CN101411891A - Degradable nano calcium phosphorous compound reinforced magnesium-zinc alloy bone fracture internal fixation material - Google Patents

Degradable nano calcium phosphorous compound reinforced magnesium-zinc alloy bone fracture internal fixation material Download PDF

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CN101411891A
CN101411891A CNA2008101536580A CN200810153658A CN101411891A CN 101411891 A CN101411891 A CN 101411891A CN A2008101536580 A CNA2008101536580 A CN A2008101536580A CN 200810153658 A CN200810153658 A CN 200810153658A CN 101411891 A CN101411891 A CN 101411891A
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nano calcium
alloy
internal fixation
bone fracture
zinc alloy
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CN101411891B (en
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陈民芳
叶新羽
刘德宝
由臣
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Tianjin University of Technology
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Tianjin University of Technology
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Abstract

The invention discloses a degradable nano calcium-phosphor compound reinforced magnesium-zinc alloy fracture inner fixing material. The inner fixing material comprises the following components in weight percentage: 1 to 10 percent of nano calcium-phosphor compound, 1 to 6 percent of Zn, and the balance being Mg. Nano hydroxyapatite rod-like granule or beta-calcium phosphate is used as a reinforcement to prepare a nano calcium-phosphor compound reinforced Mg-Zn composite material. Magnesium matrix is reinforced by an alloy element Zn, and refined grains of trace nano calcium-phosphor compound are added, so as to further reinforce alloy, improve alloy plasticity, and improve erosion resistance; and at the same time, the nano grains can effectively adsorb the matrix eroding product, namely hydrogen, and is induced to form a protection layer. The degrading rate of the composite material is controlled by the adding amount of the nano calcium-phosphor compound; the degraded products Mg<2+>, Zn<2+>, Ca<2+> and the like are necessary trace elements for human body. The material does not contain toxic elements, has favorable mechanical property, degrading rate and biocompatibility, can become a degradable fracture inner fixing material of new generation, avoids secondary operations, and meets clinical use requirements.

Description

A kind of degradable nano calcium phosphorous compound reinforced magnesium-zinc alloy bone fracture internal fixation material
Technical field
The present invention relates to biological bone renovating material, particularly a kind of biodegradable nano calcium phosphorous compound reinforced magnesium-zinc alloy bone fracture internal fixation material.
Background technology
Widely used clinically at present bone fracture internal fixation material is rustless steel and titanium alloy, but its stress shielding effect, harmful ion stripping phenomenon often cause graft failure.Particularly implant alloy is not degraded, and must take out by second operation after the injury of the bone healing, has increased the misery of patient's economy and the psychological burden and the human body greatly.Therefore, in operation on bone injury, replace traditional metal materials more and more to come into one's own with absorbable material.With polylactic acid and composite thereof is that the degradable polymer of representative is applied recently clinically.Yet such material mechanical performance index is on the low side, and shaping processing difficulties, price height are restricted its application.For this reason, research and development have good mechanical properties, processing characteristics, biology and a mechanical compatibility, but and the embedded material of vivo degradation become the big research in one in the field, current biomaterial forward position focus.
Magnesium alloy possesses good mechanical performance, processing characteristics, its light weight, elastic modelling quantity and bone photo are near simultaneously, biological corrosion degradation characteristic particularly, be that a kind of up-and-coming adsorbable bone is repaired substitution material by understanding recently, and corrosion product magnesium is the trace element of needed by human, and is nontoxic, can be absorbed or excrete with urine.Therefore, develop intensity height of new generation, in light weight, modulus is low, degradable absorbs bone fracture internal fixation material, not only can support and fixedly hinder body, guide new osteanagenesis, and can be after fracture recovery from illness degraded and absorbed voluntarily, stop second operation, the research that makes human body hard tissue repair the substitution material field makes a breakthrough.
Present research is thought: the corrosion degraded in vivo of magnesium alloy implantation body can make the bone regeneration around implant magnesium ion concentration increase, therefore and stimulated osteoblastic activity, during 6 weeks, the conversion of magnesium alloy surrounding bone is active, after 18 weeks, the new bone zone that forms has shown magnesium alloy excellent biological compatibility and bone guided obviously greater than degradable polymer.
At present, the research of relevant magnesium alloy biomaterial both at home and abroad mainly concentrates on the existing trade mark magnesium alloy, one class is for containing 2-10wt%Al, add the Zn of trace and the AZ series magnesium alloy of Mn element again, another kind of ZE and the serial magnesium alloy of LAE for the zinc that adds rare earth element and trace, silver and zr element that can crystal grain thinning, because human body is very harsh to the requirement of embedded material, alloy element Al can be poisoned nervous system, is to cause mentally deranged and chief culprit senile dementia; Rare earth element may cause liver poisoning; Zirconium also has the potential danger of the pulmonary carcinoma of causing, hepatocarcinoma and nasopharyngeal carcinoma.Therefore, the magnesium alloy that contains above-mentioned element all is not suitable for implant into body, especially need the material of degraded in a short time, cause the instantaneous of harmful ion concentration to exceed standard fastest period easilier, stay potential hidden danger to human body at material degradation for this class of magnesium alloy synthetism device.
Conclude the mechanical property and the biological property data of the domestic and international at present relevant magnesium alloy biomaterial research of contrast, be not difficult to find: the Mg-Zn-RE series alloy of low Zn has high relatively intensity (greater than 250MPa) and good plasticity (greater than 25%), be suitable for the bone anchor material that deep processing becomes different shape, and because wild phase I phase-Mg 3Zn 6The existence of Y and have corrosion stability preferably.Regrettably still contain rare earth composition Y in the alloying component, the biological safety of alloy is doubted.The design of alloy of bio-safety is the Mg-1Ca alloy the most in research at present, its extruding attitude tensile strength 239.63 ± 7.21, elongation 10.63 ± 0.64 (%), 2.28 ± 0.13mg/mm in the external corrosion rate 1.74mm/yr, body 2/ yr.Obviously, on the low side as its intensity of bone immobilizing material, particularly lower ductility has limited the further machine-shaping of product.In addition, the inside and outside corrosion rate also remains further to be reduced.The tensile strength 264.3 ± 10 of AZ91D-HA composite, hardness (HV 0.1) 73, elastic modelling quantity 40GPa, immersion corrosion speed 2.0-3.2mm/yr; Electrochemical corrosion speed 1.25 ± 0.16mm/yr.The requirement of the basic compound fracture immobilization material of these performances is reunited but micron order strengthens granule partial, and skewness makes the composite materials property index be lower than matrix.Although article does not provide the data of material ductility, and we know that the percentage elongation of commercially available as cast condition AZ91D alloy has only 3%, be not suitable for processing equally.And bio-safety Mg-Zn-Mn-Ca tensile strength of alloys only is 180MPa, and percentage elongation 14% is on the low side as the mechanical property of fracture fixation material.
Obviously, carry out biological safety design of alloy, improve magnesium alloy plastic deformation ability and intensity, control its corrosion degradation speed, be the problem that the biodegradable magnesium alloy fracture of exploitation internal fixation material must solve.The present invention propose to use with bone in nanometer hydroxyapatite (n-HA) or the β-Ca of inanimate matter with identical component, structure 3(PO 4) 2As the enhancing body of the function of Mg-Zn alloy and the core of grain refinement, degradation rate by nano-particle shape and addition regulation and control composite, adopt Double helix high shear melt stirring technique to prepare material simultaneously, making nanometer strengthen uniform particles is distributed on the alloy substrate, give full play to crystal grain thinning and enhancing, toughness reinforcing effect, obtain the nano calcium phosphorous compound reinforced magnesium-zinc alloy bone fracture internal fixation material.Correlational study does not appear in the newspapers both at home and abroad as yet.
Summary of the invention
The purpose of this invention is to provide a kind of poisonous element that do not contain, and have suitable mechanical property and degradation rate, satisfy the processing of bone fracture internal fixing device spare and functionating Biodegradable nano calcium phosphorous compound reinforced magnesium-zinc alloy bone fracture internal fixation material to the requirement of material.
The present invention has designed a kind of degradable nano calcium phosphorous compound reinforced magnesium-zinc alloy bone fracture internal fixation material of bio-safety for achieving the above object.Material component of the present invention is by weight percentage: nanometer hydroxyapatite (HA) or β-Ca 3(PO 4) 2Content is 1-10%, and Zn content is 1-6%, and all the other are Mg; The purity of described raw material Mg is more than or equal to 99.99%; The purity of described raw material Zn is more than or equal to 99.99%.
Preferred described nanometer hydroxyapatite is diameter 10-15nm, the stub of long 100-200 nanometer.
Preferred described β-Ca 3(PO 4) 2Spherical particle for diameter 50-80nm.
The preparation method of Biodegradable nano calcium phosphorous compound reinforced magnesium-zinc alloy bone fracture internal fixation material has following steps:
A) 1-6%Zn, 1-10% nanometer hydroxyapatite or β-Ca are got in raw-material preparation 3(PO 4) 2, all the other are Mg;
B) Zn, Mg are put into graphite crucible, be evacuated to 1 * 10 -2Pa feeds BF 6With CO 2Mist is protected, and heats 5-20min under 700-800 ℃ of temperature, makes the Mg-Zn alloy melt;
C) with nanometer hydroxyapatite or β-Ca 3(PO 4) 2Directly pour in the Double helix rheology pulper with the Mg-Zn alloy melt, feed BF 6With CO 2Mist is protected, and at 700 ℃-800 ℃, the powerful stirring after 15-45 minute is deposited in the crystallizer, obtains the pole of diameter 50-70mm;
D) extruding of material and heat treatment are heated to 400-450 ℃ with the pole of φ 50-70mm, be incubated after 5-10 hour, with its hot extrusion to φ 8-12mm; At 400-450 ℃ of solution treatment 1-3h, carry out the timeliness heat treatment between 100-200 ℃ then, the time is 10～24h.
Superiority of the present invention is: the present invention is that alloy adds element with the necessary trace elements zn of human body, improves the intensity and the corrosion resistance of magnesium; The special nano calcium phosphorous compound grain refine crystal grain that adds, when further strengthening the Mg-Zn alloy substrate, n-HA (or β-Ca 3(PO 4) 2) also can adsorb the hydrogen that the alloy substrate corrosion produces effectively, and form Ca-P chemical compound protective layer at spatial induction, the degradation rate of control alloy.The mechanical property of institute's invention material satisfies: hot strength: 250-300MPa; Elastic modelling quantity: 40-45GPa; Ductility 20-25%; Degradation rate: external, 1.0mm/ days, interior 0.1mm/ days of body.Can be processed into bone fracture internal fixing device spare-nail and hone lamella, satisfy the clinical instructions for use of human bearing's bone renovating material.
The specific embodiment
Embodiment 1:
With 4 gram Zn, 194 gram Mg put into the graphite crucible of smelting furnace, are evacuated to 1 * 10 -2Pa feeds BF 6With CO 2Mist is protected, and heats 15min under 750 ℃ of temperature, makes the Mg-Zn alloy melt;
2 gram n-HA and Mg-Zn alloy melt are directly poured in the Double helix rheology pulper, feed BF 6With CO 2Mist is protected, and at 750 ℃, the powerful stirring after 30 minutes is deposited in the crystallizer, obtains the pole of diameter 60mm;
The extruding of material and heat treatment: the pole of φ 60mm is heated to 425 ℃, is incubated after 5 hours, with its hot extrusion to φ 8mm.At 400 ℃ of solution treatment 1h, 170 ℃ are carried out the timeliness heat treatment then, and the time is 10h.
The Biodegradable nano calcium phosphorous compound reinforced magnesium-zinc alloy bone fracture internal fixation material that obtains, weight percentages of components is: n-HA 1%, Zn 2%, Mg97%.
Embodiment 2:
With 4 gram Zn, 186 gram Mg put into the graphite crucible of smelting furnace, are evacuated to 1 * 10 -2Pa feeds BF 6With CO 2Mist is protected, and heats 15min under 750 ℃ of temperature, makes the Mg-Zn alloy melt;
10 gram nanometer HA and Mg-Zn alloy melt are directly poured in the Double helix rheology pulper, feed BF 6With CO 2Mist is protected, and at 750 ℃, the powerful stirring after 30 minutes is deposited in the crystallizer, obtains the pole of diameter 60mm;
The extruding of material and heat treatment: the pole of φ 60mm is heated to 425 ℃, is incubated after 5 hours, with its hot extrusion to φ 8mm.At 400 ℃ of solution treatment 1h, 170 ℃ are carried out the timeliness heat treatment then, and the time is 10h.
The Biodegradable nano calcium phosphorous compound reinforced magnesium-zinc alloy bone fracture internal fixation material that obtains, weight percentages of components is: n-HA 5%, Zn 2%, Mg93%.
Embodiment 3:
With 4 gram Zn, 176 gram Mg put into the graphite crucible of smelting furnace, are evacuated to 1 * 10 -2Pa feeds BF 6With CO 2Mist is protected, and heats 15min under 750 ℃ of temperature, makes the Mg-Zn alloy melt;
20 gram n-HA and Mg-Zn alloy melt (total amount is 200g) are directly poured in the Double helix rheology pulper, feed BF 6With CO 2Mist is protected, and at 750 ℃, the powerful stirring after 30 minutes is deposited in the crystallizer, obtains the pole of diameter 60mm;
The extruding of material and heat treatment: the pole of φ 60mm is heated to 425 ℃, is incubated after 5 hours, with its hot extrusion to φ 8mm.At 400 ℃ of solution treatment 1h, 170 ℃ are carried out the timeliness heat treatment then, and the time is 10h.
The Biodegradable nano calcium phosphorous compound reinforced magnesium-zinc alloy bone fracture internal fixation material that obtains, weight percentages of components is: n-HA 10%, Zn 2%, Mg88%.
Embodiment 4:
With 4 gram Zn, 194 gram Mg put into the graphite crucible of smelting furnace, are evacuated to 1 * 10 -2Pa feeds BF 6With CO 2Mist is protected, and heats 15min under 750 ℃ of temperature, makes the Mg-Zn alloy melt;
With 2 gram nanometer β-Ca 3(PO 4) 2Directly pour in the Double helix rheology pulper with Mg-Zn alloy melt (total amount is 200g), feed BF 6With CO 2Mist is protected, and at 750 ℃, the powerful stirring after 30 minutes is deposited in the crystallizer, obtains the pole of diameter 60mm;
The extruding of material and heat treatment: the pole of φ 60mm is heated to 425 ℃, is incubated after 5 hours, with its hot extrusion to φ 8mm.At 400 ℃ of solution treatment 1h, 170 ℃ are carried out the timeliness heat treatment then, and the time is 10h.
The Biodegradable nano calcium phosphorous compound reinforced magnesium-zinc alloy bone fracture internal fixation material that obtains, weight percentages of components is: nanometer β-Ca 3(PO 4) 21%, Zn 2%, Mg97%.
Embodiment 5:
With 4 gram Zn, 186 gram Mg put into the graphite crucible of smelting furnace, are evacuated to 1 * 10 -2Pa feeds BF 6With CO 2Mist is protected, and heats 15min under 750 ℃ of temperature, makes the Mg-Zn alloy melt;
With 10 gram nanometer β-Ca 3(PO 4) 2Directly pour in the Double helix rheology pulper with Mg-Zn alloy melt (total amount is 200g), feed BF 6With CO 2Mist is protected, and at 750 ℃, the powerful stirring after 30 minutes is deposited in the crystallizer, obtains the pole of diameter 60mm;
The extruding of material and heat treatment: the pole of φ 60mm is heated to 425 ℃, is incubated after 5 hours, with its hot extrusion to φ 8mm.At 400 ℃ of solution treatment 1h, 170 ℃ are carried out the timeliness heat treatment then, and the time is 10h.
The Biodegradable nano calcium phosphorous compound reinforced magnesium-zinc alloy bone fracture internal fixation material that obtains, weight percentages of components is: nanometer β-Ca 3(PO 4) 25%, Zn 2%, Mg93%.
Embodiment 6:
With 4 gram Zn, 176 gram Mg put into the graphite crucible of smelting furnace, are evacuated to 1 * 10 -2Pa feeds BF 6With CO 2Mist is protected, and heats 15min under 750 ℃ of temperature, makes the Mg-Zn alloy melt;
With 20 gram nanometer β-Ca 3(PO 4) 2Directly pour in the Double helix rheology pulper with Mg-Zn alloy melt (total amount is 200g), feed BF 6With CO 2Mist is protected, and at 750 ℃, the powerful stirring after 30 minutes is deposited in the crystallizer, obtains the pole of diameter 60mm;
The extruding of material and heat treatment: the pole of φ 60mm is heated to 425 ℃, is incubated after 5 hours, with its hot extrusion to φ 8mm.At 400 ℃ of solution treatment 1h, 170 ℃ are carried out the timeliness heat treatment then, and the time is 10h.
The Biodegradable nano calcium phosphorous compound reinforced magnesium-zinc alloy bone fracture internal fixation material that obtains, weight percentages of components is: nanometer β-Ca 3(PO 4) 210%, Zn 2%, Mg88%.
Embodiment 7:
With 8 gram Zn, 182 gram Mg put into the graphite crucible of smelting furnace, are evacuated to 1 * 10 -2Pa feeds BF 6With CO 2Mist is protected, and heats 15min under 750 ℃ of temperature, makes the Mg-Zn alloy melt;
10 gram nanometer HA and Mg-Zn alloy melt are directly poured in the Double helix rheology pulper, feed BF 6With CO 2Mist is protected, and at 750 ℃, the powerful stirring after 30 minutes is deposited in the crystallizer, obtains the pole of diameter 60mm;
The extruding of material and heat treatment: the pole of φ 60mm is heated to 425 ℃, is incubated after 5 hours, with its hot extrusion to φ 8mm.At 400 ℃ of solution treatment 1h, 170 ℃ are carried out the timeliness heat treatment then, and the time is 15h.
The biodegradable n-HA that obtains strengthens magnesium-zinc alloy bone fracture internal fixation material, and weight percentages of components is: n-HA 5%, Zn 4%, Mg91%.
Embodiment 8:
With 8 gram Zn, 182 gram Mg put into the graphite crucible of smelting furnace, are evacuated to 1 * 10 -2Pa feeds BF 6With CO 2Mist is protected, and heats 15min under 750 ℃ of temperature, makes the Mg-Zn alloy melt;
With 10 gram nanometer β-Ca 3(PO 4) directly pour in the Double helix rheology pulper with the Mg-Zn alloy melt, feed BF 6With CO 2Mist is protected, and at 750 ℃, the powerful stirring after 30 minutes is deposited in the crystallizer, obtains the pole of diameter 60mm;
The extruding of material and heat treatment: the pole of φ 60mm is heated to 425 ℃, is incubated after 5 hours, with its hot extrusion to φ 8mm.At 400 ℃ of solution treatment 1h, 170 ℃ are carried out the timeliness heat treatment then, and the time is 15h.
The biodegradable n-HA that obtains strengthens magnesium-zinc alloy bone fracture internal fixation material, and weight percentages of components is: β-Ca 3(PO 4) 5%, Zn 4%, Mg91%.
Embodiment 9:
With 12 gram Zn, 178 gram Mg put into the graphite crucible of smelting furnace, are evacuated to 1 * 10 -2Pa feeds BF 6With CO 2Mist is protected, and heats 15min under 750 ℃ of temperature, makes the Mg-Zn alloy melt;
10 gram nanometer HA and Mg-Zn alloy melt are directly poured in the Double helix rheology pulper, feed BF 6With CO 2Mist is protected, and at 750 ℃, the powerful stirring after 30 minutes is deposited in the crystallizer, obtains the pole of diameter 60mm;
The extruding of material and heat treatment: the pole of φ 60mm is heated to 425 ℃, is incubated after 5 hours, with its hot extrusion to φ 8mm.At 400 ℃ of solution treatment 1h, 180 ℃ are carried out the timeliness heat treatment then, and the time is 15h.
The biodegradable n-HA that obtains strengthens magnesium-zinc alloy bone fracture internal fixation material, and weight percentages of components is: n-HA 5%, Zn 6%, Mg89%.
Embodiment 10:
With 12 gram Zn, 178 gram Mg put into the graphite crucible of smelting furnace, are evacuated to 1 * 10 -2Pa feeds BF 6With CO 2Mist is protected, and heats 15min under 750 ℃ of temperature, makes the Mg-Zn alloy melt;
With 10 gram nanometer β-Ca 3(PO 4) directly pour in the Double helix rheology pulper with the Mg-Zn alloy melt, feed BF 6With CO 2Mist is protected, and at 750 ℃, the powerful stirring after 30 minutes is deposited in the crystallizer, obtains the pole of diameter 60mm;
The extruding of material and heat treatment: the pole of φ 60mm is heated to 425 ℃, is incubated after 5 hours, with its hot extrusion to φ 8mm.At 400 ℃ of solution treatment 1h, 180 ℃ are carried out the timeliness heat treatment then, and the time is 15h.
The biodegradable n-HA that obtains strengthens magnesium-zinc alloy bone fracture internal fixation material, and weight percentages of components is: β-Ca 3(PO 4) 5%, Zn 6%, Mg89%.

Claims (4)

1, a kind of Biodegradable nano calcium phosphorous compound reinforced magnesium-zinc alloy bone fracture internal fixation material is characterized in that described material component is by weight percentage:
Nanometer hydroxyapatite (n-HA) or β-Ca 3(PO 4) 2: 1-10%;
Zn:1-6%, the purity of Zn is more than or equal to 99.99%;
All the other are Mg, and the purity of Mg is more than or equal to 99.99%.
2, Biodegradable nano calcium phosphorous compound reinforced magnesium-zinc alloy bone fracture internal fixation material according to claim 1 is characterized in that described nanometer HA is diameter 10-15nm, the stub of long 100-200 nanometer.
3, Biodegradable nano calcium phosphorous compound reinforced magnesium-zinc alloy bone fracture internal fixation material according to claim 1 is characterized in that described β-Ca 3(PO 4) 2Spherical particle for diameter 50-80nm.
4, the preparation method of Biodegradable nano calcium phosphorous compound reinforced magnesium-zinc alloy bone fracture internal fixation material as claimed in claim 1 has following steps:
A) 1-6% Zn, 1-10% nanometer hydroxyapatite or β-Ca are got in raw-material preparation 3(PO 4) 2, all the other are Mg;
B) Zn, Mg are put into graphite crucible, be evacuated to 1 * 10 -2Pa feeds BF 6With CO 2Mist is protected, and heats 5-20min under 700-800 ℃ of temperature, makes the Mg-Zn alloy melt;
C) with nanometer hydroxyapatite or β-Ca 3(PO 4) 2With above-mentioned b) the Mg-Zn alloy melt that makes directly pours in the Double helix rheology pulper, feeds BF behind the evacuation 6With CO 2Mist is protected, and at 700 ℃-800 ℃, the powerful stirring after 15-45 minute is deposited in the crystallizer, obtains the pole of diameter 50mm-70mm;
D) extruding of material and heat treatment are with c) the 50mm-70mm pole that makes is heated to 400-450 ℃, is incubated after 5-10 hour, and hot extrusion is to φ 8-12mm; At 400-450 ℃ of solution treatment 1-3h, carry out the timeliness heat treatment between 100-200 ℃ then, the time is 10～24h.
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CN102634716A (en) * 2012-04-28 2012-08-15 中南大学 Preparation method of magnesium-zinc-tricalcium phosphate composite material by powder hot pressed sintering
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CN104313439A (en) * 2014-11-04 2015-01-28 哈尔滨理工大学 Preparation method of degradable magnesium alloy bone plate set
CN104313439B (en) * 2014-11-04 2016-05-11 哈尔滨理工大学 A kind of preparation method of degradable magnesium alloy bone plate
CN106904958A (en) * 2017-04-07 2017-06-30 重庆大学 Preparation method of HA porous ceramics with suitable porosity and mechanical strength and products thereof
CN106904958B (en) * 2017-04-07 2020-07-14 重庆大学 Preparation method of HA porous ceramic with proper porosity and mechanical strength and product thereof
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