CN109112361A - A kind of biological kirsite and preparation method thereof of tiny lamellar eutectic structure - Google Patents
A kind of biological kirsite and preparation method thereof of tiny lamellar eutectic structure Download PDFInfo
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Abstract
The present invention relates to a kind of biological kirsites and preparation method thereof of tiny lamellar eutectic structure, belong to biological kirsite design and fabrication technology field.The eutectic biology kirsite includes following components by percentage to the quality: zinc 98.9-99.1wt%, aluminium 0.8wt%, zirconium 0.1-0.3wt%.Zinc powder, aluminium powder and zirconium powder are taken by design component, 250-400r/min ball milling 2-4h, obtains mixed-powder under protective atmosphere；Then under protective atmosphere, zinc-aluminum-zirconium eutectic biology kirsite is prepared using SLM technique.The present invention passes through the heterogeneous forming core and constitutional supercooling of zr element, so that rich aluminium phase and zinc-rich in matrix is alternated and solidification is precipitated, to generate synusia eutectic structure in allumen, and the content for improving zirconium can further refine synusia eutectic structure；In addition, forming core growth is able to suppress using the fast feature of SLM technology setting rate, to further refine the lamellar eutectic structure of kirsite.The formation and refinement of lamellar eutectic structure improve the mechanical property of biological kirsite, promote it in the application in tissue repair field.
Description
Technical field
The invention belongs to biomaterial design and preparation technical field, in particular to a kind of life of tiny lamellar eutectic structure
Object kirsite and preparation method thereof.
Background technique
The standard electrode potential of zinc has between magnesium and iron and grows suitable degradation rate with body bone tissue, because
This is considered as a kind of bone renovating material of great potential.In addition, zinc has good biocompatibility and excellent processability
Can, and numerous physiological reaction processes such as the growth of energy participant's somatocyte development, gene expression, immune system and nervous system.So
And the mechanical property of zinc especially intensity and toughness is poor, is also difficult to reach the requirement of bone defect healing at present, this is greatly limited
Its application is made.Therefore, the mechanical property for improving zinc becomes it and is used for degradable bone implant problem in the urgent need to address.
In recent years a large number of studies show that, addition alloying element and to improve preparation process be to improve zinc mechanical property to have efficacious prescriptions
Method.The improvement result to zinc mechanical property is not only considered when selecting alloying element, while being also contemplated that the life of alloying element
Object compatibility.Domestic and foreign scholars have done a series of researchs for zinc-containing alloy at present, obtain many alloy systems, as zinc-magnesium,
Zinc-calcium, zinc-strontium etc., the different degrees of mechanical strength for improving zinc of the addition of these alloying elements, but simultaneously also in zinc-base
The second hard and crisp phase is generated in body, so that the fracture toughness of these kirsites and elongation percentage reduce, is still difficult to meet to make
With requiring.
According to Zinc-aluminum binary alloy phase diagram, eutectic reaction can occur under special ratios and form sheet for aluminium element and Zn-ef ficiency
Eutectic structure.Therefore, it if can be added to aluminium as alloying element in zinc, is expected to generate the eutectic structure of lamellar, thus
Improve the mechanical property of kirsite.But the aluminium content at allumen eutectic point is 5.1wt%, so high aluminium content is not only
Human tissue organ can be caused to damage, and it is coarse to will cause lamellar eutectic structure, weakens its mechanics strengthening effect.Cause
This efficiently uses the lamellar eutectic between aluminum and zinc and reacts and effectively play it how on the basis of keeping biological safety
Invigoration effect becomes the key that allumen is applied in Bone Defect Repari.
Summary of the invention
The disadvantages of in order to overcome the above-mentioned alloy mechanical property of biological zinc in the prior art insufficient, it is an object of the invention to mention
For a kind of biological kirsite and preparation method thereof of tiny lamellar eutectic structure.
To achieve the goals above, the technical solution adopted by the present invention is that:
A kind of biological kirsite of tiny lamellar eutectic structure, by zinc 98.9-99.1wt%, aluminium 0.8wt% and zirconium 0.1-
0.3wt% composition, wherein rich aluminium phase and zinc-rich alternate to be precipitated to solidify and form tiny lamellar eutectic structure.
The biological zinc alloy grain size of the tiny lamellar eutectic structure reduces with the raising of zirconium content.
Preferably, the synusia spacing of the tiny lamellar eutectic structure is less than 1 μm.
In the present invention, the content of the zirconium is higher, and the synusia spacing of tiny lamellar eutectic structure is smaller, and compressive strength is got over
It is high.
Preferably, the content of the aluminium is 0.8wt%, and the content of zirconium is 0.1-0.2wt%.It is highly preferred that the aluminium
Content is 0.8wt%, and the content of zirconium is 0.2wt%.
The present invention also provides the preparation methods of the biological kirsite of the tiny lamellar eutectic structure, including following steps
It is rapid:
Step 1:
With zinc powder, aluminium powder and zirconium powder is taken, ball milling obtains zinc-aluminium zirconium mixed-powder under protective atmosphere；
Step 2:
Using zinc-aluminium zirconium mixed-powder obtained by step 1 as raw material, under protective atmosphere, lamellar eutectic is prepared using SLM technique
The biological kirsite of structure.
Preferably, in the step 1, ball material mass ratio 10:1-30:1, rotational speed of ball-mill 250-400r/min, ball milling 2-
4h.In the step 2, control laser power is 50-70W, and sweep speed 10-15mm/s, spot diameter is 50 μm, laser
Sweep span is 20-30 μm, and powdering is with a thickness of 0.1-0.2mm.
It is highly preferred that ball material mass ratio is 20:1-30:1, rotational speed of ball-mill 350-400r/min, ball in the step 1
Grind 3-4h；In the step 2, control laser power is 60-70W, and sweep speed 12-15mm/s, spot diameter is 50 μm,
Laser scanning pitch is 20 μm, and powdering is with a thickness of 0.1mm.
Preferably, in the step 1 and step 2, protective atmosphere is the high-purity argon that purity is more than or equal to 99.999%
Gas.
The biological kirsite of of the invention designed and preparation tiny lamellar eutectic structure has as degradable implantation material
There is apparent advantage.
The principle of the present invention and advantage:
The present invention has attempted directly to make an addition to aluminium and zirconium in biological kirsite using SLM technique for the first time, prepares tiny layer
The biological kirsite of lamellar eutectic structure.By controlling the dosage of zirconium while ensuring appropriate degradation rate and biocompatibility
The mechanical property of product is promoted as far as possible.
By Zinc-aluminum binary phasor it is found that Al content is lower than its solid solubility (1.1wt%) in zinc in Zn-0.8Al alloy,
And it is far below its eutectic composition (5.1wt%), therefore Al can be solid-solubilized in Zinc Matrix completely in laser preparation process, it can not shape
At synusia eutectic structure.And after adding zirconium, one side zirconium can form the second phase of zinc-aluminium zirconium with zinc and aluminium, and this second phase can
As effective heterogeneous forming core site, promote alternating precipitation and the forming core of zinc-rich phase and rich aluminium phase；On the other hand, the high fusing point of zirconium
It is capable of increasing constitutional supercooling and promotes forming core, more rich aluminium are precipitated mutually, the two collective effect promotes the shape of lamellar eutectic structure
At.And as zirconium content increases, more the second phases of zinc-aluminium zirconium are formd, more zinc-rich phases and rich aluminium phase forming core are promoted,
Therefore the lamellar eutectic quantity in unit volume is increased, and then has refined lamellar eutectic structure.Meanwhile utilizing SLM technique
High cooling rate makes alloy quick solidification, promotes lamellar eutectic structure and is formed in grain boundary, has further refined layer
Piece eutectic structure.The eutectic structure of refinement increases lamellar boundary, enhances the pinning effect of lamellar boundary, can effectively hinder
The climb motion of dislocation and the movement for passing through interface, to improve the mechanical property of biological kirsite.
On this basis, the present invention obtains the second phase of zinc-aluminium zirconium of small and dispersed, this is by optimization zinc-aluminum-zirconium component
It obtains lamellar eutectic structure and provides precondition；By optimizing milling parameters, aluminium powder, zirconium powder and zinc powder are realized
Uniformly mixing, this provides necessary condition for the lamellar eutectic structure being evenly distributed；After the completion of ball milling, it is aided with specific ginseng
Several SLM technique realizes the quick preparation of biological kirsite.When zirconium content is too low, zirconium can be dissolved into matrix, can not be formed
The second phase of zinc-aluminium zirconium, so that eutectic structure cannot be generated；When zirconium content is excessive, the zinc-aluminium of coarse or mutual bridging is easily formed
The second phase of zirconium, and then increase the synusia spacing of eutectic structure.When Ball-milling Time is too short, three kinds of powder mixing are uneven, obtain
The lamellar eutectic structure of Random Discrete distribution has been arrived, or even has formed coarse the second phase of zinc-aluminium zirconium；When Ball-milling Time is too long,
The cold welding between powder is exacerbated, the excessive powder of granularity has been obtained, so that powder agglomeration occurs, increases synusia
Spacing.For SLM technique, when power is too low or scanning speed is too fast, laser energy density is too small, and metal powder can hardly
Molding；And energy density is excessive, keeps bath temperature excessively high, promotes matrix grain and the second phase is grown up, and increases between synusia
Away from.Coarse synusia spacing and the second phase inevitably reduces the mechanical property of biological kirsite.
Compared with prior art, advantage of the present invention is as follows:
(1) heterogeneous forming core is promoted by zr element and increases constitutional supercooling, form synusia eutectic structure；And pass through raising
Zr element content further refines the spacing and size of synusia eutectic structure, increases lamellar boundary to the pinning effect of crackle, into
And improve the mechanical property of biological kirsite.
(2) the characteristics of utilizing SLM technology high energy rapid cooling, promotes lamellar eutectic in the formation of crystal boundary, to obtain more
Mostly tiny lamellar eutectic structure.
(3) zinc developed-aluminum-zirconium alloy system can not only obtain the biological kirsite of lamellar eutectic structure, and
And there is excellent biocompatibility and degradation rate appropriate, it can be used in tissue reparation.
Detailed description of the invention
Fig. 1 is the surface topography map of Zn-Al-Zr alloy of the present invention.
The XRD diagram of alloy when Fig. 2 is Zr content 0.4wt%.
Specific embodiment
The embodiment that the present invention will be described in detail with reference to the accompanying drawings and examples.
Embodiment 1
0.02g zirconium powder, 0.08g aluminium powder and 9.9g zinc powder are weighed respectively by the mass ratio of 0.2:0.8:99, by three
Person is added in ball grinder and with the ball material mass ratio of 20:1, under 99.999% high-purity argon gas protective atmosphere, with revolving speed 350r/
Min ball milling 3h, to obtain zinc-aluminium zirconium mixed-powder.Using above-mentioned mixed-powder as raw material, in laser power 65W, scanning speed
14mm/s, 50 μm of spot diameter, sweep span 0.01mm, powdering protect gas with a thickness of 0.1mm and 99.999% high-purity argon gas
Under the process conditions of atmosphere, biological kirsite is prepared using SLM technique.
Micro-structural test discovery forms the lamellar zinc-aluminium eutectic structure of a large amount of fine uniform distributions, such as Fig. 1 a institute
Show, synusia spacing is 0.34 μm, is found through mechanical test, ultimate compression strength 260MPa improves 86% relative to zinc.
Embodiment 2
0.01g zirconium powder, 0.08g aluminium powder and 9.91g zinc powder are weighed respectively by the mass ratio of 0.1:0.8:99.1, it will
Three is added in ball grinder and with the ball material mass ratio of 20:1, under 99.999% high-purity argon gas protective atmosphere, with revolving speed
350r/min ball milling 3h, to obtain zinc-aluminium zirconium mixed-powder.Using above-mentioned mixed-powder as raw material, in laser power 65W, scanning
Speed 14mm/s, 50 μm of spot diameter, sweep span 0.01mm, powdering are protected with a thickness of 0.1mm and 99.999% high-purity argon gas
It protects under the process conditions of atmosphere, prepares biological kirsite using SLM technique.
Micro-structural test discovery, joined in zinc obtained after 0.1wt% zirconium and 0.8wt% aluminium it is a small amount of tiny
The lamellar eutectic structure of even distribution, as shown in Figure 1 b, synusia spacing are 0.37 μm.It is found through mechanical test, limited compression is strong
Spend 235MPa.
Embodiment 3
0.03g zirconium powder, 0.08g aluminium powder and 9.89g zinc powder are weighed respectively by the mass ratio of 0.3:0.8:98.9, it will
Three is added in ball grinder and with the ball material mass ratio of 20:1, under 99.999% high-purity argon gas protective atmosphere, with revolving speed
350r/min ball milling 3h, to obtain zinc-aluminium zirconium mixed-powder.Using above-mentioned mixed-powder as raw material, in laser power 65W, scanning
Speed 14mm/s, 50 μm of spot diameter, sweep span 0.01mm, powdering are protected with a thickness of 0.1mm and 99.999% high-purity argon gas
It protects under the process conditions of atmosphere, prepares biological kirsite using SLM technique.
Micro-structural test discovery, joined in zinc and has obtained tiny synusia after 0.3wt% zirconium and 0.8wt% aluminium
Shape eutectic structure, as illustrated in figure 1 c, synusia spacing are 0.51 μm.It is found through mechanical test, ultimate compression strength 220MPa.
Embodiment 4
0.02g zirconium powder, 0.08g aluminium powder and 9.9g zinc powder are weighed respectively by the mass ratio of 0.2:0.8:99, by three
Person is added in ball grinder and with the ball material mass ratio of 20:1, under 99.999% high-purity argon gas protective atmosphere, with revolving speed 250r/
Min ball milling 2h, to obtain zinc-aluminium zirconium mixed-powder.Using above-mentioned mixed-powder as raw material, in laser power 65W, scanning speed
14mm/s, 50 μm of spot diameter, sweep span 0.01mm, powdering protect gas with a thickness of 0.1mm and 99.999% high-purity argon gas
Under the process conditions of atmosphere, biological kirsite is prepared using SLM technique.
Micro-structural test discovery, joined in zinc and has obtained a large amount of lamellars after 0.2wt% zirconium and 0.8wt% aluminium
Eutectic structure, as shown in Figure 1 d, synusia spacing are 0.93 μm.Discovery ultimate compression strength 215MPa is tested through mechanical test.
In the technology of the present invention development process, following scheme (such as comparative example 1, comparative example 2, comparative example 3, right has also been attempted
Ratio 4), but the performance of products obtained therefrom is much worse than embodiment.
Comparative example 1
Other conditions are consistent with embodiment 1, the difference is that: 0.04g is weighed by the mass ratio of 0.4:0.8:98.8
Zirconium powder, 0.08g aluminium powder, 9.88g zinc powder.There is apparent the second phase of zinc-aluminium zirconium in test discovery products obtained therefrom, such as Fig. 2 institute
Show, form coarse lamellar eutectic, as shown in fig. le, synusia spacing is 1.56 μm, ultimate compression strength 160MPa.
Comparative example 2
Other conditions are consistent with embodiment 1, the difference is that: it is weighed by the mass ratio of 0.05:0.8:99.15
0.005g zirconium powder, 0.08g aluminium powder, 9.915g zinc powder.Test discovery products obtained therefrom does not have forming layer lamellar eutectic, limit pressure
Contracting intensity 140MPa.
Comparative example 3
Other conditions are consistent with embodiment 1, the difference is that: when carrying out ball milling with revolving speed 200r/min ball milling
2h.Test discovery products obtained therefrom middle layer lamellar eutectic Tissue distribution is extremely uneven, ultimate compression strength 150MPa.
Comparative example 4
Other conditions are consistent with embodiment 1, the difference is that: at laser power 65W, scanning speed 8mm/s
To product.It was found that products obtained therefrom forms coarse lamellar eutectic structure, ultimate compression strength 180MPa.
To sum up, the present invention passes through the heterogeneous forming core and constitutional supercooling of zr element, makes rich aluminium phase and zinc-rich intersection in matrix
For solidification is precipitated, to generate synusia eutectic structure in allumen, and the content for improving zirconium being capable of further refinement layer
Piece eutectic structure；In addition, forming core growth is able to suppress using the fast feature of SLM technology setting rate, to further refine zinc
The lamellar eutectic structure of alloy.The formation and refinement of lamellar eutectic structure improve the mechanical property of biological kirsite, promote
Its application in tissue repair field.
Claims (10)
1. a kind of biological kirsite of tiny lamellar eutectic structure, which is characterized in that by zinc 98.9-99.1wt%, aluminium 0.8wt%
It is formed with zirconium 0.1-0.3wt%, wherein rich aluminium phase and zinc-rich alternate to be precipitated to solidify and form tiny lamellar eutectic structure.
2. the biological kirsite of tiny lamellar eutectic structure according to claim 1, which is characterized in that the zirconium content is got over
The crystal grain of height, biological kirsite is smaller, and the synusia spacing of tiny lamellar eutectic structure is smaller, and compressive strength is higher.
3. the biological kirsite of tiny lamellar eutectic structure according to claim 1, which is characterized in that the tiny synusia is total
The synusia spacing of crystal structure is less than 1 μm.
4. the biological kirsite of tiny lamellar eutectic structure according to claim 1, which is characterized in that the content of the aluminium is
0.8wt%, the content of zirconium are 0.1-0.2wt%.
5. the biological kirsite of tiny lamellar eutectic structure according to claim 1, which is characterized in that the content of the aluminium is
0.8wt%, the content of zirconium are 0.2wt%.
6. a kind of preparation method of the biological kirsite of tiny lamellar eutectic structure described in claim 1, which is characterized in that including
Following step:
Step 1:
With zinc powder, aluminium powder and zirconium powder is taken, ball milling obtains zinc-aluminium zirconium mixed-powder under protective atmosphere；
Step 2:
Using zinc-aluminium zirconium mixed-powder obtained by step 1 as raw material, under protective atmosphere, lamellar eutectic structure is prepared using SLM technique
Biological kirsite.
7. the preparation method of the biological kirsite of tiny lamellar eutectic structure according to claim 6, which is characterized in that described
In step 1, ball material mass ratio 10:1-30:1, rotational speed of ball-mill 250-400r/min, ball milling 2-4h.
8. the preparation method of the biological kirsite of tiny lamellar eutectic structure according to claim 6, which is characterized in that described
In step 2, control laser power is 50-70W, and sweep speed 10-15mm/s, spot diameter is 50 μm, laser scanning pitch
It is 20-30 μm, powdering is with a thickness of 0.1-0.2mm.
9. the preparation method of the biological kirsite of tiny lamellar eutectic structure according to claim 6, which is characterized in that described
In step 1, ball material mass ratio is 20:1-30:1, rotational speed of ball-mill 350-400r/min, ball milling 3-4h；In step 2, control
Laser power is 60-70W, and sweep speed 12-15mm/s, spot diameter is 50 μm, and laser scanning pitch is 20 μm, and powdering is thick
Degree is 0.1mm.
10. the preparation method of the biological kirsite of tiny lamellar eutectic structure according to claim 6, which is characterized in that institute
It states in step 1 and step 2, protective atmosphere is the high-purity argon gas that purity is more than or equal to 99.999%.
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