Background technology
Medical metal material future will occupy an important position in technical field of biological material, this is because medical metal material has
Standby excellent mechanical performance.316L stainless steels, titanium or titanium alloy and Co-Cr alloys etc. have been obtained extensively with excellent mechanical property
General application.But it is the power with biological bone there are a common problem in the existing metal implant material such as stainless steel and titanium alloy
Learn poor compatibility.5 times higher than nature bone of tensile strength of stainless steel, titanium alloy etc. or more, elasticity modulus be even more high 10 times with
On.Very big " stress shielding " effect can be generated to local bone tissue after such material implantation human body.Due to suffered by matrix bone
Stress stimulation declines, and bone remodeling negative balance occurs, bone information is caused to increase, and bon e formation is reduced, and induces blocking property bone loss.Together
When these materials taken, it is necessary to carry out second operation when as provisional implantation material such as intravascular stent, nail, bone plate, spicule
Go out, economy and the burden of body are caused to patient.
To solve the above-mentioned problems, related technical staff researches and develops biodegradable absorbing material, with regard to current
Speech, biodegradable absorbing material are mainly polymer and some ceramic materials, such as polylactic acid, calcium phosphate, but due to mesh
The property of preceding polymer material used in itself influences, as mechanical property is relatively low, processing difficulties, the more acid of decomposition generation in vivo
And easily trigger the problem of inflammation and swelling, limit its application;The plasticity and toughness of ceramic material are poor, and volume is made very with this material
Small vascular stent material is extremely difficult, and rejection rate is high.
Magnesium is biomechanical property and the immediate metal material of human body bone in current all metal materials.The bullet of magnesium alloy
Property be about 45GPa, than the biomaterial titanium alloy (100GPa) that is widely used at present closer to the elasticity modulus of people's bone
(20GPa) can be reduced effectively " stress-shielding effect ", promote symphysis.Magnesium alloy has higher yield strength simultaneously, can
To bear larger load, applied to bone tissue carrying position, endovascular stent can also be applied to, play the work of support blood vessels
With.But there are corrosion resistance is poor, plastic deformation ability force difference for traditional magnesium alloy.Therefore, it is strong, high resistance to develop plastic deformation ability
The biological medical magnesium alloy of corrosion is effectively to reduce its corrosion degradation rate in human body for magnesium alloy is promoted to be cured in biology
The application in field is most important.
Alloying is to improve magnesium alloy plastic deformation ability, improve corrosion stability of magnesium alloy energy, solve its corrosion degradation rate
The effective way of too fast problem.The study found that aluminium, which is added in magnesium alloy, can improve the corrosion resisting property of alloy, play solution strengthening and
Precipitation enhancement, but Al elements can generate health harm, should not be used in biological medical magnesium alloy material.It is in addition, dilute
The addition of earth elements can also significantly improve the corrosion resistance of magnesium alloy, and stress-free corrosion is inclined to, but have been reported that show it is dilute
Earth elements are easily enriched in brain, lack certain biological safety.At present, the more biocompatibility requirement that meets is studied
Complex magnesium alloy has Mg-Mn-Sr-Ca, Mg-Zn-Ca, Mg-Zn-Mn-Ca etc., but the comprehensive performance of these above-mentioned materials is still
Have much room for improvement.
The content of the invention
The purpose of the present invention is be directed to current anastomosis staple material to take into account good plastic deformation ability and higher anti-corrosion
It the problem of property, provides in a kind of organism with high corrosion-resistant, good plastic deformation ability and good biocompatibility
Degradable anastomosis staple and its production technology.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of biology degradable in vivo anastomosis staple, it is composed of the following components by mass percentage:
Zn 2-6%, Mn 2-5%, Sn 0.1-1%, Ag 1.5-2%, HA powder 0.5-2%, surplus Mg.
Preferably, the HA powder is nano bar-shape HA powder, grain size 20-60nm.
Hydroxyapatite(HA)As a kind of ingredient of nature bone, the solubility in human body environment is very low, is closed in magnesium
On the one hand addition in gold can adjust the mechanical performance of magnesium alloy bracket, make the mechanical performance of stent and organism difference portion
The mechanical property of the bone of position matches, and alleviates or avoids stress-shielding effect, the addition of another aspect hydroxyapatite is conducive to
The growth of osteocyte and multiplication can improve the corrosion resisting property of magnesium alloy bracket to a certain extent.The HA selected in the present invention
The HA that the article No. provided for Nanjing Ai Purui nano materials Co., Ltd is MH01.
Preferably, the degree of purity of the Zn is more than 99.99%.
Zinc(Zn)It is alloying element relatively common in a kind of magnesium alloy, the creep-resistant property of casting can be improved, it can be with
Increase the mobility of melt, weak grain refiner to form Micro shrinkage tendency, there is precipitation enhancement.
Preferably, the degree of purity of the Sn is more than 99.99%.
Tin(Sn)The corrosion resistance and intensity of magnesium alloy can be improved.
Preferably, the degree of purity of the Ag is more than 99.99%.
Silver(Ag)Solid solubility maximum in Mg can reach 15%, and after Ag is dissolved in Mg, clearance-type solid solution atom causes non-
Spherical symmetric distorts, so as to generate very strong solid solution strengthening effect and ageing strengthening effect, in magnesium alloy the addition of Ag can compare
The tensile strength and yield strength of alloy are improved more significantly.
Preferably, the degree of purity of the Mg is more than 99.99%.
Preferably, the degree of purity of the Mn is more than 99.99%.
Manganese(Mn)Solid solubility in Mg is small, does not form compound with Mg.Mn with crystal grain thinning, can improve the weldering of alloy
Connect performance.It is but smaller to the invigoration effect of alloy.In other cast magnesium alloys or wrought magnesium alloy, often add in a small amount of
Mn, improve the corrosion resisting property of magnesium alloy.Mn can form high-melting-point chemical combination with the impurity F e of serious damage corrosion stability of magnesium alloy energy
Object and be precipitated out, refine precipitated product, increase creep resistance, improve the corrosion resisting property of alloy.
A kind of production technology of above-mentioned biological degradable in vivo anastomosis staple, comprises the following steps:
1. the preparation process of magnesium alloy:
1)Each component is weighed in proportion;
2)The above-mentioned each component weighed is dried in 100 DEG C of baking oven 1-2 it is small when;
3)Zn, Mn, Sn, Ag and Mg for weighing are added in graphite crucible, after vacuumizing, are passed through BF3And CO2Gaseous mixture
Body after being completely dissolved each component under conditions of 700-800 DEG C, keeps 10-20min as protective gas;
4)HA powder is added to melting has in the graphite crucible of Zn, Mn, Sn, Ag and Mg, and stirs evenly, and it is molten to obtain melting
Liquid;
5)Melting solution is poured into the graphite jig dried in advance, obtains magnesium alloy ingot;
2. the heat treatment process of magnesium alloy:
1)By the magnesium alloy ingot obtained in the preparation process of magnesium alloy when solid solution 10 is small under conditions of 540 DEG C;
2)Magnesium alloy ingot after solid solution is put into the mold preheated in advance, preheating temperature is 220-480 DEG C, in 300-
Section bar, i.e. anastomosis staple are squeezed at a temperature of 500 DEG C;
3)By step 2)In section bar made annealing treatment under conditions of 500 DEG C;
4)To step 3)The section bar of the processing of middle annealing carries out alkali heat-treatment.
Preferably, the base extraction includes the following steps:
1)In NaHCO3-NaOH-Mg(OH)2Solution(pH9.3)It is middle impregnate 24 it is small when, take out natural air drying;
2)10h is kept the temperature in 773K, it is air-cooled.
Advantages of the present invention and advantageous effect are:
(1) a kind of biological degradable in vivo anastomosis staple of the present invention can natural degradation in vivo, reach medical effect
It can be avoided second operation from internal degradation and cause economy and the burden of body to patient within the regular hour after fruit.
(2) a kind of biological degradable in vivo anastomosis staple of the present invention is avoided in composition design using Al and rare earth gold
Belong to, the biological safety of material is ensure that from the selection of material.
(3) a kind of biological degradable in vivo anastomosis staple of the present invention have high corrosion-resistant, good plastic deformation ability and
Good biocompatibility meets requirement of the inner implantation material to corrosion rate, and the material is without apparent cytotoxicity, blood
Liquid phase capacitive is good, can meet requirement of the inner implantation material to biocompatibility.
(4)A kind of biological degradable in vivo anastomosis staple of the present invention uses hydroxyapatite(HA), on the one hand can adjust magnesium
The mechanical performance of alloy bracket, the mechanical performance and the mechanical property of the bone of organism different parts for making stent match, and alleviate
Or stress-shielding effect is avoided, the opposing party is conducive to growth and the multiplication of osteocyte, can improve magnesium alloy to a certain extent
The corrosion resisting property of stent.
(5)A kind of production technology of biological degradable in vivo anastomosis staple of the present invention, in heat treatment process, is squeezed in section bar
After molded, section bar at 500 DEG C is made annealing treatment, the corrosion resistance of magnesium alloy is improved from inside;At subsequent alkali heat
Manage the corrosion resistance that magnesium alloy is improved from outside.
Specific embodiment
The present invention is described in further detail now.
A kind of biology degradable in vivo anastomosis staple, by mass percentage its component composition see the table below:
A kind of production technology of biology degradable in vivo anastomosis staple, comprises the following steps:
1)Each component is weighed in proportion;
2)The above-mentioned each component weighed is dried in 100 DEG C of baking oven 1-2 it is small when;
3)Zn, Mn, Sn, Ag and Mg for weighing are added in graphite crucible, after vacuumizing, are passed through BF3And CO2Gaseous mixture
Body after being completely dissolved each component under conditions of 700-800 DEG C, keeps 10-20min as protective gas;
4)HA powder is added to melting has in the graphite crucible of Zn, Mn, Sn, Ag and Mg, and stirs evenly, and it is molten to obtain melting
Liquid;
5)Melting solution is poured into the graphite jig dried in advance, obtains magnesium alloy ingot;
2. the heat treatment process of magnesium alloy:
1)By the magnesium alloy ingot obtained in the preparation process of magnesium alloy when solid solution 10 is small under conditions of 540 DEG C;
2)Magnesium alloy ingot after solid solution is put into the mold preheated in advance, preheating temperature is 220-480 DEG C, in 300-
Section bar, i.e. anastomosis staple are squeezed at a temperature of 500 DEG C;
3)By step 2)In section bar made annealing treatment under conditions of 500 DEG C;
4)To step 3)The section bar of the processing of middle annealing is in NaHCO3-NaOH-Mg(OH)2Solution(pH9.3)Middle immersion 24 is small
When, take out natural air drying;
5)By step 4)Obtained section bar keeps the temperature 10h in 773K, air-cooled, obtains biological degradable in vivo anastomosis staple.
Mechanical property, corrosion resistance and cytotoxicity are carried out to the anastomosis staple section bar that each embodiment obtains to test,
Its structure such as following table:
Anastomosis staple provided by the invention not only has good mechanical property, with more excellent corrosion resisting property, solves
Anastomosis staple material cannot take into account good plastic deformation ability and the problem of compared with high corrosion-resistant at present, and catabolite is nontoxic,
Good biocompatibility has larger potential application in biomedical sector.
Using above-mentioned desirable embodiment according to the invention as enlightenment, by above-mentioned description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property scope is not limited to the content on specification, it is necessary to determine its technical scope according to right.