CN104131245B - A kind of biomedical titanium base block amorphous alloy of low noble metal constituent content and preparation method thereof - Google Patents
A kind of biomedical titanium base block amorphous alloy of low noble metal constituent content and preparation method thereof Download PDFInfo
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Abstract
The invention provides biomedical titanium base block amorphous alloy of a kind of low noble metal constituent content and preparation method thereof, the composition formula of this titanium-based amorphous alloy is: TiaCubZrcTMdSneSifMs(TM is Fe or Co, M is precious metal element Ag, Pd, Pt, Au, Ru, Rh or Ir), a, b, c, d, e, f, s are atomic percentage, 40≤a≤60,30≤b≤45,0.01≤c≤15,1≤d≤10,0≤e≤10,0≤f≤5,0.01≤s≤8, and a+b+c+d+e+f+s=100. Alloy adopts copper mold casting preparation, and maximum cut off diameter size is up to 7mm. This system block amorphous alloy is while having high amorphous formation ability, and without harmful high bio-toxicity Ni, Be element, and low noble metal constituent content can reduce production cost, therefore can be applicable to biomedical materials field.
Description
Technical field
The invention belongs to titanium (Ti) base block amorphous alloy technical field, it is specifically related to a kind of low noble metal constituent content and has Ti-Cu-Zr-TM-Sn-Si-M (TM=Fe or Co, M=Ag, Pd, Pt, Au, Ru, Rh and Ir) the series bulk amorphous Alloy And Preparation Method of high amorphous formation ability.
Background technology
Non-crystaline amorphous metal is a kind of under condition of fast cooling, atom is frozen in melted configuration and the metastable state material that can keep relative stability in certain temperature range that obtains. During non-crystaline amorphous metal solid-state, atomic arrangement presents the feature of shortrange order, longrange disorder, and the three dimensions of atom is the arrangement of topological disorder shape. Due to the atomic arrangement structure that it is special, non-crystaline amorphous metal does not have the defects such as crystal boundary that crystalline material has and dislocation, is absent from segregation, the second equal undulating composition yet. Determining its special physics, chemical property just because of this special atomic structure of non-crystaline amorphous metal, compared with tradition crystalline material, non-crystaline amorphous metal has high intensity, high rigidity, low elastic modulus, high-wearing feature and high-corrosion resistance.
Titanium (Ti) base noncrystal alloy has the corrosion resistance of higher intensity, less Young's modulus and brilliance compared with crystalline state titanium alloy, therefore has broad application prospects in bio-medical material. But, compare the amorphous alloys such as Zr base, Pd base, Fe base, the Forming ability of Ti base noncrystal alloy system is less, it is possible to the critical dimension of the block amorphous alloy material prepared is less.At present, the block amorphous alloy with bigger Forming ability developed, generally based on Ti-Zr-Ni-Cu, adds what other element obtained by the method for alloying. This kind of Ti base noncrystal alloy contains the contour bio-toxicity element of Ni, Be, limits the application in biomedical materials field of the Ti base noncrystal alloy. Amorphous formation ability reaches the Ti-Zr-Cu-Pd-Sn non-crystaline amorphous metal of Centimeter Level, though without the contour bio-toxicity element of Ni, Be, but its precious metal element Pd content higher (14at%) causes that its cost is too high and limits the extensive use in biomedical materials field of this alloy system. Therefore, developing the titanio block amorphous alloy material of the high amorphous formation ability not containing Ni, Be contour bio-toxicity element and advantage of lower cost is that titanium-based amorphous alloy can the inexorable trend of extensive use development.
Summary of the invention
It is an object of the invention to carry out alloying by interpolation precious metal element in Ti-Cu-Zr-Fe (Co)-Sn-Si alloy, obtain the titanio block amorphous alloy with high amorphous formation ability, high specific strength, excellent anti-corrosion performance and advantage of lower cost, the preparation method that this non-crystaline amorphous metal is provided simultaneously.
The following technical proposals of the present invention is used to realize above-mentioned goal of the invention:
The biomedical titanium base block amorphous alloy of a kind of low noble metal constituent content, elementary composition by Ti, Cu, Zr, Fe or Co, Sn, Si and precious metal element seven kinds, chemical composition is TiaCubZrcTMdSneSifMsWherein TM to be Fe or Co, M be precious metal element Ag or Pd or Pt or Au or Ru or Rh or Ir, a, b, c, d, e, f, s are atomic percentage, 40≤a≤60,30≤b≤45,0.01≤c≤15,1≤d≤10,0≤e≤10,0≤f≤5,0.01≤s≤8, and a+b+c+d+e+f+s=100.
Biomedical titanium base block amorphous alloy according to described a kind of low noble metal constituent content, its maximum critical dimension is up to 7mm.
Biomedical titanium base block amorphous alloy according to described a kind of low noble metal constituent content, its nickel not containing high bio-toxicity and beryllium element, precious metal element content is low.
Biomedical titanium base block amorphous alloy according to described a kind of low noble metal constituent content, it has higher amorphous formation ability and heat stability, has wide supercooling liquid phase region.
Biomedical titanium base block amorphous alloy according to described a kind of low noble metal constituent content, it has the decay resistance of excellence in simulation people's liquid solution, has good biocompatibility simultaneously.
The method that present invention also offers the biomedical titanium base block amorphous alloy of the described a kind of low noble metal constituent content of preparation, comprises the following steps:
Step 1: alloying ingredient is pressed TiaCubZrcTMdSneSifMsAtomic percent be converted into mass percent, measure with the balance of precision 0.001g and carry out alloying ingredient; Atomic percentage chemical composition is: TiaCubZrcTMdSneSifMsWherein TM is Fe or Co, M is precious metal element Ag, Pd, Pt, Au, Ru, Rh or Ir, and a, b, c, d, e, f, s are atomic percentage, 40≤a≤60,30≤b≤45,0.01≤c≤15,1≤d≤10,0≤e≤10,0≤f≤5,0.01≤s≤8, and a+b+c+d+e+f+s=100;
Step 2: needed raw material step 1 claimed is put in vacuum smelting furnace, the vacuum regulating vacuum smelting furnace vacuum chamber is 3 × 10-3Pa～6 × 10-3Pa, is then charged with the argon that purity is 99.8% and makes the vacuum of vacuum chamber to 0.1 × 105Pa～0.5 × 105Pa;When arc current is 330A～380A and smelting time is 120～300s, by alloy pig melting 3～5 times to guarantee that alloying component is uniform;
Step 3: the foundry alloy that step 2 melting prepares is put into vaccum sensitive stove, regulating induction furnace vacuum degree in vacuum chamber is 2 × 10-3～5 × 10-3Pa, is then charged with the argon that purity is 99.8% and makes the vacuum of vacuum chamber to 0.1 × 105～0.5 × 105Pa; Spurt in copper mold after smelting time 1～3min at temperature sensor 1000～1250 DEG C, prepare the Ti of certain diameteraCubZrcTMdSneSifMsBlock amorphous alloy bar.
Method according to the described biomedical titanium base large amorphous alloy preparing a kind of low noble metal constituent content, wherein step 3 is further to prepared TiaCubZrcTMdSneSifMsBlock amorphous alloy bar carries out the performance test of the anodic polarization curves test in non crystalline structure test, heat 3 analysis test, simulation people's liquid solution and biocompatibility test.
The present invention is a kind of bio-medical type titanium block base noncrystal alloy, and its atomic percentage chemical composition is TiaCubZrcTMdSneSifMs(TM is Fe or Co, M is precious metal element Ag, Pd, Pt, Au, Ru, Rh or Ir), a, b, c, d, e, f, s are atomic percentage, 40≤a≤60,30≤b≤45,0.01≤c≤15,1≤d≤10,0≤e≤10,0≤f≤5,0.01≤s≤8, and a+b+c+d+e+f+s=100.
Compared with prior art, the advantage of titanium (Ti) base bulk (block) non-crystaline amorphous metal of the present invention is in that:
1. the Ti base block amorphous alloy of the present invention has high amorphous formation ability and wide supercooling liquid phase region.
2. the Ti base block amorphous alloy of the present invention does not contain nickel and the beryllium element of high bio-toxicity, and its potential source biomolecule toxicity is substantially reduced, and precious metal element content is low, greatly reduces cost of alloy.
3. the Ti base block amorphous alloy of the present invention is simulated at PBS and is shown good corrosion resistance in people's liquid solution, and has mechanical property and the biocompatibility of excellence.
Accompanying drawing explanation
Fig. 1 is the Ti that the present invention prepares48Cu37Zr7.5Fe2.5Sn2Si1Ag2、Ti47Cu38Zr7.5Fe2.5Sn2Si1Ag2And Ti48Cu36Zr7.5Fe2.5Sn2Si1Pd3The XRD figure spectrum of block amorphous alloy critical dimension;
Fig. 2 is the Ti that the present invention prepares48Cu37Zr7.5Fe2.5Sn2Si1Ag2The room temperature compressive stress strain curve of block amorphous alloy;
Fig. 3 is the Ti that the present invention prepares47Cu38Zr7.5Fe2.5Sn2Si1Ag2The DSC curve of block amorphous alloy;
Fig. 4 is the Ti that the present invention prepares47Cu38Zr7.5Fe2.5Sn2Si1Ag2Non-crystaline amorphous metal polarization curve in simulation people's liquid solution;
Fig. 5 is the Ti that the present invention prepares47Cu38Zr7.5Fe2.5Sn2Si1Ag2The osteoblastic pattern of MC3T3-E1 mice embryonic after 3 days is cultivated on block amorphous alloy surface.
Detailed description of the invention
Below in conjunction with accompanying drawing, with embodiments of the invention, the present invention is described in further detail, but does not limit the present invention with this.
The present invention is the bio-medical Ti base block amorphous alloy of a kind of low noble metal constituent content, and the composition formula of this titanium-based amorphous alloy is: TiaCubZrcTMdSneSifMs(TM is Fe or Co, M is precious metal element Ag or Pd or Pt or Au or Ru or Rh or Ir), a, b, c, d, e, f, s are atomic percentage, 40≤a≤60,30≤b≤45,0.01≤c≤15,1≤d≤10,0≤e≤10,0≤f≤5,0.01≤s≤8, and a+b+c+d+e+f+s=100.
Copper mold casting method is adopted to prepare the Ti of the present inventionaCubZrcTMdSneSifMsBlock amorphous alloy comprises the following steps:
Step 1: alloying ingredient is pressed TiaCubZrcTMdSneSifMsAtomic percent be converted into mass percent, measure with the balance of precision 0.001g and carry out alloying ingredient; Atomic percentage chemical composition is: TiaCubZrcTMdSneSifMs(TM is Fe or Co, M is precious metal element Ag or Pd or Pt or Au or Ru or Rh or Ir), a, b, c, d, e, f, s are atomic percentage, 40≤a≤60,30≤b≤45,0.01≤c≤15,1≤d≤10,0≤e≤10,0≤f≤5,0.01≤s≤8, and a+b+c+d+e+f+s=100;
Step 2: needed raw material step one claimed is put in vacuum smelting furnace; Regulate the vacuum 3 × 10 of vacuum smelting furnace vacuum chamber-3Pa～6 × 10-3Pa, is then charged with the argon that purity is 99.8% and makes the vacuum of vacuum chamber to 0.1 × 105Pa～0.5 × 105Pa; When arc current is 330A～380A and smelting time is 120～300s, by alloy pig melting 3～5 times to guarantee that alloying component is uniform;
Step 3: the foundry alloy that melting prepares is put into vaccum sensitive stove, regulating induction furnace vacuum degree in vacuum chamber is 2 × 10-3～5 × 10-3Pa, is then charged with the argon that purity is 99.8% and makes the vacuum of vacuum chamber to 0.1 × 105～0.5 × 105Pa; Spurt in copper mold after smelting time 1～3min at temperature sensor 1000～1250 DEG C, prepare the Ti of certain diameteraCubZrcTMdSneSifMsBlock amorphous alloy bar. To prepared TiaCubZrcTMdSneSifMsBlock amorphous alloy bar carries out performance test: as non crystalline structure test, heat are analyzed the anodic polarization curves in test, simulation people's liquid solution and tested and biocompatibility test.
Embodiment 1
Copper mold casting method is adopted to prepare the Ti that diameter is 6mm48Cu37Zr7.5Fe2.5Sn2Si1Ag2Block amorphous alloy:
Step one: alloying ingredient is pressed Ti48Cu37Zr7.5Fe2.5Sn2Si1Ag2Atomic percent be converted into mass percent, measure alloying ingredient with the balance of precision 0.001g, choose purity to be the titanium of 99.99wt%, purity be the zirconium of 99.99wt%, purity is the copper of 99.99wt%, purity is the ferrum of 99.8wt%, purity is the stannum of 99.9wt%, purity is the silicon of 99.8wt%, purity is 99wt% silver carries out alloying ingredient configuration;
Step 2: needed raw material step one claimed is put in vacuum smelting furnace; Regulate the vacuum 2 × 10 of vacuum smelting furnace vacuum chamber-3Pa, is then charged with the purity argon higher than 99.8% and makes the vacuum of vacuum chamber to 0.1 × 105Pa; When arc current is 380A and smelting time is 120s, by alloy pig melting 4 times to guarantee that alloying component is uniform;
Step 3: the foundry alloy that melting prepares is put into vacuum high-frequency induction furnace, the vacuum regulating induction furnace vacuum chamber is 2 × 10-3Pa, then fills the purity argon higher than 99.8% and makes the vacuum of vacuum chamber to 0.1 × 105Pa; It is molded in copper mold after smelting time 40～60s at temperature sensor 1150～1300 DEG C, prepares the Ti that diameter is 6mm48Cu37Zr7.5Fe2.5Sn2Si1Ag2Block amorphous alloy bar;
Step 4: by prepared Ti48Cu37Zr7.5Fe2.5Sn2Si1Ag2Block amorphous alloy bar intercepts its cross section, carries out X-ray diffraction test, and its X ray diffracting spectrum is shown in Fig. 1. In figure, abscissa is 2 θ angles, and vertical coordinate is diffracted intensity (intensity); From diffracting spectrum, can be seen that this sample does not have obvious crystallization peak to be non crystalline structure;
Step 5: from prepared Ti48Cu37Zr7.5Fe2.5Sn2Si1Ag2Non-crystaline amorphous metal pole intercepts the non-crystaline amorphous metal bar that specification is 2mm (diameter) × 4mm (highly), adopting the room temperature Compressive Mechanical Properties that testing machine for mechanical properties tests this block amorphous alloy to see Fig. 2, this alloy has the fracture strength higher than 2000MPa and the plastic deformation more than 2%.
Embodiment 2
Copper mold casting method is adopted to prepare the Ti that diameter is 7mm47Cu38Zr7.5Fe2.5Sn2Si1Ag2Block amorphous alloy:
Step one: alloying ingredient is pressed Ti47Cu38Zr7.5Fe2.5Sn2Si1Ag2Atomic percent be converted into mass percent, measure alloying ingredient with the balance of precision 0.001g, choose purity to be the titanium of 99.99wt%, purity be the zirconium of 99.99wt%, purity is the copper of 99.99wt%, purity is the ferrum of 99.8wt%, purity is the stannum of 99.9wt%, purity is the silicon of 99.8wt%, purity is 99wt% silver carries out alloying ingredient configuration;
Step 2: needed raw material step one claimed is put in vacuum smelting furnace; Regulate the vacuum 2 × 10 of vacuum smelting furnace vacuum chamber-3Pa, is then charged with the purity argon higher than 99.8% and makes the vacuum of vacuum chamber to 0.1 × 105Pa; When arc current is 380A and smelting time is 120s, by alloy pig melting 4 times to guarantee that alloying component is uniform;
Step 3: the foundry alloy that melting prepares is put into vacuum high-frequency induction furnace, the vacuum regulating induction furnace vacuum chamber is 2 × 10-3Pa, then fills the purity argon higher than 99.8% and makes the vacuum of vacuum chamber to 0.1 × 105Pa; It is molded in copper mold after smelting time 40～60s at temperature sensor 1150～1300 DEG C, prepares the Ti that diameter is 7mm47Cu38Zr7.5Fe2.5Sn2Si1Ag2Block amorphous alloy bar;
Step 4: by prepared Ti47Cu38Zr7.5Fe2.5Sn2Si1Ag2Block amorphous alloy bar intercepts its cross section, carries out X-ray diffraction test, and its X ray diffracting spectrum is shown in Fig. 1. In figure, abscissa is 2 θ angles, and vertical coordinate is diffracted intensity (intensity); From diffracting spectrum, can be seen that this sample does not have obvious crystallization peak to be non crystalline structure;
Step 5: by prepared Ti47Cu38Zr7.5Fe2.5Sn2Si1Ag2Block amorphous alloy bar intercepts its heart portion pocket, it is carried out heat and analyzes test, it is thus achieved that thermodynamic parameter. Its DSC curve is shown in that in Fig. 3, figure, abscissa is temperature (unit K); Vertical coordinate is heat (heatflow), and in downward direction for heat release (Exothermic), it has wider supercooling liquid phase region (Tx=Tx-Tg) it is about 50K;
Step 6: adopt electrochemical workstation test Ti47Cu38Zr7.5Fe2.5Sn2Si1Ag2 block amorphous alloy polarization curve in simulation people's liquid solution (PBS) is shown in Fig. 4. This alloy has higher OCP and Pitting Potential and relatively low passive current density in PBS solution, thus has the decay resistance of excellence in PBS solution;
Step 7: by MC3T3-E1 mice embryonic osteoblast at Ti47Cu38Zr7.5Fe2.5Sn2Si1Ag2The cell culture experiments on block amorphous alloy surface carrys out the biocompatibility of preliminary assessment alloy. Experimental result is Fig. 5 such as, the long and narrow cell morphology of healthy state, and compact siro spinning technology between cell as can be observed from Figure, and this is conducive to the material between cell and information exchange, cell has breeds growth activity preferably, it was shown that this block amorphous alloy can support cell absorption and propagation preferably.
Embodiment 3
Copper mold casting method is adopted to prepare the Ti that diameter is 3mm48Cu36Zr7.5Fe2.5Sn2Si1Pd3Block amorphous alloy:
Step one: alloying ingredient is pressed Ti48Cu36Zr7.5Fe2.5Sn2Si1Pd3Atomic percent be converted into mass percent, measure alloying ingredient with the balance of precision 0.001g, choose zirconium that purity be the titanium of 99.99wt%, purity is 99.99%, stannum that ferrum that copper that purity is 99.99%, purity are 99.8%, purity are 99.9%, purity be 99.8% silicon, purity be 99% palladium carry out alloying ingredient configuration; Choose purity to be the titanium of 99.99wt%, purity be the zirconium of 99.99wt%, purity is the copper of 99.99wt%, purity is the ferrum of 99.8wt%, purity is the stannum of 99.9wt%, purity is the silicon of 99.8wt%, purity is 99wt% palladium carries out alloying ingredient configuration;
Step 2: needed raw material step one claimed is put in vacuum smelting furnace; Regulate the vacuum 2 × 10 of vacuum smelting furnace vacuum chamber-3Pa, is then charged with the purity argon higher than 99.8% and makes the vacuum of vacuum chamber to 0.1 × 105Pa; When arc current is 380A and smelting time is 120s, by alloy pig melting 4 times to guarantee that alloying component is uniform;
Step 3: the foundry alloy that melting prepares is put into rapid solidification induction furnace, the vacuum regulating induction furnace vacuum chamber is 4 × 10-3Pa, is then charged with the purity argon higher than 99.8% and makes the vacuum of vacuum chamber to 0.5 × 105Pa; Spurt in copper mold after smelting time 5～7s at temperature sensor 1100～1200 DEG C, prepare the Ti that diameter is 3mm48Cu36Zr7.5Fe2.5Sn2Si1Pd3Block amorphous alloy bar;
Step 4: by prepared Ti48Cu36Zr7.5Fe2.5Sn2Si1Pd3Block amorphous alloy bar intercepts its vertical section, carries out X-ray diffraction test, and its X ray diffracting spectrum is shown in Fig. 1. In figure, abscissa is 2 θ angles, and vertical coordinate is diffracted intensity (intensity); From diffracting spectrum, can be seen that this sample does not have obvious crystallization peak to be non crystalline structure.
To sum up, from the above it can be concluded that
Compared with prior art, the advantage of titanium (Ti) base bulk (block) non-crystaline amorphous metal of the present invention is in that:
The Ti base block amorphous alloy of the present invention has high amorphous formation ability and wide supercooling liquid phase region.
The Ti base block amorphous alloy of the present invention does not contain nickel and the beryllium element of high bio-toxicity, and its potential source biomolecule toxicity is substantially reduced, and precious metal element content is low, greatly reduces cost of alloy.
The Ti base block amorphous alloy of the present invention is simulated at PBS and is shown good corrosion resistance in people's liquid solution, and has mechanical property and the biocompatibility of excellence.
Claims (2)
1. the biomedical titanium base block amorphous alloy of a low noble metal constituent content, it is characterised in that: it is elementary composition by Ti, Cu, Zr, Fe, Sn, Si and precious metal element seven kinds, and chemical composition is TiaCubZrcFedSneSifMs, wherein M is precious metal element Ag, 40≤a≤60,30≤b≤45,0.01≤c≤15,1≤d≤10,0≤e≤10,0≤f≤5,0.01≤s≤8, and a+b+c+d+e+f+s=100; Its maximum critical dimension is 7mm.
2. the method for the biomedical titanium base block amorphous alloy of the preparation a kind of low noble metal constituent content described in claim 1, it is characterised in that comprise the following steps:
Step 1: alloying ingredient is pressed TiaCubZrcFedSneSifMsAtomic percent be converted into mass percent, measure with the balance of precision 0.001g and carry out alloying ingredient; Atomic percentage chemical composition is: TiaCubZrcFedSneSifMs, wherein M is precious metal element Ag, 40≤a≤60,30≤b≤45,0.01≤c≤15,1≤d≤10,0≤e≤10,0≤f≤5,0.01≤s≤8, and a+b+c+d+e+f+s=100;
Step 2: needed raw material step 1 claimed is put in vacuum smelting furnace, the vacuum regulating vacuum smelting furnace vacuum chamber is 3 × 10-3Pa～6 × 10-3Pa, is then charged with the argon that purity is 99.8% and makes the vacuum of vacuum chamber to 0.1 × 105Pa～0.5 × 105Pa; When arc current is 330A～380A and smelting time is 120～300s, by alloy pig melting 3～5 times to guarantee that alloying component is uniform;
Step 3: the foundry alloy that step 2 melting prepares is put into vaccum sensitive stove, regulating induction furnace vacuum degree in vacuum chamber is 2 × 10-3～5 × 10-3Pa, is then charged with the argon that purity is 99.8% and makes the vacuum of vacuum chamber to 0.1 × 105～0.5 × 105Pa; Spurt in copper mold after smelting time 1～3min at temperature sensor 1000～1250 DEG C, prepare the titanio block amorphous alloy bar of certain diameter.
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| CN106868431A (en) * | 2017-02-27 | 2017-06-20 | 盘固新型合金材料（常州）有限公司 | New material pedicle screw and its manufacture method |
| CN106901846A (en) * | 2017-02-27 | 2017-06-30 | 盘固新型合金材料（常州）有限公司 | Non-crystaline amorphous metal endodontic file and its manufacture method |
| CN111394665B (en) * | 2020-04-26 | 2021-04-16 | 山东大学 | TiCuZrPdFe amorphous composite material and preparation method thereof |
| CN111979501B (en) * | 2020-08-18 | 2021-09-24 | 新沂市锡沂高新材料产业技术研究院有限公司 | High-antibacterial-property medical metal glass and preparation method thereof |
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