CN101580907A - Ni-free super elastic Ti-based shape memory alloy and products thereof - Google Patents
Ni-free super elastic Ti-based shape memory alloy and products thereof Download PDFInfo
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Abstract
The invention relates to a Ni-free super elastic Ti-based shape memory alloy and products thereof. Because of adding rare earths metal element Ce, the Ti-Zr-Nb-Fe-Al-Ce Ni-free super elastic Ti-based shape memory alloy has high erosion resistance and oxidation resistance as well as excellent welding performance, cold workability, phase-changing super elasticity, shape memory property and biocompatibility. The welding performance, the cold workability and the biocompatibility of the alloy are better than those of TiNi shape memory alloy, while the super elasticity and the shape memory property are equivalent to those of the TiNi shape memory alloy. The Ti-Zr-Nb-Fe-Al-Ce Ni-free super elastic Ti-based shape memory alloy not only can be used as biomaterial capable of being implanted in a human body for a long time, but also can be used as hyperelastic alloy manufacturing industrial products such as spectacle frame, bra support, golf club head, pipe joint, spring and drive element; moreover, the alloy has the advantages of easy processing, low cost and wide application range.
Description
Technical field
The present invention relates to Ti-based shape memory alloy, and preparation method thereof and goods, particularly Ni-free super elastic Ti-based shape memory alloy, its preparation method and goods.
Background technology
TiNi shape memory alloy (trade(brand)name: the Nitinol alloy) have excellent shape-memory properties and phase transformation super-elasticity, and passed through international biological assessment test, thereby over nearly 20 years, obtained using widely at medical field.But because the Ni element carinogenicity that can produce anaphylaxis and have the part crowd, fears are entertained that behind long-term implant into body has toxic Ni ion because of wearing and tearing and corrosion discharge, thereby hope can be developed Ni-free super elastic Ti-based shape memory alloy.
September in 1988, Kathy K.Wang on the 9th etc. were in U.S. Pat 4,857, proposed a kind of new titanium alloy in 269, added No. 1 component and were selected from: Mo, and Ta, Nb, Zr accounts for 0-24wt%; Adding No. 2 components is selected from: Al, and La accounts for 0-3wt%; Adding No. 3 components is selected from: Fe, Mg, Cr, Co, Ni, 0-3wt%; Surplus is Ti.The typical component of recommending is: 10-20wt%Nb, and 1-4wt%Zr, 2wt%Fe, 1wt%Al, surplus is Ti.January in 1991, James A.Davidson on the 28th etc. were in U.S. Pat 5,169, proposed a kind of new titanium zirconium-niobium alloy in 597, and the component of patent protection is: 0-20wt%Zr, and 10-20wt%Nb, surplus is Ti; Perhaps 0-20wt%Zr, 35-50wt%Nb, surplus is Ti.June in 1994, JamesA.Davidson on the 20th etc. were again in U.S. Pat 5,545, and 227 have proposed a kind of new titanium niobium alloy, and the component of protection is: 10-20wt%Nb, surplus is Ti.Above alloy is the low modulus medical titanium alloy, what attempt to solve is the stress shielding effect that the elastic modulus difference of the Young's modulus of metal implant and skeleton causes greatly, has reduced osseous tissue and has been absorbed risk with the implant fracture.Yet there are no the open report and the patent application of the functional capability such as super-elasticity, shape memory of this class material.
In May, 2004, the Yu Yang etc. of Beijing Non-Ferrous Metal Research General Academy on the 17th disclosed a kind of beta-titanium alloy and made product thereof in Chinese patent ZL200410038061.3, its chemical ingredients and weight percent thereof are: zirconium 20～40%, niobium 20～30%, hafnium 0.5～3%, tantalum 0.0～2%, oxygen 0.05～0.20%, carbon 0.0～0.15%, nitrogen 0.0～0.01%, hydrogen 0.0～0.02%, surplus is a titanium; Wherein, the weight ratio of zirconium and hafnium is 30～50.By the made product of this beta-titanium alloy is spectacle frame, implant frame, tooth section orthopedic instruments, artificial joint prosthesis or golf club.Claim that this beta-titanium alloy has low Young's modulus, higher-strength, very big cold working property.
In November, 2004, the Hao Yulin etc. of Metal Inst., Chinese Academy of Sciences on the 17th disclosed a kind of Ti-Nb-Zr series titanium alloy in Chinese patent ZL200410092858.1, its chemical ingredients is 20～35wt%Nb, 2～12wt%Zr, surplus is Ti and unavoidable impurities element.Claim that this system alloy has good cold-forming property and very low work hardening rate, can carry out the big scale cold deformation by cold machining process such as cold rolling and hand-drawn wires; This system alloy has super-elasticity, shape memory and damping function and low elastic modulus, high strength, corrosion-resistant and high human compatibility; This system alloy can prepare the nano material of crystal grain at nanoscale through cold deformation, can obtain the nano material of superstrength by thermal treatment.In addition, claimed at 20～35wt%Nb in claim 3,2～12wt%Zr, surplus is that the Ti-Nb-Zr of Ti is at least a element that also contains in the alloy among Sn, the Al, its content is that the Ti-Nb-Zr of 0.1～12wt% is an alloy.
The Song Xi equality of University of Science ﹠ Technology, Beijing disclosed a kind of Young's modulus adjustable type and straightened one's teeth with beta-titanium alloy and preparation technology thereof in Chinese patent ZL200610113509.2 on September 29th, 2006.The chemical ingredients of this alloy and weight percent thereof are: iron 3～5%, niobium 10～20%, zirconium 2～10%, aluminium 2～5%, tin 2～15%, carbon 0.1～0.3%, nitrogen 0.0～0.01, hydrogen 0.0～0.02%.Preparation technology handles for vacuum consumes melting+rolling+room temperature cold-drawn+vacuum aging in vain.The Young's modulus value of claiming this alloy can change between 40GPa～120GPa scope along with the variation of aging time.This titanium alloy can be applicable to orthodontic filament, orthodontic rack and the miniature orthodontic spring of mouth cavity orthodontic aspect.
On May 13rd, 2005, Wang Xin quickly disclosed a kind of shape memory alloy and preparation method thereof in Chinese patent ZL200510013500.X, and this alloy contains main alloy element Ti, Zr, Nb and adds element and comprises MO, V, Cr, Sn, and addition element Al; Each weight percentages of components is respectively: Ti:46-60, Zr:15＜Zr≤25, Nb:15-25; Add element choose MO, V, Cr, Sn wherein one or both, its weight percent＜2.0; Al:0.5-2.5.Claim that this alloy has outstanding shape-memory properties and super-elasticity characteristics, and can surpass 50% and even 99% cold deformation.Alloy through solid solution, ageing treatment can have higher shape memory recovery function in wider scope, higher cold working plasticity reaches premium propertiess such as human body nontoxicitys.Therefore can be used for imbedding for a long time intravital living body and function metal of people and industrial goods material, and easily processing, cost are low, applied range.In addition, Wang Xinmin etc. also disclose a kind of Ti-Nb-Zr alloy that is used for spectacle frame in application number is 200680028660.4 Chinese patent, this alloy compositions is: 40-75wt%Ti, 18-30wt%Nb, at least a additional metal element that is selected from Al, Sn, In and Ga of 10-30wt%Zr and 0.2-3.7wt%.
Scientific literature, patent about no nickel shape memory alloy research and development are many in addition.But still do not have a kind of shape-memory properties, phase transformation superelastic properties of not having nickel shape memory alloy so far, can compare favourably, thereby need the new no nickel shape memory alloy of research and development with Ti-Ni marmem.
Summary of the invention
The objective of the invention is to overcome above-mentioned weak point, be intended to develop a kind of excellent performance Ni-free super elastic Ti-based shape memory alloy, preparation method and goods are provided.
Ni-free super elastic Ti-based shape memory alloy is characterized in that described alloy contains main alloy element Ti, Zr, Nb, Al, and adds Elements C e; Each weight percentages of components is respectively: Zr:13-26%, and Nb:13-26%, Al:0.3-2.8%, Ce:0.1-1.3%, surplus is Ti and unavoidable impurities element.
Described Ni-free super elastic Ti-based shape memory alloy goods adopt the present invention's Ni-free super elastic Ti-based shape memory alloy manufacturing, include but not limited to: mechanicals and medical treatment product.
Further, above-mentioned mechanicals comprises: spectacle frame, brassiere holder, golf club, tube stub, spring, driving element etc.
Above-mentioned medical treatment product include but not limited to: medical stent, surgical implant, dental orthodontic material, seal wire, conduit, plantation tooth, intramedullary nail, Steel Plate For Fixation Of Fracture etc.
Described unavoidable impurities element mainly comprises: H, O, N, C.Its maximum level: H :≤0.05wt%, O :≤0.20wt%, N :≤0.03wt%, C :≤0.20wt%.
The alloying thinking of the present invention's Ni-free super elastic Ti-based shape memory alloy is: Ti is the metallic substance of the good biocompatibility of generally acknowledging, can implant in that human body is medium-term and long-term, thereby new Ni-free super elastic shape memory alloy still is body material with the titanium.Because Ti normal temperature is hexagonal close packed lattice (α phase) down, the work hardening phenomenon appears in cold working easily, can't realize 99% cold-forming property.And Ti is more than 882 ℃, and the α phase Ti of hexagonal close packed lattice changes the β phase Ti of body centered structure into, known very big extension property occurred.Therefore, if the Ti alloy can keep the existence of β phase, just have very big plastic deformation ability.Add an amount of metallic Z r and Nb,, improve the cold-forming property of Ti base alloy if help the existence that the Ti alloy can keep the β phase.Through experimental study, reasonable addition is to add the Zr of 13～26wt% and the Nb of 13～26wt% simultaneously, can not only strengthen Ti base alloy, also can significantly improve the cold-forming property of Ti base alloy.The too high levels of Zr and Nb or the low excessively alloy that all is unfavorable for obtaining performance the best.Another benefit that adds Nb is the Young's modulus that has reduced Ti base alloy, the Nb that adds 13-26wt%, the Young's modulus of Ti base alloy can be able to be reduced between the 40Gpa-65Gpa, close to the Young's modulus (about 28Gpa) of skeleton, to weaken the stress shielding effect.Al is a kind of compound formation element in the Ti alloy, can make Ti alloy generation martensitic transformation.Experiment shows that (13～26wt%) Zr-(add the Al of 0.3～2.8wt%, can make alloy have shape-memory properties and superelastic properties more in the Ti base alloy of 13～26wt%) Nb at Ti-.
What be worth paying special attention to is that the present invention's Ni-free super elastic Ti-based shape memory alloy has increased key element Ce on the basis of Ti-Zr-Nb-Al quad alloy system.Rare earth metal cerium (Ce) joined to have played in the Ti-Zr-Nb-Al quad alloy system strengthened alloy, reduce the harmful effect of impurity, change the form and the distribution of inclusion, improve effects such as anticorrosive, antioxidant property, welding property, cold-workability, phase transformation super-elasticity and shape-memory properties.Particularly Ce joins Ti-Zr-Nb-Al quad alloy system following effect:
(1) alleviates the harmful effect of nonmetallic impurity.Hydrogen is the detrimental impurity of titanium alloy, when solidifying, the hydrogen that dissolves in liquid metal separates out with atomic state, be gathered into molecule, cause occurring hydrogen-induced defects such as intergranular crack, loose and pin hole, bring serious harm for casting, plastic working and performance, experiment shows that adding The addition of C e (0.1～0.5%) in the Ti-Zr-Nb-Al quad alloy will significantly reduce the content of hydrogen, plays the damaging effect that reduces hydrogen, improves the performance of alloy.Ce also has the effect that reduces oxygen level in the alloy in addition.Ce has very high chemically reactive, and is active unusually in chemical reaction, very easily with gas, nonmetal and metal function, generates corresponding stable compound, these compounds, fusing point height, light specific gravity, come-up slagging.Their small particle then becomes the heterogeneous nucleus of alloy crystallisation process, plays the effect of crystal grain thinning.
(2) crystal grain thinning.In the Ti-Zr-Nb-Al quad alloy, add Ce, but the as-cast structure of refinement alloy, thus improve the thermoplasticity of alloy.The solid-state particle that rare earth compound is small provides heterogeneous nucleus or has gathered partially on crystalizing interface and hinder growing up of structure cell, for titanium liquid crystallization refinement provides thermal condition preferably.
(3) form and the distribution of change inclusion.Add Ce in the Ti-Zr-Nb-Al quad alloy, Ce and impurity form compound, separate out at crystal boundary, and the inclusion amount is reduced.
(4) produce strengthening effect.In the Ti-Zr-Nb-Al quad alloy, add Ce, hydrogen, oxygen and inclusion amount are reduced, again refinement crystal grain and dendritic network, rare earth metal Ce and non-metallic element effect produce the compound disperse of high melting-point in matrix, both eliminated thick massive texture, stablize crystal boundary again, these have all played the effect that improves the strength of materials.
(5) erosion resistance, high temperature oxidation resistance have been improved.The Ce that adds 0.3～0.8wt% in the Ti-Zr-Nb-Al quad alloy has significantly improved erosion resistance, the high temperature oxidation resistance of Ti-Zr-Nb-Al alloy.
(6) improved welding property.The Ce that adds 0.2～1.3wt% in the Ti-Zr-Nb-Al quad alloy has significantly improved the welding property of Ti-Zr-Nb-Al alloy.
(7) improve cold-forming property.The Ce that adds 0.1～1.3wt% in the Ti-Zr-Nb-Al quad alloy has significantly improved the cold-forming property of Ti-Zr-Nb-Al alloy, can surpass 50% and even 99% cold deformation.
(8) improve superelastic properties.The Ce that adds 0.1～1.3wt% in the Ti-Zr-Nb-Al quad alloy has significantly improved the superelastic properties of Ti-Zr-Nb-Al alloy.
(9) improve shape-memory properties.The Ce that adds 0.1～1.3wt% in the Ti-Zr-Nb-Al quad alloy has significantly improved the shape performance of Ti-Zr-Nb-Al alloy.Can recover shape in a wider context.
The present invention's Ti-Zr-Nb-Al-Ce Ni-free super elastic Ti-based shape memory alloy, because the adding of thulium Ce, make alloy have high anticorrosive, antioxidant property, and good welding property, cold-workability, phase transformation super-elasticity, shape-memory properties and biocompatibility.Its welding property, cold-workability and biocompatibility are better than the TiNi shape memory alloy, and super-elasticity and shape-memory properties are then suitable with the TiNi shape memory alloy.The present invention's Ni-free super elastic Ti-based shape memory alloy can be used for imbedding for a long time intravital biomaterial of people and industrial goods material, and easily processing, cost are low, applied range.
Description of drawings
Fig. 1 is the principle explanatory view with stress-strain curve evaluating material super-elasticity and shape-memory properties.
Fig. 2 is the extension recovery graphic representation of the alloy of the embodiment of the invention (1).
Fig. 3 is the extension recovery graphic representation of the alloy of the embodiment of the invention (2).
Fig. 4 is the extension recovery graphic representation of the alloy of the embodiment of the invention (3).
Fig. 5 is the extension recovery graphic representation of the alloy of the embodiment of the invention (4).
Fig. 6 is the extension recovery graphic representation of the alloy of the embodiment of the invention (5).
Fig. 7 is the industrial goods that the alloy of the embodiment of the invention (6) is made.
Fig. 8 is the medical treatment product that the alloy of the embodiment of the invention (7) is made.
Fig. 9 is the orthopaedic medical treatment equipment internal fixing clamping plate that the alloy of the embodiment of the invention (8) is made.
Among the above-mentioned figure, ordinate zou is tensile stress (Stress), and X-coordinate is strain (Strain); 1 is the present invention's spectacle frame, and 2 is Jing Quan, and 3 is that the bridge of the nose, 4 is the mirror leg, and 5 is pile crown, and 6 is the nose holder, and 7 is crossbeam; 8 are stationary jaw within the present invention.
Embodiment
Main evaluation means of the present invention is in the differing temps interval, by stretching experiment, and estimates its stress-strain curve, judges the super-elasticity and the shape-memory properties of material.With sample tensile deformation, unloading then, and note its loading, the stress-strain curve when unloading, with reference to figure 1.Among Fig. 1, the stress-strain curve of solid line for loading; Dotted line is near the stress-strain curve (unloading back strain energy is got back to the initial point) when having the unloading of hyperelastic material; Near stress-strain curve (unloading back strain can not be got back to the initial point, and residual strain is bigger) when long and short dash line is non-hyperelastic material unloading.
After the unloading,, promptly be referred to as superelastic alloy, with reference to figure 1 if strain can be got back near the initial point alloy by dotted line.
After the unloading, reply if long and short dash line is pressed in strain, and be in more than the transformation temperature of material when temperature, strain energy is returned near the initial point, is referred to as shape memory alloy.If shape memory effect is arranged, also should estimate its phase transition parameter (being transformation temperature), with reference to figure 1.
After the unloading, reply if long and short dash line is pressed in strain, even heating, strain can not turn back near the alloy the initial point, is referred to as non-shape memory (non-super-elasticity) alloy, and promptly alloy does not possess shape memory (or super-elasticity), with reference to figure 1.
In like manner, Fig. 2 to Fig. 6 has showed alloy loading, the stress-strain curve when unloading at normal temperatures of the present invention's different chemical composition respectively, confirms that intuitively it has or not shape-memory properties and superelastic properties.
Embodiment 1: the Ti-21.5Zr-23.5Nb-1.2Al-0.6Ce alloy
Chemical ingredients scope according to the present invention's alloy:
Zr：13-26wt％；
Nb：13-26wt％；
Al：0.3-2.8wt％；
Ce：0.1-1.3wt％，
Ti and unavoidable impurities element: surplus.
Unavoidable impurities element described here mainly comprises: elements such as H, O, N, C.
Specific to embodiment 1, the alloying constituent that obtains after the melting is:
The chemical ingredients of the Ti-21.5Zr-Nb-1.2Al-0.6Ce alloy of table 1: embodiment 1
| Element | Ti | Zr | Nb | Al | Ce | H | O | N | C |
| wt％ | 53.07 | 21.50 | 23.50 | 1.20 | 0.60 | 0.01 | 0.08 | 0.01 | 0.03 |
Embodiment 2: the Ti-21.5Zr-23.5Nb-1.5Al-0.8Ce alloy
According to following table 2 preparation and smelting titanium alloys, with the alloy that obtains through solution treatment: make tension specimen after (850 ℃ of temperature are incubated 30 minutes, water-cooled), under room temperature (25 ± 2 ℃), test by the stretching experiment machine.Maximum strain is set in 4.2%, and the stress-strain curve when measuring and writing down its loading, unloading is with reference to figure 3.Experimental results show that embodiment 2 alloys have good super-elasticity.
The chemical ingredients of the Ti-21.5Zr-23.5Nb-1.5Al-0.8Ce alloy of table 2: embodiment 2
| Element | Ti | Zr | Nb | Al | Ce | H | O | N | C |
| wt％ | 52.57 | 21.50 | 23.50 | 1.50 | 0.80 | 0.01 | 0.07 | 0.01 | 0.04 |
Embodiment 3: the Ti-22.6Zr-24.4Nb-1.8Al-0.5Ce alloy
According to following table 3 preparation and smelting titanium alloys, with the alloy that obtains through solution treatment: make tension specimen after (850 ℃ of temperature are incubated 30 minutes, water-cooled), under room temperature (25 ± 2 ℃), test by the stretching experiment machine.Maximum strain is set in 4.2%, and the stress-strain curve when measuring and writing down its loading, unloading is with reference to figure 4.Experimental results show that embodiment 3 alloys have good super-elasticity.
The Ti-22.6Zr-24.4Nb-1.8Al-0.5Ce alloy of table 3: embodiment 3
| Element | Ti | Zr | Nb | Al | Ce | H | O | N | C |
| wt％ | 50.56 | 22.60 | 24.40 | 1.80 | 0.50 | 0.02 | 0.06 | 0.01 | 0.05 |
Embodiment 4: the Ti-19.5Zr-23.5Nb-1.6Al-0.5Ce alloy
According to following table 4 preparation and smelting titanium alloys, with the alloy that obtains through solution treatment: make tension specimen after (850 ℃ of temperature are incubated 30 minutes, water-cooled), under room temperature (25 ± 2 ℃), test by the stretching experiment machine.Maximum strain is set in 4.2%, and the stress-strain curve when measuring and writing down its loading, unloading is with reference to figure 5.Experimental results show that embodiment 4 alloys have good super-elasticity.
The Ti-19.5Zr-23.5Nb-1.6Al-0.5Ce alloy of table 4: embodiment 4
| Element | Ti | Zr | Nb | Al | Ce | H | O | N | C |
| wt％ | 54.74 | 19.50 | 23.50 | 1.60 | 0.50 | 0.01 | 0.08 | 0.01 | 0.06 |
Embodiment 5: the Ti-21Zr-23.5Nb-0.8Al-0.6Ce alloy
According to following table 5 preparation and smelting titanium alloys, with the alloy that obtains through solution treatment: (850 ℃ of temperature, be incubated 30 minutes, water-cooled) back and through solution treatment: (850 ℃ of temperature are incubated 30 minutes, water-cooled), (temperature is ageing treatment: 250 ℃, time is: 20 minutes) after make tension specimen respectively, under room temperature (25 ± 2 ℃), test by the stretching experiment machine.Maximum strain is set in 4.2%, and the stress-strain curve when measuring and writing down its loading, unloading is with reference to figure 6.Experimental results show that embodiment 5 alloys have good super-elasticity.
The Ti-21Zr-23.5Nb-0.8Al-0.6Ce alloy of table 5: embodiment 5
| Element | Ti | Zr | Nb | Al | Ce | H | O | N | C |
| wt％ | 53.95 | 21.00 | 23.50 | 0.80 | 0.60 | 0.01 | 0.06 | 0.01 | 0.07 |
Embodiment 6: adopt and add rare-earth element cerium, research rare earth element cerium content is to the influence of titanium zirconium Nb-Al alloy super-elasticity, tensile property.Smelting titanium alloy, with the alloy that obtains through solution treatment: make tension specimen after (850 ℃ of temperature are incubated 30 minutes, water-cooled), under room temperature (25 ± 2 ℃), test by the stretching experiment machine.
Table 1. rare earth element cerium content is to the influence of Ti-21.5Zr-23.5Nb-Al alloy super-elasticity, tensile property
| Cerium content (wt%) | Super-elasticity (%) | Intensity (MPa) | Plasticity (%) |
| 0 | 3.90 | 700 | 20 |
| 0.3 | 4.00 | 750 | 25 |
| 0.6 | 4.20 | 850 | 34 |
| 0.8 | 4.18 | 850 | 34 |
| 1.0 | 4.10 | 860 | 33 |
| 1.2 | 3.80 | 860 | 32 |
Embodiment 7: the spectacle frame that the present invention's Ni-free super elastic Ti-based shape memory alloy is made
The present invention's Ni-free super elastic Ti-based shape memory alloy can be used for the process industry product, as spectacle frame.Compare with the spectacle frame that TiNi shape memory alloy (as: Nitinol alloy) is made, because the welding property and the cold-forming property of the present invention's Ni-free super elastic Ti-based shape memory alloy all are better than the Nitinol alloy, simplified manufacturing process not only, cost reduces; And can make complicated more and meticulous spectacle frame.The present invention's Ni-free super elastic Ti-based shape memory alloy can be used for making Jing Quan, the bridge of the nose, pile crown, nose holder or the mirror leg of spectacle frame, with reference to figure 7.
Embodiment 8: the orthopaedics material that the present invention's Ni-free super elastic Ti-based shape memory alloy is made
The present invention's Ni-free super elastic Ti-based shape memory alloy can be used for making medical treatment product, as orthopaedics material, medical stent, dental orthodontic material etc.Be used for making the internal fixing clamping plate after the fracture in the present embodiment.
According to the chemical ingredients preparation and the molten alloy of the present invention's Ni-free super elastic Ti-based shape memory alloy, hot rolling then, cold rolling one-tenth panel material.Panel material is processed into the half-moon-shaped of design,, promptly obtains the stationary jaw of the present invention's alloy manufacturing, with reference to figure 8 again through typing thermal treatment.
During clinical use, in being lower than the cold water of transformation temperature, stationary jaw is opened earlier, be placed on then and fracture, under the effect of body temperature, the temperature of stationary jaw is higher than the temperature of transformation temperature, design shape when stationary jaw recovers to finalize the design thermal treatment automatically fixes fracture.
Claims (4)
1, Ni-free super elastic Ti-based shape memory alloy is characterized in that described alloy contains main alloy element Ti, Zr, Nb, Al, and adds Elements C e; Each weight percentages of components is respectively: Zr:13-26%, and Nb:13-26%, Al:0.3-2.8%, Ce:0.1-1.3%, surplus is Ti and unavoidable impurities element.
2, described Ni-free super elastic Ti-based shape memory alloy goods include but not limited to: mechanicals and medical treatment product is characterized in that described goods have adopted the described Ni-free super elastic Ti-based shape memory alloy manufacturing of claim 1.
3, mechanicals according to claim 2 comprises: spectacle frame, brassiere holder, golf club, tube stub, spring, driving element.
4, medical treatment product according to claim 2 include but not limited to: medical stent, surgical implant, dental orthodontic material, seal wire, conduit, plantation tooth, intramedullary nail, Steel Plate For Fixation Of Fracture.
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| CN103060612A (en) * | 2012-12-26 | 2013-04-24 | 宁波市瑞通新材料科技有限公司 | Elastic memory alloy material for spectacle frame |
| CN103060611A (en) * | 2012-12-26 | 2013-04-24 | 宁波市瑞通新材料科技有限公司 | Preparation method of elastic memory alloy material for spectacle frame |
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| CN106676325A (en) * | 2017-01-18 | 2017-05-17 | 燕山大学 | As-cast fine-grain high-strength titanium-zirconium-aluminum-niobium alloy and preparation method thereof |
| CN112899544A (en) * | 2021-01-18 | 2021-06-04 | 中国科学院金属研究所 | Nanoscale B2 phase precipitation strengthened TixZrNbAlyMulti-principal-element alloy and preparation method thereof |
| CN113667877A (en) * | 2021-08-12 | 2021-11-19 | 北京理工大学 | TiZrVNb-based high-entropy alloy containing rare earth elements and preparation method thereof |
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| CN103054651B (en) * | 2012-12-18 | 2015-06-03 | 浙江工业大学 | Individuation orthodontic method based on shape memory polymer arch wire |
| CN103060612A (en) * | 2012-12-26 | 2013-04-24 | 宁波市瑞通新材料科技有限公司 | Elastic memory alloy material for spectacle frame |
| CN103060611A (en) * | 2012-12-26 | 2013-04-24 | 宁波市瑞通新材料科技有限公司 | Preparation method of elastic memory alloy material for spectacle frame |
| CN103060611B (en) * | 2012-12-26 | 2015-06-03 | 宁波市瑞通新材料科技有限公司 | Preparation method of elastic memory alloy material for spectacle frame |
| CN103060612B (en) * | 2012-12-26 | 2015-12-09 | 宁波市瑞通新材料科技有限公司 | A kind of Elastic memory alloy material for spectacle frame |
| CN106676325A (en) * | 2017-01-18 | 2017-05-17 | 燕山大学 | As-cast fine-grain high-strength titanium-zirconium-aluminum-niobium alloy and preparation method thereof |
| CN112899544A (en) * | 2021-01-18 | 2021-06-04 | 中国科学院金属研究所 | Nanoscale B2 phase precipitation strengthened TixZrNbAlyMulti-principal-element alloy and preparation method thereof |
| CN112899544B (en) * | 2021-01-18 | 2022-05-31 | 中国科学院金属研究所 | Nanoscale B2 phase precipitation strengthened TixZrNbAlyMulti-principal-element alloy and preparation method thereof |
| CN113667877A (en) * | 2021-08-12 | 2021-11-19 | 北京理工大学 | TiZrVNb-based high-entropy alloy containing rare earth elements and preparation method thereof |
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