CN107794424B - A kind of Biological magnesium alloy and preparation method thereof with antibacterial functions - Google Patents

A kind of Biological magnesium alloy and preparation method thereof with antibacterial functions Download PDF

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CN107794424B
CN107794424B CN201711017081.6A CN201711017081A CN107794424B CN 107794424 B CN107794424 B CN 107794424B CN 201711017081 A CN201711017081 A CN 201711017081A CN 107794424 B CN107794424 B CN 107794424B
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magnesium alloy
tio
biological magnesium
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antibacterial functions
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CN107794424A (en
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帅词俊
高成德
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Central South University
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Abstract

The present invention relates to a kind of Biological magnesium alloy with antibacterial functions and the methods for preparing the Biological magnesium alloy using selective laser smelting technology.The Biological magnesium alloy with antibacterial functions is by Biological magnesium alloy matrix and the nano-TiO being uniformly distributed in magnesium alloy substrate2It constitutes；In the Biological magnesium alloy with antibacterial functions, nano-TiO2Mass percentage be 3-7%.Preparation method are as follows: design proportion is pressed, with taking nano-TiO2Powder and Biological magnesium alloy powder under protective atmosphere, through high speed ball milling, will obtain mixed-powder with taking powder to be placed in ball mill；Then under protective atmosphere, there is the Biological magnesium alloy of antibacterial functions by selective laser fusing preparation.Biological magnesium alloy prepared by the present invention has both excellent anti-microbial property and cell compatibility and improved mechanical property and degradation rate appropriate.When it is used as implant material, advantage is had more than current material.

Description

A kind of Biological magnesium alloy and preparation method thereof with antibacterial functions
Technical field
(SLM) technology system is melted the present invention relates to a kind of Biological magnesium alloy with antibacterial functions and using selective laser The method of the standby Biological magnesium alloy, belongs to Biological magnesium alloy and designs and manufactures field.
Background technique
In recent years, Biological magnesium alloy becomes new with its good biocompatibility, mechanical property and biodegradable characteristics The medical embedded material of a generation.As metal material, the fracture toughness of Biological magnesium alloy is higher than bioceramic material, and its bullet Property modulus and compressive yield strength then than other metal implant materials closer to human body bone, conventional metals implantation can be effectively relieved in this The stress-shielding effect that material generates, plays a significant role tissue repair, union etc..And Biological magnesium alloy Yi Ti Corrode in interior environment, to realize degradable, can avoid second operation to patient bring pain and financial burden, together When degradation generate magnesium ion be one of substance needed for human metabolism.However, Biological magnesium alloy lacks antibacterial functions, plant Easily there is bacterium infection after entering in vivo, and then leads to treatment failure.Therefore, a kind of Biological magnesium alloy for having antibacterial functions is developed It is of great significance.
Antibacterial agent is to be divided into organic antibacterial agent and inorganic anti-to inhibit and kill microorganism growth preparation as the main purpose Microbial inoculum two types.Wherein inorganic antiseptic has many advantages, such as long-acting, broad-spectrum, is the research hotspot in the current field.Inorganic anti- In microbial inoculum, nano-TiO2It is a kind of excellent oxide semiconductor photoactivation antibacterial agent, sterilization process is under illumination condition It carries out: TiO2Oxygen effect in light absorbing energy production electrons and holes, subsequent electronics and environment generates negative oxygen ion, and Hole can generate hydroxyl radical free radical with water.Negative oxygen ion and hydroxyl radical free radical have strong oxidizing property, can damage the thin of bacterium Born of the same parents' plate, cell membrane and DNA, to achieve the effect that sterilization.These characteristics make nano-TiO2Improving Biological magnesium alloy antibacterial Aspect of performance has shown great potentiality.
However, existing study limitation is in by nano-TiO2It is applied to biological magnesium as surface covering or coating additive to close Jin Zhong, surface covering can only make Biological magnesium alloy have antibacterial action at implantation initial stage, and after coating breaks down falls off, implantation material Still easily there is bacterium infection situation in surrounding.Also, the TiO of surface covering high level2It may be enriched with and lead in implant site It causes local concentration excessively high, and then toxicity is generated to surrounding tissue cells.Therefore, how Biological magnesium alloy to be made to have anti-microbial property Meanwhile it avoiding becoming the histiocytic adverse effect of implant site the key for realizing the application of its tissue repair.
Summary of the invention
The existing Biological magnesium alloy of the present invention provides a kind of life with antibacterial functions in deficiency present on structure and function Object magnesium alloy and preparation method thereof.
A kind of Biological magnesium alloy with antibacterial functions of the present invention, the Biological magnesium alloy with antibacterial functions is by biology Magnesium alloy substrate and the nano-TiO being uniformly distributed in magnesium alloy substrate2It constitutes；The Biological magnesium alloy with antibacterial functions In, nano-TiO2Mass percentage be 3-7%, preferably 4-6%, further preferably 5%.
A kind of Biological magnesium alloy with antibacterial functions of the present invention, nano-TiO2It is uniformly dispersed in Biological magnesium alloy matrix Crystal boundary on.
A kind of Biological magnesium alloy with antibacterial functions of the present invention, nano-TiO2Partial size be 10-100nm, preferably 30- 80nm。
A kind of preparation method of the Biological magnesium alloy with antibacterial functions of the present invention, includes the following steps:
Step 1
By design proportion, with taking nano-TiO2Powder and Biological magnesium alloy powder, will be with the TiO taken2Powder and biological magnesium close Bronze end is placed in ball mill, and under protective atmosphere, control rotational speed of ball-mill is 200-400rad/min, and ball milling 4-8h is mixed Close powder.
Step 2
Using mixed-powder obtained by step 1 as raw material, it is passed through argon gas protective gas, controls H2O and O2Concentration is lower than 20ppm, There is the Biological magnesium alloy of antibacterial functions by selective laser fusing preparation；Selective laser fusing preparation has the life of antibacterial functions When object magnesium alloy, control laser power is 70-120W, preferably 85-100W, further preferably 90W, scanning speed 100- 600mm/min, preferably 200-350mm/min, further preferably 300mm/min, spot diameter are 50-200 μm, are preferably 80-150 μm, further preferably 90 μm.
A kind of preparation method of the Biological magnesium alloy with antibacterial functions of the present invention, the nano-TiO2The partial size of powder is small In equal to 100nm.
A kind of preparation method of the Biological magnesium alloy with antibacterial functions of the present invention, the partial size of the Biological magnesium alloy powder It is 50-70 μm.
A kind of preparation method of the Biological magnesium alloy with antibacterial functions of the present invention, the Biological magnesium alloy is preferably AZ91 Magnesium alloy powder.
The present invention promotes the uniform mixing of powder by optimizing milling parameters as far as possible, to guarantee nano-TiO2Powder The chemical activity of itself and big specific surface area.When Ball-milling Time is too long and/or rotational speed of ball-mill is excessively high, then impurity can be introduced, no The biocompatibility of Biological magnesium alloy is only reduced, and easily generates stress and concentrates damage magnesium alloy mechanical property, is aggravated simultaneously The degradation process of potential corrosion quickening magnesium alloy.When rotational speed of ball-mill is too low and/or Ball-milling Time is too short, it may appear that than more serious Nano-TiO2Agglomeration, second prepared is mutually thicker or volume becomes larger, this makes the mechanical property and drop of alloy Solve reduced performance, and nano-TiO2Chemical activity can reduce.Meanwhile the present invention is to nano-TiO2The dosage of powder is also to have It is strict with, works as nano-TiO2When powder is exceeded, during ball milling, titanium dioxide is difficult to disperse, and is exceedingly fast in this technique Solidification rate under conditions of, assemble to form titanium dioxide phase in grain boundaries, generate stress concentrate, reduce mechanical property；And and Galvanic corrosion occurs for matrix, accelerates degradation rate.Work as nano-TiO2When powder dosage is less, the anti-microbial property of magnesium alloy sharply under Drop, is not achieved demand.
A kind of preparation method of the Biological magnesium alloy with antibacterial functions of the present invention, the protective atmosphere are high-purity argon gas gas Atmosphere.The high-purity argon gas is the argon gas that purity is more than or equal to 99.999%.
Principle and advantage
The present invention has been attempted for the first time by nano-TiO2It makes an addition in Biological magnesium alloy, realizes prepared finished product sustained anti-microbial Function.In the present invention, nano-TiO2It is present in Biological magnesium alloy as the second phase, it can be along with Biological magnesium alloy not Disconnected degradation, continues efficiently to play antibacterial action.
The present invention is realized by the control of feedstock Particle size, cooperation high speed ball milling and distinctive sintering process parameter Nano-TiO2Be uniformly distributed and avoid as far as possible nano-TiO2Reunion and grow up, this for realize its antibacterial functions Provide necessary condition.The present invention is under the synergistic effect of feedstock Particle size, high speed ball milling and SLM technique, nano-TiO2 It can be uniformly dispersed on magnesium alloy crystal boundary, to mutually improve the mechanical property of Biological magnesium alloy as nano-diffusion.Simultaneously In right amount, the TiO of appropriate size2The degradation speed of Biological magnesium alloy can also be adjusted, this is used as material designed by the present invention plants Enter body, there is more favorable advantage.
The present invention is after high speed ball milling, and using the SLM technique of special parameter, the high cooling rate of SLM technique can make Biological magnesium alloy quickly solidifies, to reduce component segregation, obtains the uniform microstructure of ingredient.Since ingredient is not just deposited uniformly In the inconsistent situation appearance of degradation rate, (when not having coating or uneven components, the degradation rate easily occurred is not Consistent phenomenon).
Specific embodiment
A specific embodiment of the invention is illustrated below by an example:
Embodiment 1
Using nano-TiO2Powder and AZ91 magnesium alloy powder are raw material, weigh 9.5g AZ91 magnesium alloy powder (partial size~ 70 μm) and 0.5g nano-TiO2Powder (partial size~60nm) is under protection of argon gas 350rad/min in ball mill rotor speed After ball milling 6h, finely dispersed nano-TiO is obtained2/ AZ91 mixed-powder.Laser power 90W, scanning speed 300mm/min, 90 μm of spot diameter, sweep span 0.08mm, powdering thickness 0.1mm, are prepared nano-TiO using SLM technology2/ AZ91 magnesium Alloy.
Test discovery, nano-TiO2Stable structure can be kept in SLM forming process, and is uniformly divided as the second phase It is dispersed on magnesium alloy crystal boundary.With count of bacteria method to AZ91 magnesium alloy and nano-TiO2/ AZ91 magnesium alloy carries out antibacterial detection, i.e., With 1 × 107After the E. coli suspension of cfu/mL co-cultures for 24 hours, the bacterial concentration of AZ91 magnesium alloy co-culture media is 0.45 ×107Cfu/mL, antibiotic rate 55%, and nano TiO 2/AZ91 magnesium alloy co-culture media bacterial concentration is 1 × 106cfu/ ML, antibiotic rate 99% find nano-TiO2The anti-microbial property of/AZ91 magnesium alloy significantly improves compared with AZ91 magnesium alloy, energy Quickly and effectively inhibit the growth of Escherichia coli.Cell culture experiments prove nano-TiO2/ AZ91 magnesium alloy has good cell Compatibility will not generate apparent bio-toxicity to cell.Nano-TiO2/ AZ91 magnesium alloy degradation rate is 0.18mm/year, Ultimate tensile strength is 210MPa.
Embodiment 2
Using nano-TiO2Powder and AZ91 magnesium alloy powder are raw material, weigh 9.3g AZ91 magnesium alloy powder (partial size~ 70 μm) and 0.7g nano-TiO2Powder (partial size~60nm) is under protection of argon gas 350rad/min in ball mill rotor speed After ball milling 6h, finely dispersed nano-TiO is obtained2/ AZ91 mixed-powder.Laser power 90W, scanning speed 300mm/min, Spot diameter 0.5mm, sweep span 0.08mm, powdering thickness 0.1mm, nano-TiO is prepared using SLM technology2/AZ91 Magnesium alloy.
Test discovery, nano-TiO2Stable structure can be kept in SLM forming process, and is uniformly divided as the second phase It is dispersed on magnesium alloy crystal boundary.With count of bacteria method to AZ91 magnesium alloy and nano-TiO2/ AZ91 magnesium alloy carries out antibacterial detection, i.e., With 1 × 107After the E. coli suspension of cfu/mL co-cultures for 24 hours, the bacterial concentration of AZ91 magnesium alloy co-culture media is 0.45 ×107Cfu/mL, antibiotic rate 55%, and nano TiO 2/AZ91 magnesium alloy co-culture media bacterial concentration be 0.04 × 106Cfu/mL, antibiotic rate 96% find nano-TiO2The anti-microbial property of/AZ91 magnesium alloy improves compared with AZ91 magnesium alloy, Also it can inhibit the growth of Escherichia coli.Cell culture experiments prove nano-TiO2/ AZ91 magnesium alloy has good cytocompatibility Property, apparent bio-toxicity will not be generated to cell.Nano-TiO2/ AZ91 magnesium alloy degradation rate is 0.12mm/year, the limit Tensile strength is 175MPa.
Embodiment 3
Using nano-TiO2Powder and AZ91 magnesium alloy powder are raw material, weigh 9.7g AZ91 magnesium alloy powder (partial size~ 70 μm) and 0.3g nano-TiO2Powder (partial size~60nm) is under protection of argon gas 350rad/min in ball mill rotor speed After ball milling 6h, finely dispersed nano-TiO is obtained2/ AZ91 mixed-powder.Laser power 90W, scanning speed 300mm/min, 90 μm of spot diameter, sweep span 0.08mm, powdering thickness 0.1mm, are prepared nano-TiO using SLM technology2/ AZ91 magnesium Alloy.
Test discovery, nano-TiO2Stable structure can be kept in SLM forming process, and is uniformly divided as the second phase It is dispersed on magnesium alloy crystal boundary.With count of bacteria method to AZ91 magnesium alloy and nano-TiO2/ AZ91 magnesium alloy carries out antibacterial detection, i.e., With 1 × 107After the E. coli suspension of cfu/mL co-cultures for 24 hours, the bacterial concentration of AZ91 magnesium alloy co-culture media is 0.45 ×107Cfu/mL, antibiotic rate 55%, and nano-TiO2The bacterial concentration of/AZ91 magnesium alloy co-culture media be 0.22 × 106Cfu/mL, antibiotic rate 88% find nano-TiO2The anti-microbial property of/AZ91 magnesium alloy improves compared with AZ91 magnesium alloy, Also it can inhibit the growth of Escherichia coli.Cell culture experiments prove nano-TiO2/ AZ91 magnesium alloy has good cytocompatibility Property, apparent bio-toxicity will not be generated to cell.Nano-TiO2/ AZ91 magnesium alloy degradation rate is 0.25mm/year, the limit Tensile strength is 226MPa.
In the technology of the present invention development process, have also been attempted following scheme (such as comparative example 1, comparative example 2, comparative example 3), but The performance of products obtained therefrom is much worse than embodiment.
Comparative example 1
Other conditions be that embodiment 1 is consistent, the difference is that, weigh 9.9g AZ91 magnesium alloy powder and 0.1g Nano-TiO2Powder；With count of bacteria method to AZ91 magnesium alloy and nano-TiO2/ AZ91 magnesium alloy carries out antibacterial detection, i.e., with 1 × 107After the E. coli suspension of cfu/mL co-cultures for 24 hours, the bacterial concentration of AZ91 magnesium alloy co-culture media is 0.45 × 107Cfu/mL, antibiotic rate 55%, and nano TiO 2/AZ91 magnesium alloy co-culture media bacterial concentration is 0.57 × 107cfu/ ML, antibiotic rate 63%, demand is not achieved in antibacterial effect.Cell culture experiments prove nano-TiO2/ AZ91 magnesium alloy has good Good cell compatibility will not generate apparent bio-toxicity to cell.Nano-TiO2/ AZ91 magnesium alloy degradation rate is 0.65mm/year, ultimate tensile strength 219MPa.
Comparative example 2
Other conditions be that embodiment 1 is consistent, the difference is that, when ball milling, the revolving speed of ball mill is 100rad/ Min ball milling 3h；Antibacterial detection is carried out to AZ91 magnesium alloy and nano TiO 2/AZ91 magnesium alloy with count of bacteria method, i.e., with 1 × 107After the E. coli suspension of cfu/mL co-cultures for 24 hours, the bacterial concentration of AZ91 magnesium alloy co-culture media is 0.45 × 107Cfu/mL, antibiotic rate 55%, and nano TiO 2/AZ91 magnesium alloy co-culture media bacterial concentration is 1 × 106Cfu/mL, Antibiotic rate is 99%, and antibacterial ability and embodiment 1 are suitable.But nano-TiO2/ AZ91 magnesium alloy degradation rate is up to 2.3mm/ Year, ultimate tensile strength are only 167MPa.
Comparative example 3
Other conditions be that embodiment 1 is consistent, the difference is that, in laser power 135W, scanning speed 80mm/ Nano-TiO is prepared using SLM technology in min2/ AZ91 magnesium alloy.With count of bacteria method to AZ91 magnesium alloy and nanometer TiO2/AZ91 magnesium alloy carries out antibacterial detection, i.e., with 1 × 107After the E. coli suspension of cfu/mL co-cultures for 24 hours, AZ91 The bacterial concentration of magnesium alloy co-culture media is 0.45 × 107Cfu/mL, antibiotic rate 55%, and nano TiO 2/AZ91 magnesium alloy The bacterial concentration of co-culture media is 1 × 106Cfu/mL, antibiotic rate 99%, antibacterial ability and embodiment 1 are suitable.But nanometer TiO2/ AZ91 magnesium alloy degradation rate is up to 3.1mm/year, and ultimate tensile strength is only 152MPa.

Claims (9)

1. a kind of Biological magnesium alloy with antibacterial functions, it is characterised in that: the Biological magnesium alloy with antibacterial functions by Biological magnesium alloy matrix and the nano-TiO being uniformly distributed in magnesium alloy substrate2It constitutes；The biological magnesium with antibacterial functions In alloy, nano-TiO2Mass percentage be 3-7%；
The Biological magnesium alloy with antibacterial functions, is prepared by following step:
Step 1
By design proportion, with taking nano-TiO2Powder and Biological magnesium alloy powder, will be with the TiO taken2Powder and Biological magnesium alloy powder End is placed in ball mill, and under protective atmosphere, control rotational speed of ball-mill is 200-400rad/min, and ball milling 4-8h obtains mixed powder End；
Step 2
Using mixed-powder obtained by step 1 as raw material, it is passed through argon gas protective gas, controls H2O and O2Concentration is lower than 20ppm, passes through Selective laser fusing preparation has the Biological magnesium alloy of antibacterial functions；Selective laser fusing preparation has the biological magnesium of antibacterial functions When alloy, in preparation process, control laser power is 70-120W, scanning speed 100-600mm/min, spot diameter 50- 200 μm, sweep span 0.06-0.15mm, powdering is controlled with a thickness of 0.07-0.15mm.
2. a kind of Biological magnesium alloy with antibacterial functions according to claim 1, it is characterised in that: nano-TiO2Uniformly Be dispersed on the crystal boundary of Biological magnesium alloy matrix.
3. a kind of Biological magnesium alloy with antibacterial functions according to claim 1, it is characterised in that: nano-TiO2Grain Diameter is 10-100nm.
4. a kind of Biological magnesium alloy with antibacterial functions according to claim 1, it is characterised in that: described that there is antibacterial In the Biological magnesium alloy of function, nano-TiO2Mass percentage be 4-6%.
5. a kind of Biological magnesium alloy with antibacterial functions according to claim 4, it is characterised in that: described that there is antibacterial In the Biological magnesium alloy of function, nano-TiO2Mass percentage be 5%.
6. a kind of Biological magnesium alloy with antibacterial functions according to claim 1, it is characterised in that: the nano-TiO2 The partial size of powder is less than or equal to 100nm.
7. a kind of Biological magnesium alloy with antibacterial functions according to claim 1, it is characterised in that: the biology magnesium closes The partial size at bronze end is 50-70 μm.
8. a kind of Biological magnesium alloy with antibacterial functions according to claim 1, it is characterised in that: the biology magnesium closes Gold is AZ91 magnesium alloy powder.
9. a kind of Biological magnesium alloy with antibacterial functions according to claim 1, it is characterised in that: the protective atmosphere For high-purity argon gas atmosphere；The high-purity argon gas is the argon gas that purity is more than or equal to 99.999%.
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Publication number Priority date Publication date Assignee Title
CN108588520B (en) * 2018-04-28 2019-06-18 淮阴工学院 Laser in-situ Strengthening and Toughening Mg-based nanocomposite bone implant and its manufacturing process
CN109014184B (en) * 2018-08-10 2020-03-31 中南大学 Biomedical magnesium alloy with dual corrosion resistance and preparation method thereof
CN110614367A (en) * 2019-10-22 2019-12-27 中南大学 Interface coating enhanced biological magnesium-based metal ceramic and preparation method and application thereof
CN111020327A (en) * 2019-11-25 2020-04-17 温州广立生物医药科技有限公司 Tissue-regenerating absorbable magnesium alloy and preparation method thereof
CN110882424B (en) * 2019-12-13 2021-07-06 浙江瑞谷生物科技有限公司 Oral cavity guided bone regeneration barrier membrane
CN111187069B (en) * 2020-02-21 2021-10-22 四川大学 Titanium dioxide and magnesium oxide composite biomedical ceramic material and preparation method thereof
CN114178534B (en) * 2020-08-25 2023-12-12 香港大学 Antibacterial stainless steel powder and preparation method and application thereof
CN113289059A (en) * 2021-06-02 2021-08-24 江西理工大学 Copper-containing mesoporous bioglass-magnesium metal composite antibacterial material and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1837392A (en) * 2006-04-03 2006-09-27 重庆大学 Composite material of magnesium alloy and method for preparing the same
CN104150934A (en) * 2013-05-14 2014-11-19 中南大学 Method for reinforcing akermanite bone scaffold in selective laser sintering by utilization of nano titanium oxide
CN105803271A (en) * 2016-03-18 2016-07-27 南京航空航天大学 Aluminium-based nanocomposite based on SLM forming and preparation method of nanocomposite
CN106337180A (en) * 2015-07-13 2017-01-18 中南大学 Anti-oxidation method used for preparing magnesium alloy artificial bone by laser

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014174437A1 (en) * 2013-04-22 2014-10-30 Sandvik Intellectual Property Ab Method for drug loading hydroxyapatite coated implant surfaces

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1837392A (en) * 2006-04-03 2006-09-27 重庆大学 Composite material of magnesium alloy and method for preparing the same
CN104150934A (en) * 2013-05-14 2014-11-19 中南大学 Method for reinforcing akermanite bone scaffold in selective laser sintering by utilization of nano titanium oxide
CN106337180A (en) * 2015-07-13 2017-01-18 中南大学 Anti-oxidation method used for preparing magnesium alloy artificial bone by laser
CN105803271A (en) * 2016-03-18 2016-07-27 南京航空航天大学 Aluminium-based nanocomposite based on SLM forming and preparation method of nanocomposite

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