Background technology
Medical metal material will occupy critical role in technical field of biological material future, this is because medical metal material tool
Standby excellent mechanical performance.316L rustless steel, titanium or titanium alloy and Co-Cr alloy etc. have obtained wide with excellent mechanical property
General application.But there is a common problem in the existing metal implant material such as rustless steel and titanium alloy is the power with biological bone
Learn poor compatibility.The tensile strength of rustless steel, titanium alloy etc. is higher more than 5 times than nature bone, elastic modelling quantity the highest 10 times with
On.Such material can produce the biggest " stress shielding " effect to local bone tissue after implanting human body.Suffered by matrix bone
Stress stimulation declines, and negative balance occurs in bone remodeling, causes bone resorption to increase, and bone formation reduces, and induces blocking property bone loss.With
Time these materials when as provisional embedded material such as intravascular stent, nail, hone lamella, spicule, need to carry out second operation and take
Go out, patient is caused the burden of economy and health.
In order to solve the problems referred to above, biodegradable absorbing material is researched and developed by relevant technical staff, the most at present and
Speech, biodegradable absorbing material is mainly polymer and some ceramic material, such as polylactic acid, calcium phosphate etc., but due to mesh
The character impact of polymeric material used by before itself, as on the low side in mechanical property, processing difficulties, the internal decomposition more acid of generation
And easily cause inflammation and the problem of swelling, limit its application;The plasticity and toughness of ceramic material are poor, make volume very with this material
Little vascular stent material is extremely difficult, and percent defective is high.
Magnesium is biomechanical property and the immediate metal material of human bone in current all metal materials.The bullet of magnesium alloy
Property is about 45GPa, than the biomaterial titanium alloy (100GPa) being widely used at present closer to the elastic modelling quantity of people's bone
(20GPa), can effectively reduce " stress-shielding effect ", promote symphysis.Magnesium alloy has higher yield strength simultaneously, can
To bear bigger load, it is applied to osseous tissue carrying position, endovascular stent can also be applied to, play the work of support blood vessels
With.But, traditional magnesium alloy exists that corrosion resistance is poor, plastic deformation ability is poor.Therefore, exploitation plastic deformation ability is strong, high resistance to
The biological medical magnesium alloy of erosion property is effectively to reduce its corrosion degradation speed in human body for promoting that magnesium alloy is cured at biology
The application in field is most important.
Alloying is raising magnesium alloy plastic deformation ability, improves corrosion stability of magnesium alloy energy, solves its corrosion degradation speed
The effective way of too fast problem.Research finds, aluminum adds in magnesium alloy can put forward heavy alloyed corrosion resisting property, play solution strengthening and
Precipitation strength effect, but Al element can produce harm, should not be used in biological medical magnesium alloy material health.It addition, it is dilute
The addition of earth elements also can significantly improve the decay resistance of magnesium alloy, and stress-free corrosion tendency, but have been reported that and show, dilute
Earth elements is easily enriched with in brain, lacks certain biological safety.At present, study and more meet biocompatibility requirement
Complex magnesium alloy has Mg-Mn-Sr-Ca, Mg-Zn-Ca, Mg-Zn-Mn-Ca etc., but the combination property of these materials above-mentioned is still
Have much room for improvement.
Summary of the invention
It is an object of the invention to take into account good plastic deformation ability and higher anti-corrosion for current anastomosis staple material
The problem of property, it is provided that in a kind of organism with high corrosion-resistant, good plastic deformation ability and good biocompatibility
Degradable anastomosis staple and production technology thereof.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of biological degradable in vivo anastomosis staple, the most composed of the following components:
Zn 2-6%, Mn 2-5%, Sn 0.1-1%, Ag 1.5-2%, HA powder 0.5-2%, surplus is Mg.
As preferably, described HA powder is nano bar-shape HA powder, and its particle diameter is 20-60nm.
Hydroxyapatite (HA) is as a kind of composition of nature bone, and the dissolubility in human body environment is the lowest, and it closes at magnesium
Interpolation in gold, on the one hand can regulate the mechanical performance of magnesium alloy bracket, make the mechanical performance portion different from organism of support
The mechanical property of the bone of position matches, and alleviates or avoids stress-shielding effect, on the other hand the interpolation of hydroxyapatite, is conducive to
The growth of osteocyte and propagation, can improve the corrosion resisting property of magnesium alloy bracket to a certain extent.The HA selected in the present invention
The HA that article No. is MH01 provided for Nanjing Ai Purui nano material company limited.
As preferably, the degree of purity of described Zn is more than 99.99%.
Zinc (Zn) is alloying element relatively common in a kind of magnesium alloy, can improve the creep-resistant property of foundry goods, permissible
Increase the mobility of melt, weak grain refiner, have formation Micro shrinkage tendency, have precipitation strength effect.
As preferably, the degree of purity of described Sn is more than 99.99%.
Stannum (Sn) can improve corrosion resistance and the intensity of magnesium alloy.
As preferably, the degree of purity of described Ag is more than 99.99%.
Silver (Ag) solid solubility maximum in Mg can reach 15%, and after Ag dissolves in Mg, clearance-type solid solution atom causes non-
Spherical symmetric distorts, thus produces the strongest solid solution strengthening effect and ageing strengthening effect, and in magnesium alloy, the addition of Ag can be compared
Put forward heavy alloyed tensile strength and yield strength more significantly.
As preferably, the degree of purity of described Mg is more than 99.99%.
As preferably, the degree of purity of described Mn is more than 99.99%.
The manganese (Mn) solid solubility in Mg is little, does not forms compound with Mg.Mn can propose heavy alloyed welding with crystal grain thinning
Performance.But the invigoration effect to alloy is smaller.In Castingother magnesium alloy or wrought magnesium alloy, often add a small amount of
Mn, improves the corrosion resisting property of magnesium alloy.Mn can form high melting compound with the impurity F e of serious infringement corrosion stability of magnesium alloy energy
And be precipitated out, refine precipitated product, increase creep resistance, put forward heavy alloyed corrosion resisting property.
The production technology of a kind of above-mentioned biological degradable in vivo anastomosis staple, comprises the following steps:
1. the preparation technology of magnesium alloy:
1) each component is weighed in proportion;
2) the above-mentioned each component weighed is dried 1-2 hour in the baking oven of 100 DEG C;
3) Zn, Mn, Sn, Ag and Mg of weighing are added to graphite crucible, after evacuation, be passed through BF6And CO2Mixed gas make
For protective gas, after making each component be completely dissolved under conditions of 700-800 DEG C, keep 10-20min.
4) HA powder is joined melting to have in the graphite crucible of Zn, Mn, Sn, Ag and Mg, and stir, obtain melting molten
Liquid;
5) melting solution is poured in the graphite jig dried in advance, obtain magnesium alloy ingot;
2. the Technology for Heating Processing of magnesium alloy:
1) magnesium alloy ingot solid solution 10 hours under conditions of 540 DEG C that will obtain in the preparation technology of magnesium alloy;
2) being put into by the magnesium alloy ingot after solid solution in the mould preheated in advance, preheating temperature is 220-480 DEG C, at 300-500 DEG C
At a temperature of be squeezed into section bar, i.e. anastomosis staple;
3) by step 2) in section bar make annealing treatment under conditions of 500 DEG C;
4) section bar of the process of annealing in step 3) is carried out alkali heat-treatment.
As preferably, described base extraction comprises the steps:
1) at NaHCO3-NaOH-Mg(OH)2Solution (pH9.3) soaks 24 hours, takes out natural air drying;
2) it is incubated 10h, air cooling at 773K.
Advantages of the present invention and providing the benefit that:
(1) one biology degradable in vivo anastomosis staple of the present invention can natural degradation in vivo, reach after medical effect
In regular hour can be from vivo degradation, it is to avoid second operation causes the burden of economy and health to patient.
(2) one biology degradable in vivo anastomosis staple of the present invention avoids use Al and rare earth gold in composition design
Belong to, from the selection of material, ensure that the biological safety 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 the inner implantation material requirement to corrosion rate, and this material is without obvious cytotoxicity, blood
Liquid phase capacitive is good, can meet the inner implantation material requirement to biocompatibility.
(4) one biology degradable in vivo anastomosis staple of the present invention uses hydroxyapatite (HA), on the one hand can regulate magnesium
The mechanical performance of alloy bracket, makes the mechanical performance of support match with the mechanical property of the bone of organism different parts, alleviates
Or avoid stress-shielding effect, the opposing party to be conducive to growth and the propagation of osteocyte, magnesium alloy can be improved to a certain extent
The corrosion resisting property of support.
(5) production technology of a kind of biological degradable in vivo anastomosis staple of the present invention, in heat treatment process, at profile extrusion
After molding, section bar is made annealing treatment at 500 DEG C, improve the corrosion resistance of magnesium alloy from inside;Follow-up alkali heat-treatment
The corrosion resistance of magnesium alloy is improve from outside.
Detailed description of the invention
The present invention is further detailed explanation now.
A kind of biological degradable in vivo anastomosis staple, its component composition see table by mass percentage:
The production technology of a kind of biological 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 1-2 hour in the baking oven of 100 DEG C;
3) Zn, Mn, Sn, Ag and Mg of weighing are added to graphite crucible, after evacuation, be passed through BF6And CO2Mixed gas make
For protective gas, after making each component be completely dissolved under conditions of 700-800 DEG C, keep 10-20min.
4) HA powder is joined melting to have in the graphite crucible of Zn, Mn, Sn, Ag and Mg, and stir, obtain melting molten
Liquid;
5) melting solution is poured in the graphite jig dried in advance, obtain magnesium alloy ingot;
2. the Technology for Heating Processing of magnesium alloy:
1) magnesium alloy ingot solid solution 10 hours under conditions of 540 DEG C that will obtain in the preparation technology of magnesium alloy;
2) being put into by the magnesium alloy ingot after solid solution in the mould preheated in advance, preheating temperature is 220-480 DEG C, at 300-500 DEG C
At a temperature of be squeezed into section bar, i.e. anastomosis staple;
3) by step 2) in section bar make annealing treatment under conditions of 500 DEG C;
4) to the section bar of the process of annealing in step 3) at NaHCO3-NaOH-Mg(OH)2Solution (pH9.3) soaks 24 hours,
Take out natural air drying;
5) section bar step 4) obtained is incubated 10h, air cooling at 773K, obtains biological degradable in vivo anastomosis staple.
The anastomosis staple section bar obtaining each embodiment carries out mechanical property, decay resistance and cytotoxicity to be tested,
Its structure such as following table:
The anastomosis staple that the present invention provides not only has good mechanical property, has more the corrosion resisting property of excellence, solves at present
Anastomosis staple material can not take into account good plastic deformation ability and the problem of relatively high corrosion-resistant, and catabolite is nontoxic, biological
The compatibility is good, has bigger potential application at biomedical sector.
With the above-mentioned desirable embodiment according to the present invention for enlightenment, by above-mentioned description, relevant staff is complete
Entirely can carry out various change and amendment in the range of without departing from this invention technological thought.The technology of this invention
The content that property scope is not limited in description, it is necessary to determine its technical scope according to right.