alloy；
(4) subsequent processing
Medical degradable corrosion-resistant magnesium alloy prepared by step (3), which carries out laser engraving, becomes holder, is then polished, and throws
It is cleaned with the acid solution of 10-15wt% after light and uses ultrasonic cleaning again, ultrasonic frequency 50-60khz is cleaned 3 times repeatedly, single
Secondary scavenging period is 10 minutes；Drug-carried coat processing is carried out by spraying collagen to the holder later, coating layer thickness is
0.1-0.2mm。
Comparative example 10
A kind of medical degradable corrosion-resistant magnesium alloy bracket of implantation heart, it is characterised in that：By the member of following mass percent
Element composition：Zn 12.8, Nd 3.75, Ca 3.7, Mn 1.25, Y 0.75, Zr 0.35, Sn 0.35, Gd 0.48, Sr 0.1,
Nd/Y5, Gd/Zr 1.37, remaining be Mg and inevitable impurity element, the component of the inevitable impurity element and
Each component weight percent is：Fe 0.002-0.005%, Ni 0.005-0.008%, Si 0.015-0.05%.
The preparation method of the medical degradable corrosion-resistant magnesium alloy bracket of the implantation heart, it is characterised in that：
(1) raw material is chosen
Purity be 99.99% Mg ingots, purity be 99.99% Zn ingots, Zn mass ratioes account for 53wt% Mg-Zn intermediate alloys,
Nd mass ratioes account for the Mg-Nd intermediate alloys of 18wt%, Gd mass ratioes account for 25% Mg-Gd intermediate alloys, Y mass ratioes account in Mg-Y
Between alloy, Zr mass ratioes account for 30% Mg-Zr intermediate alloys, other required elements are in the form of intermediate alloy or simple substance according to mesh
Mark magnesium alloy ingredient is stocked up；
(2) alloy melting
Alloy melting carries out in gas shield resistance furnace, and the fused salt for being first 2: 1 with KCl: NaCl weight ratio cleans plant crucible,
Then crucible is put into resistance furnace and is preheated to 530-550 DEG C, be packed into Mg ingots and be warming up to 700 DEG C, after Mg ingots all fusing
It is warming up to 750-800 DEG C, sequentially adds Zn ingots and Mg-Zn intermediate alloys, Mg-Nd intermediate alloys, Mg-Gd intermediate alloys, Mg-Y
Intermediate alloy, Mg-Zr intermediate alloys and remaining raw material are sufficiently stirred fusing and stand 20-30min, and melting whole process is passed through guarantor
Gas is protected, protection gas group becomes：CO2 volume ratios are that 50%, SF6 volume ratios are 1-2%, and surplus is argon gas；What fusion process was added
Refining agent accounts for the 1.2-1.5% of alloy solution weight, and refining agent ingredient is that magnesium chloride accounts for 65wt%, potassium chloride accounts for 15wt%, chlorine
Barium accounts for 15wt%, gadolinium chloride accounts for 5wt% for change, and after alloy is cooled to 720 DEG C, slagging-off is cast in is preheated to clean diameter in advance
In the mold of 30mm, to wait for that temperature reaches room temperature, casting rod is taken out, hot extrusion technique processing is ready for；
(3) hot extrusion
Homogenizing annealing is first carried out, under the conditions of 450 DEG C, 12 hours is kept the temperature, eliminates the microsegregation formed in casting process, so
Water cooling afterwards forms supersaturated solid solution；Before extrusion, using the oxide skin on coarse sandpaper removal raw material surface, it is placed on heat preservation
In stove, 30min is kept the temperature under the conditions of 200 DEG C, the temperature of extruding is set to 350 DEG C, while by mold and extrusion cylinder respectively in extruder
On holding furnace in kept the temperature, the temperature of heat preservation is identical as temperature is squeezed, and the lubricating oil used squeezes fast for vegetable lhybricant
Degree is 40-50mm/s, extrusion ratio 16:1, obtain medical degradable corrosion-resistant magnesium alloy；
(4) subsequent processing
Medical degradable corrosion-resistant magnesium alloy prepared by step (3), which carries out laser engraving, becomes holder, is then polished, and throws
It is cleaned with the acid solution of 10-15wt% after light and uses ultrasonic cleaning again, ultrasonic frequency 50-60khz is cleaned 3 times repeatedly, single
Secondary scavenging period is 10 minutes；Drug-carried coat processing is carried out by spraying collagen to the holder later, coating layer thickness is
0.1-0.2mm。
Comparative example 11
A kind of medical degradable corrosion-resistant magnesium alloy bracket of implantation heart, it is characterised in that：By the member of following mass percent
Element composition：Zn 13, Nd 3.8, Ca 3.8, Mn 1.3, Y 0.8, Zr 0.35, Sn 0.7, Gd 0.5, Sr 0.3, Nd/Y
4.75, Gd/Zr 1.43, remaining is Mg and inevitable impurity element, the component of the inevitable impurity element and each
Weight percentages of components is：Fe 0.002-0.005%, Ni 0.005-0.008%, Si 0.015-0.05%.
The preparation method of the medical degradable corrosion-resistant magnesium alloy bracket of the implantation heart, it is characterised in that：
(1) raw material is chosen
Purity be 99.99% Mg ingots, purity be 99.99% Zn ingots, Zn mass ratioes account for 53wt% Mg-Zn intermediate alloys,
Nd mass ratioes account for the Mg-Nd intermediate alloys of 18wt%, Gd mass ratioes account for 25% Mg-Gd intermediate alloys, Y mass ratioes account in Mg-Y
Between alloy, Zr mass ratioes account for 30% Mg-Zr intermediate alloys, other required elements are in the form of intermediate alloy or simple substance according to mesh
Mark magnesium alloy ingredient is stocked up；
(2) alloy melting
Alloy melting carries out in gas shield resistance furnace, and the fused salt for being first 2: 1 with KCl: NaCl weight ratio cleans plant crucible,
Then crucible is put into resistance furnace and is preheated to 530-550 DEG C, be packed into Mg ingots and be warming up to 700 DEG C, after Mg ingots all fusing
It is warming up to 750-800 DEG C, sequentially adds Zn ingots and Mg-Zn intermediate alloys, Mg-Nd intermediate alloys, Mg-Gd intermediate alloys, Mg-Y
Intermediate alloy, Mg-Zr intermediate alloys and remaining raw material are sufficiently stirred fusing and stand 20-30min, and melting whole process is passed through guarantor
Gas is protected, protection gas group becomes：CO2 volume ratios are that 50%, SF6 volume ratios are 1-2%, and surplus is argon gas；What fusion process was added
Refining agent accounts for the 1.2-1.5% of alloy solution weight, and refining agent ingredient is that magnesium chloride accounts for 65wt%, potassium chloride accounts for 15wt%, chlorine
Barium accounts for 15wt%, gadolinium chloride accounts for 5wt% for change, and after alloy is cooled to 720 DEG C, slagging-off is cast in is preheated to clean diameter in advance
In the mold of 30mm, to wait for that temperature reaches room temperature, casting rod is taken out, hot extrusion technique processing is ready for；
(3) hot extrusion
Homogenizing annealing is first carried out, under the conditions of 550 DEG C, 6 hours is kept the temperature, eliminates the microsegregation formed in casting process, so
Water cooling afterwards forms supersaturated solid solution；Before extrusion, using the oxide skin on coarse sandpaper removal raw material surface, it is placed on heat preservation
In stove, 30min is kept the temperature under the conditions of 200 DEG C, the temperature of extruding is set to 450 DEG C, while by mold and extrusion cylinder respectively in extruder
On holding furnace in kept the temperature, the temperature of heat preservation is identical as temperature is squeezed, and the lubricating oil used squeezes fast for vegetable lhybricant
Degree is 30mm/s, extrusion ratio 20:1, obtain medical degradable corrosion-resistant magnesium alloy；
(4) subsequent processing
Medical degradable corrosion-resistant magnesium alloy prepared by step (3), which carries out laser engraving, becomes holder, is then polished, and throws
It is cleaned with the acid solution of 10-15wt% after light and uses ultrasonic cleaning again, ultrasonic frequency 50-60khz is cleaned 3 times repeatedly, single
Secondary scavenging period is 10 minutes；Drug-carried coat processing is carried out by spraying collagen to the holder later, coating layer thickness is
0.1-0.2mm。
Performance detection is carried out in the following manner to embodiment 1-4, comparative example 1-11 products obtained therefroms：
1, Mechanics Performance Testing
Mechanical property (intensity and elongation percentage) in testing example and comparative example, correlated results is shown in Table 1.
2, anti-microbial property, corrosion resistance detection
According to " JIS Z2801-2000《Antibacterial fabricated product-antibiotic property test method and antibacterial effect》、GB/T2591-2003
《Antibiotic plastic anti-microbial property experimental method and antibacterial effect》" etc. correlation standards, the magnesium of ingredient shown in quantitative test table 1
Alloy is to the sterilizing rate after frequent infectious bacteria (Escherichia coli, staphylococcus aureus) effect.In-vitro antibacterial performance test results
2 are shown in Table, the calculation formula of wherein sterilizing rate is：Sterilizing rate (%)=[(control sample viable count-magnesium alloy viable count)/control
Sample viable count] × 100, control sample viable count is after carrying out Bacteria Culture on control sample (control sample is culture medium)
Viable count, magnesium alloy viable count refer on magnesium alloy carry out Bacteria Culture after viable count.
It is impregnated in 37 DEG C of Hank ' s simulated body fluids according to the alloy system, after impregnating 500h, weight-loss corrosion rate, test knot
Fruit is shown in Table 2.
Table 1
| Type | Yield strength (MPa) | Tensile strength (MPa) | Elongation percentage (%) |
| Embodiment 1 | ≥180 | ≥300 | ≥35 |
| Embodiment 2 | ≥200 | ≥320 | ≥32 |
| Embodiment 3 | ≥230 | ≥350 | ≥27 |
| Embodiment 4 | ≥250 | ≥380 | ≥20 |
| Comparative example 1 | ≥130 | ≥200 | ≥20 |
| Comparative example 2 | ≥150 | ≥210 | ≥18 |
| Comparative example 3 | ≥120 | ≥190 | ≥19 |
| Comparative example 4 | ≥145 | ≥208 | ≥22 |
| Comparative example 5 | ≥170 | ≥300 | ≥22 |
| Comparative example 6 | ≥180 | ≥310 | ≥21 |
| Comparative example 7 | ≥175 | ≥310 | ≥18 |
| Comparative example 8 | ≥185 | ≥310 | ≥20 |
| Comparative example 9 | ≥200 | ≥300 | ≥22 |
| Comparative example 10 | ≥210 | ≥310 | ≥20 |
| Comparative example 11 | ≥220 | ≥320 | ≥21 |
Table 2
| Type | Anti-microbial property (sterilizing rate, %) | Weight-loss corrosion rate (mm/a) |
| Embodiment 1 | ≥98.5 | ≥0.165 |
| Embodiment 2 | ≥98.5 | ≥0.135 |
| Embodiment 3 | ≥98 | ≥0.115 |
| Embodiment 4 | ≥99 | ≥0.101 |
| Comparative example 1 | ≥90 | ≥0.192 |
| Comparative example 2 | ≥91 | ≥0.190 |
| Comparative example 3 | ≥90 | ≥0.188 |
| Comparative example 4 | ≥92 | ≥0.187 |
| Comparative example 5 | ≥92 | ≥0.180 |
| Comparative example 6 | ≥91 | ≥0.181 |
| Comparative example 7 | ≥90 | ≥0.185 |
| Comparative example 8 | ≥93 | ≥0.178 |
| Comparative example 9 | ≥92 | ≥0.221 |
| Comparative example 10 | ≥93 | ≥0.230 |
| Comparative example 11 | ≥92 | ≥0.25 |
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (7)
1. a kind of medical degradable corrosion-resistant magnesium alloy bracket of implantation heart, it is characterised in that：By following mass percent
Element forms：Zn 12.5-13、Nd 3.6-3.8、Ca 3.2-3.8、Mn 1.1-1.3、Y 0.5-0.8、Zr 0.2-0.4、Sn
0.5-0.7, Gd 0.4-0.5, Sr 0.2-0.3, Nd/Y 4.55-7, Gd/Zr 1.1-2.4, remaining is for Mg and inevitably
Impurity element, the component and each component weight percent of the inevitable impurity element are：Fe 0.002-0.005%, Ni
0.005-0.008%, Si 0.015-0.05%, Mg in metallographic structure3Nd precipitate grain sizes are 0.10-0.15 μm, Mg3Y2Zn3
Precipitate grain size is 0.15-0.20 μm, Ca in metallographic structure2Mg6Zn3Precipitate grain size is 0.3-0.5 μm, and magnesium alloy crystal grain is
50-60 μm, tensile strength 300-380MPa, yield strength 180-250MPa, elongation 20-35%.
2. the medical degradable corrosion-resistant magnesium alloy bracket of implantation heart as described in claim 1, it is characterised in that：By following
The element of mass percent forms：Zn 12.6-12.8、Nd 3.65-3.75、Ca 3.3-3.7、Mn 1.15-1.25、Y
0.55-0.75, Zr 0.25-0.35, Sn 0.55-0.65, Gd 0.42-0.48, Sr 0.22-0.28, Nd/Y 4.55-7, Gd/
Zr 1.1-2.4, remaining is Mg and inevitable impurity element, the component and each component of the inevitable impurity element
Weight percent is：Fe 0.002-0.005%, Ni 0.005-0.008%, Si 0.015-0.05%.
3. the medical degradable corrosion-resistant magnesium alloy bracket of implantation heart as claimed in claim 2, it is characterised in that：By following
The element of mass percent forms：Zn 12.5、Nd 3.6、Ca 3.2、Mn 1.1、Y 0.52、Zr 0.2、Sn 0.5、Gd
0.4,0.25 Sr, Nd/Y 6.92, Gd/Zr 2, remaining is Mg and inevitable impurity element.
4. the medical degradable corrosion-resistant magnesium alloy bracket of implantation heart as claimed in claim 2, it is characterised in that：By following
The element of mass percent forms：Zn 12.6、Nd 3.65、Ca 3.3、Mn 1.15、Y 0.55、Zr 0.25、Sn 0.55、Gd
0.42,0.22 Sr, Nd/Y 6.63, Gd/Zr 1.68, remaining is Mg and inevitable impurity element.
5. the medical degradable corrosion-resistant magnesium alloy bracket of implantation heart as claimed in claim 2, it is characterised in that：By following
The element of mass percent forms：Zn 12.8、Nd 3.75、Ca 3.7、Mn 1.25、Y 0.75、Zr 0.35、Sn 0.65、Gd
0.48,0.28 Sr, Nd/Y 5, Gd/Zr 1.37, remaining is Mg and inevitable impurity element.
6. the medical degradable corrosion-resistant magnesium alloy bracket of implantation heart as claimed in claim 2, it is characterised in that：By following
The element of mass percent forms：Zn 13、Nd 3.8、Ca 3.8、Mn 1.3、Y 0.8、Zr 0.35、Sn 0.7、Gd 0.5、
Sr 0.3, Nd/Y 4.75, Gd/Zr 1.43, remaining is Mg and inevitable impurity element.
7. the preparation side of the medical degradable corrosion-resistant magnesium alloy bracket of implantation heart as claimed in any one of claims 1 to 6
Method, it is characterised in that：
(1) raw material is chosen
Purity be 99.99% Mg ingots, purity be 99.99% Zn ingots, Zn mass ratioes account for 53wt% Mg-Zn intermediate alloys,
Nd mass ratioes account for the Mg-Nd intermediate alloys of 18wt%, Gd mass ratioes account for 25% Mg-Gd intermediate alloys, Y mass ratioes account in Mg-Y
Between alloy, Zr mass ratioes account for 30% Mg-Zr intermediate alloys, other required elements are in the form of intermediate alloy or simple substance according to mesh
Mark magnesium alloy ingredient is stocked up；
(2) alloy melting
Alloy melting carries out in gas shield resistance furnace, and the fused salt for being first 2: 1 with KCl: NaCl weight ratio cleans plant crucible,
Then crucible is put into resistance furnace and is preheated to 530-550 DEG C, be packed into Mg ingots and be warming up to 700 DEG C, after Mg ingots all fusing
It is warming up to 750-800 DEG C, sequentially adds Zn ingots and Mg-Zn intermediate alloys, Mg-Nd intermediate alloys, Mg-Gd intermediate alloys, Mg-Y
Intermediate alloy, Mg-Zr intermediate alloys and remaining raw material are sufficiently stirred fusing and stand 20-30min, and melting whole process is passed through guarantor
Gas is protected, protection gas group becomes：CO2 volume ratios are that 50%, SF6 volume ratios are 1-2%, and surplus is argon gas；What fusion process was added
Refining agent accounts for the 1.2-1.5% of alloy solution weight, and refining agent ingredient is that magnesium chloride accounts for 65wt%, potassium chloride accounts for 15wt%, chlorine
Barium accounts for 15wt%, gadolinium chloride accounts for 5wt% for change, and after alloy is cooled to 720 DEG C, slagging-off is cast in is preheated to clean diameter in advance
In the mold of 30mm, to wait for that temperature reaches room temperature, casting rod is taken out, hot extrusion technique processing is ready for；
(3) hot extrusion
Homogenizing annealing is first carried out, under the conditions of 450 DEG C, 12 hours is kept the temperature, eliminates the microsegregation formed in casting process, so
Water cooling afterwards formed guarantor and solid solution；Before extrusion, using the oxide skin on coarse sandpaper removal raw material surface, it is placed on heat preservation
In stove, 30min is kept the temperature under the conditions of 200 DEG C, the temperature of extruding is set to 350 DEG C, while by mold and extrusion cylinder respectively in extruder
On holding furnace in kept the temperature, the temperature of heat preservation is identical as temperature is squeezed, and the lubricating oil used squeezes fast for vegetable lhybricant
Degree is 40-50mm/s, extrusion ratio 16:1, obtain medical degradable corrosion-resistant magnesium alloy；
(4) subsequent processing
Medical degradable corrosion-resistant magnesium alloy prepared by step (3), which carries out laser engraving, becomes holder, is then polished, and throws
It is cleaned with the acid solution of 10-15wt% after light and uses ultrasonic cleaning again, ultrasonic frequency 50-60khz is cleaned 3 times repeatedly, single
Secondary scavenging period is 10 minutes；Drug-carried coat processing is carried out by spraying collagen to the holder later, coating layer thickness is
0.1-0.2mm。
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| CN109280828A (en) * | 2018-12-10 | 2019-01-29 | 南京工程学院 | A kind of high-strength degradable implantation instrument composite material and preparation method |
| CN109554596A (en) * | 2018-12-19 | 2019-04-02 | 曾斌 | Wrought magnesium alloy and preparation method thereof with high ductibility |
| CN111228577A (en) * | 2020-01-15 | 2020-06-05 | 太原科技大学 | Medical magnesium alloy capable of being degraded in short term and preparation method thereof |
| CN112760537A (en) * | 2020-12-22 | 2021-05-07 | 上海康德莱医疗器械股份有限公司 | Magnesium alloy and preparation method and application thereof |
| CN113106312A (en) * | 2021-04-12 | 2021-07-13 | 东莞理工学院 | Degradable medical alloy and preparation method and application thereof |
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| CN111228577A (en) * | 2020-01-15 | 2020-06-05 | 太原科技大学 | Medical magnesium alloy capable of being degraded in short term and preparation method thereof |
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| CN113106312A (en) * | 2021-04-12 | 2021-07-13 | 东莞理工学院 | Degradable medical alloy and preparation method and application thereof |
| CN113106312B (en) * | 2021-04-12 | 2022-04-19 | 东莞理工学院 | Degradable medical alloy and preparation method and application thereof |
| CN116024471A (en) * | 2022-12-01 | 2023-04-28 | 中南大学 | High-strength plastic multi-water-soluble channel magnesium alloy and preparation method thereof |
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