A kind of Ti-Nb-Mn alloy and preparation method thereofTechnical field
Present invention relates particularly to medical instruments field, in particular to a kind of Ti-Nb-Mn alloy and preparation method thereof.
Background technique
Compared with other biomedical metallic materials, titanium or titanium alloy is due to lower density, high specific strength, goodThe distinguishing features such as good corrosion resistance and biocompatibility, therefore it is outer to become the medical treatment such as orthopaedic srugery, bone displacement and joint repairWidely applied metal material in section's operation.At present, the titanium or titanium alloy applied in clinical medicine is mainly pure Ti (CP-Ti)With Ti-6Al-4V (TC4) alloy, but their elasticity modulus (>=110GPa) with higher are much higher than people's bone (3-20GPa),If being implanted into human body, " stress shielding " can be generated to the bone of surrounding, lead to occur bone resorption around implant, finally cause to plantThe sterile loosening for entering body, shortens the working life.Studies have shown that there is body-centered cubic structure in all kinds of phases for constituting titanium alloyβ phase elasticity modulus it is minimum.There is the beta-titanium alloy of lower elasticity modulus to become medical titanium alloy developing material for design and exploitationEmphasis.
Nb is identical as β-Ti lattice, can infinitely be solid-solution in β phase, without forming compound.Therefore, Ti-Nb class alloy isThe most important biomedical β-type Ti alloys researched and developed at present, including Ti-Nb binary system, Ti-Nb-Ta, Ti-Nb-Zr and Ti-The quaternary alloys such as the ternary systems such as Mo-Nb and Ti-Nb-Ta-Zr.Although Nb belongs to β phase stable element and nontoxicity, obtainThe additional amount of full β phase is big.It, could be completely by water quenching β phase only when Nb amount reaches 42% studies have shown that for Ti-Nb alloyRemain into room temperature.Nb belongs to valuable rare element, and additional amount is bound to cause greatly the raising of cost of alloy.In addition, the fusing point of NbUp to 2468 DEG C, this is bound to cause the difficulty of melting, and the tissue of formation is also easy to produce segregation, influences mechanics and corrosion resistance.CauseThis, has very big research, Development volue with the beta titanium alloy that cheap strong β phase stable element replaces Nb element to be formed.
Ti-Nb based alloy is due to low elasticity modulus and preferable shape memory effect, being that most potential exploitation makesMedical titanium alloy.Application, such as Ti-13Nb-13Zr, Ti- has been obtained in the meta-stable titanium alloy of some Ti-Nb bases35Nb-5Ta-7Zr, Ti-29Nb-13Ta-4.6Zr, Ti-39Nb-5.1Ta-7.1Zr (TNTZ) and Ti-34Nb-9Zr-8Ta.ThisA little titanium alloys but cause alloy strength lower while obtaining low elasticity modulus.Some elasticity modulus are higher, but alloyIntensity is but less than 600MPa, such as Ti-35Nb-5Ta-7Zr.The characteristics of in order to meet bio-medical material good biocompatibilityOutside, it should also make material that there is medium intensity and lower elasticity modulus.In general, the tensile strength of material is greater than650MPa, elasticity modulus in 70GPa hereinafter, orthopaedics can be met, the application of the bio-medical fields such as dentistry.
Mn is strong β phase stable element, and it has biggish solid solution strengthening effect to β phase.It is true as the World Health OrganizationOne of 14 kinds of the essential trace elements of the human bodys recognized, research shows that there is Ti-Mn alloy excellent cell to deposit as Mn≤13%Motility rate, suitable with CP-Ti, micro Mn has biological safety.Mn is safe and non-toxic strong β phase stable element, and research is suitableAdditional amount replaces Nb element to high tension (removing tension) intensity and low elasticity modulus.
Therefore, a kind of Ti-Nb-Mn alloy and preparation method thereof becomes the key to solve the problem.
Summary of the invention
As various extensive and careful research and experiment as a result, present inventors have found that: choose safetyNontoxic strong β phase stable element Mn, part substitute Nb precious metal, reduce melting difficulty, are easy to solution treatment, while avoiding tissueSegregation is generated, mechanical property is improved, improves tensile strength, keeps low elastic modulus.
One object of the present invention provides a kind of Ti-Nb-Mn alloy, has compared with high-tensile and lower springformAmount.
It is also an object of the present invention to provide the alloys of a kind of preparation method of Ti-Nb-Mn alloy, preparation to haveCompared with high-tensile and lower elasticity modulus.
To achieve the above object, the present invention provides a kind of Ti-Nb-Mn alloy, which is made of following weight percent:
Titanium 72%~73%；
Niobium 23%-24%；
Manganese 3%-5%.
Preferably, which is made of following weight percent:
Titanium 73%；
Niobium 24%；
Manganese 3%.
Preferably, the yield strength that the Ti-Nb-Mn alloy closes is 728~731MPa.
Preferably, the tensile strength that the Ti-Nb-Mn alloy closes is 737~893MPa.
Preferably, the hardness number that the Ti-Nb-Mn alloy closes is up to 328~340HV.
Preferably, the elasticity modulus that the Ti-Nb-Mn alloy closes is 82~87GPa.
A method of it being used to prepare Ti-Nb-Mn alloy described in any of the above embodiments, is included the following steps:
A, ingredient is carried out according to the titanium of weight percent 72%~73%, 23%~24% niobium, 3%~5% manganese, setIn vacuum arc smelting furnace, melt back 3~6 times, master alloy ingot is acquired after cooling；
B, the master alloy ingot obtained in step a is put into quartz ampoule, the quartz ampoule for filling master alloy ingot take out trueSky, the vacuum degree for keeping it internal reach 3 × 10-4~1 × 10-3Pa, then the quartz ampoule for filling master alloy ingot is put into well formula resistanceIt is heated to 900~920 DEG C in furnace, keeps the temperature 25~35min；Quickly quartz ampoule is quenched in saturation NaCl solution, obtains forming β typeTi-Nb-Mn alloy.
Preferably, in step a, before titanium, niobium and manganese Metal are placed in vacuum arc smelting furnace, it should also polish and remove surfaceOxide layer, ultrasonic cleaning 3~6 minutes.
Preferably, in stepb, the vacuum degree in vacuum tube is 5 × 10-4~8 × 10-4Pa。
Preferably, in stepb, heating temperature is 905~915 DEG C, keeps the temperature 28~32min.
The beneficial effects of the present invention are: 1, have compared with high-tensile and lower elasticity modulus；2, with safe and non-toxic strong βPhase stable element Mn, part substitute Nb precious metal, reduce melting difficulty, are easy to solution treatment；3, safe and non-toxic strong β phase is stableElement M n, reduces production cost.
Detailed description of the invention
The alloy XRD spectrum of Fig. 1 difference amount containing Mn；
The relation curve of the elongation σ of Fig. 2 alloy, yield strength σ s, tensile strength sigma b and the amount containing Mn；
The microhardness and elasticity modulus of Fig. 3 difference alloy of amount containing Mn.
Specific embodiment
The present invention is described in further detail combined with specific embodiments below, to enable those skilled in the art's reference sayBright book text can be implemented accordingly.
Embodiment 1
The present invention provides a kind of Ti-Nb-Mn alloy, by weight percentage, comprising:
Titanium 73%, niobium 24% and manganese 3%.
A kind of Ti-Nb-Mn alloy of the present invention the preparation method is as follows:
A, according to weight percent as above, titanium 73g, niobium 24g and manganese 3g, polishing removal surface oxide layer, ultrasonic wave are weighedCleaning 5 minutes, is placed in vacuum arc smelting furnace, melt back 5 times, acquires master alloy ingot after cooling；
B, the master alloy ingot obtained in step a is put into quartz ampoule, the quartz ampoule for filling master alloy ingot take out trueSky, the vacuum degree for keeping it internal reach 8 × 10-4Pa, then the quartz ampoule for filling master alloy ingot is put into well formula resistance furnace and is heatedTo 910 DEG C, 30min is kept the temperature；Quickly quartz ampoule is quenched in saturation NaCl solution, obtains forming β type Ti-Nb-Mn alloy.
Embodiment 2
The present invention provides a kind of Ti-Nb-Mn alloy, by weight percentage, comprising:
Titanium 72%, niobium 23% and manganese 5%.
A kind of Ti-Nb-Mn alloy of the present invention the preparation method is as follows:
A, according to weight percent as above, titanium 72g, niobium 23g and manganese 5g, polishing removal surface oxide layer, ultrasonic wave are weighedCleaning 3 minutes, is placed in vacuum arc smelting furnace, melt back 6 times, acquires master alloy ingot after cooling；
B, the master alloy ingot obtained in step a is put into quartz ampoule, the quartz ampoule for filling master alloy ingot take out trueSky, the vacuum degree for keeping it internal reach 3 × 10-4Pa, then the quartz ampoule for filling master alloy ingot is put into well formula resistance furnace and is heatedTo 920 DEG C, 25min is kept the temperature；Quickly quartz ampoule is quenched in saturation NaCl solution, obtains forming β type Ti-Nb-Mn alloy.
Embodiment 3
The present invention provides a kind of Ti-Nb-Mn alloy, by weight percentage, comprising:
Titanium 72.5%, niobium 23.5% and manganese 4%.
A kind of Ti-Nb-Mn alloy of the present invention the preparation method is as follows:
A, according to weight percent as above, titanium 72.5g, niobium 23.5g and manganese 4g are weighed, polishing removal surface oxide layer surpassesSound wave cleans 6 minutes, is placed in vacuum arc smelting furnace, melt back 3 times, acquires master alloy ingot after cooling；
B, the master alloy ingot obtained in step a is put into quartz ampoule, the quartz ampoule for filling master alloy ingot take out trueSky, the vacuum degree for keeping it internal reach 1 × 10-3Pa, then the quartz ampoule for filling master alloy ingot is put into well formula resistance furnace and is heatedTo 900 DEG C, 35min is kept the temperature；Quickly quartz ampoule is quenched in saturation NaCl solution, obtains forming β type Ti-Nb-Mn alloy.
Embodiment 4
The present invention provides a kind of Ti-Nb-Mn alloy, by weight percentage, comprising:
Titanium 72.25%, niobium 23.25% and manganese 4.5%.
A kind of Ti-Nb-Mn alloy of the present invention the preparation method is as follows:
A, according to weight percent as above, titanium 72.25g, niobium 23.25g and manganese 4.5g, polishing removal surface oxidation are weighedLayer, ultrasonic cleaning 4 minutes, is placed in vacuum arc smelting furnace, melt back 4 times, acquires master alloy ingot after cooling；
B, the master alloy ingot obtained in step a is put into quartz ampoule, the quartz ampoule for filling master alloy ingot take out trueSky, the vacuum degree for keeping it internal reach 5 × 10-4Pa, then the quartz ampoule for filling master alloy ingot is put into well formula resistance furnace and is heatedTo 905 DEG C, 32min is kept the temperature；Quickly quartz ampoule is quenched in saturation NaCl solution, obtains forming β type Ti-Nb-Mn alloy.
Embodiment 5
The present invention provides a kind of Ti-Nb-Mn alloy, by weight percentage, comprising:
Titanium 72.75%, niobium 23.5% and manganese 3.25%.
A kind of Ti-Nb-Mn alloy of the present invention the preparation method is as follows:
A, according to weight percent as above, titanium 72.75g, niobium 23.5g and manganese 3.25g, polishing removal surface oxidation are weighedLayer, ultrasonic cleaning 5 minutes, is placed in vacuum arc smelting furnace, melt back 5 times, acquires master alloy ingot after cooling；
B, the master alloy ingot obtained in step a is put into quartz ampoule, the quartz ampoule for filling master alloy ingot take out trueSky, the vacuum degree for keeping it internal reach 7.5 × 10-4Pa, then the quartz ampoule for filling master alloy ingot is put into well formula resistance furnace and is addedHeat keeps the temperature 28min to 915 DEG C；Quickly quartz ampoule is quenched in saturation NaCl solution, obtains forming β type Ti-Nb-Mn alloy.
Embodiment 6
The present invention provides a kind of Ti-Nb-Mn alloy, by weight percentage, comprising:
Titanium 72.75%, niobium 23.5% and manganese 3.75%.
A kind of Ti-Nb-Mn alloy of the present invention the preparation method is as follows:
A, according to weight percent as above, titanium 72.75g, niobium 23.5g and manganese 3.75g, polishing removal surface oxidation are weighedLayer, ultrasonic cleaning 3 minutes, is placed in vacuum arc smelting furnace, melt back 6 times, acquires master alloy ingot after cooling；
B, the master alloy ingot obtained in step a is put into quartz ampoule, the quartz ampoule for filling master alloy ingot take out trueSky, the vacuum degree for keeping it internal reach 9 × 10-4Pa, then the quartz ampoule for filling master alloy ingot is put into well formula resistance furnace and is heatedTo 912 DEG C, 30min is kept the temperature；Quickly quartz ampoule is quenched in saturation NaCl solution, obtains forming β type Ti-Nb-Mn alloy.
Embodiment 7
The present invention provides a kind of Ti-Nb-Mn alloy, by weight percentage, comprising:
Titanium 72.75%, niobium 23.75% and manganese 3.5%.
A kind of Ti-Nb-Mn alloy of the present invention the preparation method is as follows:
A, according to weight percent as above, titanium 72.75g, niobium 23.75g and manganese 3.5g, polishing removal surface oxidation are weighedLayer, ultrasonic cleaning 6 minutes, is placed in vacuum arc smelting furnace, melt back 3 times, acquires master alloy ingot after cooling；
B, the master alloy ingot obtained in step a is put into quartz ampoule, the quartz ampoule for filling master alloy ingot take out trueSky, the vacuum degree for keeping it internal reach 6.5 × 10-4Pa, then the quartz ampoule for filling master alloy ingot is put into well formula resistance furnace and is addedHeat keeps the temperature 31min to 908 DEG C；Quickly quartz ampoule is quenched in saturation NaCl solution, obtains forming β type Ti-Nb-Mn alloy.
Comparative example 1
A kind of Ti-Nb alloy, by weight percentage, comprising:
Titanium 73%, niobium 27%.
A kind of Ti-Nb alloy the preparation method is as follows:
A, according to weight percent as above, titanium 73g and niobium 27g, polishing removal surface oxide layer, ultrasonic cleaning 5 are weighedMinute, it is placed in vacuum arc smelting furnace, melt back 5 times, acquires master alloy ingot after cooling；
B, the master alloy ingot obtained in step a is put into quartz ampoule, the quartz ampoule for filling master alloy ingot take out trueSky, the vacuum degree for keeping it internal reach 8 × 10-4Pa, then the quartz ampoule for filling master alloy ingot is put into well formula resistance furnace and is heatedTo 910 DEG C, 30min is kept the temperature；Quickly quartz ampoule is quenched in saturation NaCl solution, obtains forming β type Ti-Nb alloy.
Comparative example 2
A kind of Ti-Nb-Mn alloy, by weight percentage, comprising:
Titanium 73%, niobium 26%, Mn1%.
A kind of Ti-Nb-Mn alloy of the present invention the preparation method is as follows:
A, according to weight percent as above, titanium 73g, niobium 26g and manganese 1g, polishing removal surface oxide layer, ultrasonic wave are weighedCleaning 5 minutes, is placed in vacuum arc smelting furnace, melt back 5 times, acquires master alloy ingot after cooling；
B, the master alloy ingot obtained in step a is put into quartz ampoule, the quartz ampoule for filling master alloy ingot take out trueSky, the vacuum degree for keeping it internal reach 8 × 10-4Pa, then the quartz ampoule for filling master alloy ingot is put into well formula resistance furnace and is heatedTo 910 DEG C, 30min is kept the temperature；Quickly quartz ampoule is quenched in saturation NaCl solution, obtains forming β type Ti-Nb-Mn alloy.
Comparative example 3
A kind of Ti-Nb-Mn alloy, by weight percentage, comprising:
Titanium 73%, niobium 25%, Mn2%.
A kind of Ti-Nb-Mn alloy of the present invention the preparation method is as follows:
A, according to weight percent as above, titanium 73g, niobium 25g and manganese 2g, polishing removal surface oxide layer, ultrasonic wave are weighedCleaning 5 minutes, is placed in vacuum arc smelting furnace, melt back 5 times, acquires master alloy ingot after cooling；
B, the master alloy ingot obtained in step a is put into quartz ampoule, the quartz ampoule for filling master alloy ingot take out trueSky, the vacuum degree for keeping it internal reach 8 × 10-4Pa, then the quartz ampoule for filling master alloy ingot is put into well formula resistance furnace and is heatedTo 910 DEG C, 30min is kept the temperature；Quickly quartz ampoule is quenched in saturation NaCl solution, obtains forming β type Ti-Nb-Mn alloy.
Experimental data
Detect respectively by the elongation of embodiment 1-7 and comparative example the 1-2 alloy being prepared into, yield strength, tensile strength,Hardness and elastic modulus, the result is shown in Figure 1~3 and table 1.
Table 1
As can be seen from Table 1, when the additional amount of Mn element is 3~5%, the elasticity modulus of alloy is smaller, extends simultaneouslyRate, yield strength, tensile strength and hardness are relatively suitably applied medical instruments field.
As described above, a kind of Ti-Nb-Mn alloy of the present invention and preparation method thereof, have compared with high-tensile and lowerElasticity modulus；With safe and non-toxic strong β phase stable element Mn, part substitutes Nb precious metal, reduces melting difficulty, is easy to be dissolved placeReason；Safe and non-toxic strong β phase stable element Mn, reduces production cost.
Although the embodiments of the present invention have been disclosed as above, but it is not restricted to listed fortune in bright book and embodimentWith it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily realNow other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is not limited toSpecific details.