CN104745878B - Moderate strength flexible narrow lag NiTiWCu quaternary alloy and preparation method and application thereof - Google Patents
Moderate strength flexible narrow lag NiTiWCu quaternary alloy and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a moderate strength flexible narrow lag NiTiWCu quaternary alloy and a preparation method and application thereof. The alloy comprises the following chemical components by weight: 0.55%-10.5% of W, 0.3%-0.95% of Cu, and balance of Ni and Ti, and the Ni and Ti atom ratio is 1.024-1.072. The compositely modified quaternary alloy has moderate yield strength approximate to the ordinary nickel titanium alloy yield strength, the elastic modulus is lower than that of the ordinary nickel titanium alloy, the quaternary alloy has good mechanical compatibility and good processing performance, and cold and hot processing performances are slightly better than that of the ordinary nickel titanium alloy. The product made of the alloy can be widely used in medical appliances and sporting goods and other fields, and can be used as super elastic brackets, orthodontic tooth arch wires, implantation instruments of orthopedics, and the like, and the arch wire product made of the alloy also has the advantages of flexibility and narrow lag.
Description
Technical field
The invention belongs to nickel alloy technical field and in particular to a kind of upper mounting plate intensity and lower platform strength difference low in
Flexible narrow delayed NiTiWCu quaternary alloy of equal strength and its preparation method and application.
Background technology
Nitinol has good mechanical property and excellent fatigue behaviour, abrasion resistance properties and corrosion resistance, nickel
Titanium alloy has the three zones characteristic of uniqueness, i.e. elastic performance, shape-memory properties and damping capacity, and Nitinol also has
Excellent biocompatibility.Therefore have been widely used for the fields such as Aeronautics and Astronautics, naval vessel and medicine equipment.In medicine equipment neck
Domain has extensively substituted stainless steel and has been used as body implant metal material, is clinically widely used.NiTi closes
Gold is by with intravascular stent, all kinds of non-vessel stent, spinal correction rod, bone fracture fixation plate, medical guiding wire and operation suture thread etc..
Stretched in martensite reverse transformation finishing temperature temperatures above, martensite transfor mation, shape are occurred under stress
Become stress-induced martensite.Increase martensite with stress to grow up, otherwise martensite reduces, after stress elimination, martensite disappears.Close
Gold deformation is caused due to stress-induced martensitic phase transformation, stress removal, and deformation disappears, and martensite reverses and is changed into parent phase.
This do not pass through to heat return to the phenomenon of parent phase shape and be referred to as superelastic or pseudoelastic.Common Nitinol superlastic is sluggish bent
The upper mounting plate intensity of line is higher, and often close to 600MPa, and lower platform intensity is relatively low, often below 200MPa or lower, makes
On one-tenth, lower platform strength difference is more than 300MPa, Stress resort width.
By add micro or oligo-element can change Nitinol phase transition temperature, mechanical property and elastic performance and
Memory performance.As added Nb can form wide transformation hysteresis marmem, add Cr and Fe and can drop low-alloyed phase transition temperature,
Add the marmem that Zr, Hf and Pb etc. form high phase transition temperature, the elements such as Al, Si, Mo, V, Mn, Co can also be added,
Exploitation defines multiple niti-shaped memorial alloy series, such as Ti-Ni-Cu, Ti-Ni-Nb, Ti-Ni-Pb, Ti-Ni-Fe, Ti-
The new Nitinol such as Ni-Cr.Alloying element has a significant effect to the performance of Nitinol, defines the shape with different qualities
Shape memory alloys.
Chinese patent CN103131926A discloses a kind of W/TiNi memory alloy composite material, claim volume fraction
1～12% wolfram element, its minimum weight percentage is 24%.The one kind that functions as of wolfram element strengthens phase constituent element, its surrender
Intensity reaches 900MPa.The effect of wolfram element is to increase the developability of matrix simultaneously.Chinese patent CN102719707A discloses
A kind of Ni-Ti semi-finished product and correlation technique, wherein alloying element X can be selected for W element, and scope is atomic percent is 0.1～1%,
Alloy not cupric.Chinese patent CN101457315A discloses a kind of high intensity Ni-Ti alloy, claim tungsten percentage by weight
For 0.01～0.50%, wolfram element function as a kind of dispersion-strengtherning phase constituent element.Chinese patent CN101617961A discloses
A kind of titanium-based quinary alloy, product and preparation method, claim weight of copper percentage is 1～10%, and in alloy, tungstenic is not first
Element.
When Orthodontic Treatment is applied, having the flexible narrow delayed Nitinol correction silk material of moderate strength can produce
Soft Orthodontic force, action time, persistently restoring force was high, and residual deformation is little, and patient's pain and sense of discomfort are inconspicuous.
The present invention is to add a small amount of W and Cu alloying element on the basis of binary Nitinol, using tungsten and copper, binary is closed
Gold carries out composite modified, the intensity of reduction Nitinol matrix, reduces the elastic modelling quantity of matrix, constriction lagging width simultaneously, shape
Become the flexible narrow delayed NiTiWCu quaternary alloy of moderate strength.This new Ni-Ti-W-Cu quaternary alloy good processability, cost
Low.
Content of the invention
It is an object of the invention to provide a kind of flexible narrow delayed NiTiWCu quaternary alloy of moderate strength and its preparation processing
And methods for using them.
To achieve these goals, technical scheme is as follows：
A kind of flexible narrow delayed NiTiWCu quaternary alloy of moderate strength, the percentage by weight of each composition is：Tungsten（W）：
0.55%～10.5%, copper（Cu）：0.3%～0.95%, balance of nickel（Ni）, titanium（Ti）, the atomicity ratio of wherein Ni, Ti is
1.024～1.072.
Above-mentioned quaternary alloy also includes the inevitable impurity of following percentage by weight：Fe：0.01-0.04%；Si：
0.01-0.03%；C：0.005-0.03%；O：0.02-0.05%.
The preparation method of the flexible narrow delayed NiTiWCu quaternary alloy of above-mentioned moderate strength, concrete preparation method include as
Lower step：Raw material containing Ni, Ti, W, Cu is pressed into electrode, becomes ingot casting through vacuum induction melting；By ingot casting 850～
1000 DEG C of Homogenization Treatments 60～240min；Then carry out hot-working；Last 350 DEG C～600 DEG C Ageing Treatment 5～
180min.
The raw material of above-mentioned Ni is pure nickel plate, electrolytic nickel or tungsten nickel；The raw material of Ti is that Titanium board, titanium sponge or tungsten titanium close
Gold；The raw material of Cu is fine copper plate；The raw material of W is tungsten-titanium alloy or tungsten nickel.
Above-mentioned hot worked technique includes：Hammer cogging, roll, swage, drawing step；The temperature of hammer cogging is 850-
1000 DEG C, the temperature of rolling is 850-950 DEG C, and the temperature swaged is 750-850 DEG C, and the temperature of wire drawing is 680-700 DEG C, wire drawing
Temperature be 680-700 DEG C, every time deflection of wire drawing be 10～30%, total deformation be 80～95%.
Application in preparing medicine equipment for the flexible narrow delayed NiTiWCu quaternary alloy of above-mentioned moderate strength.
Above-mentioned medicine equipment is gear division orthopedic instruments, super-elasticity human body implants support or orthopaedics implantation instrument.
Above-mentioned gear division orthopedic instruments is dental arch filament.
Above-mentioned dental arch filament is circular dental arch filament or side's bow dental arch filament, and circular dental arch filament specification is 0.31～0.51mm, Fang Gong
Dental arch filament specification is 0.41mm*0.41mm～0.51mm*0.61mm.
Beneficial effects of the present invention are as follows：The present invention adds W element and Cu element on the basis of binary Nitinol, obtains
In effect and prior art that a kind of flexible narrow delayed NiTiWCu quaternary alloy of moderate strength, W element and Cu element are played
The effect of report is entirely different, strengthens function from enhancing yield strength, developability of increase matrix etc. in conventional art different,
After composite modified, quaternary alloy only has medium yield strength, and after adding W element and Cu element, matrix strength does not substantially increase
Plus, the matrix strength after adding tungsten and copper of some alloys within the specific limits slightly reduces on the contrary, and common Nitinol
Yield strength is close；But lower platform strength difference only has 200MPa, Stress resort on the quaternary alloy after composite modified
Narrow, elastic modelling quantity is less than common Nitinol, has good mechanical compatibility；And the quaternary alloy processability after composite modified
Can be good, hot and cold processability is slightly better than common Nitinol, it is possible to use the traditional preparation processing method of Nitinol manufactures.This
Invention alloy is made product and be can be widely used for the fields such as medicine equipment and sports goods.
Brief description
Fig. 1 is the superlastic curve of the dental arch filament prepared for material with the NiTiWCu quaternary alloy of embodiment 1-4.
In figure, (a)-embodiment 1, (b)-embodiment 2；(c)-embodiment 3；(d)-embodiment 4.
Specific embodiment
Below by specific embodiment, the present invention will be further described, but is not meant to the scope of the present invention
Restriction.
Embodiment 1
With titanium sponge, electrolytic nickel, tungsten-titanium alloy, fine copper plate, tungsten nickel as raw material, gross weight is 27 kilograms, each group
The designing quality divided is respectively：Tungsten（W）：2.835 kilogram, Cu：0.175 kilogram, nickel（Ni）：13.407 kilogram, titanium（Ti）：
10.583 kilograms.The electrode of 2.3 kilograms of compacting, becomes cylinder ingot casting through vacuum induction melting, melting useful vacuum degree is not
More than 7Pa.Ingot casting test chemical composition after melting, actual measurement tungsten percentage by weight is 10.5%, and weight of copper percentage is 0.7%, nickel
Percentage by weight is 49.80%, and oxygen percentage by weight is 0.033%, and carbon weight percentage is 0.026%, and silicon percentage by weight is
0.03%, iron percentage by weight is 0.032%, and other elements percentage by weight is less than 0.025%.Titanium percentage by weight is surplus.Casting
Ingot after 1000 DEG C of homogenization insulation 60min, in 900 DEG C of temperature hammer coggings, through 860 DEG C of rollings, 800 DEG C swage, 680
Silk material, bar are processed in DEG C wire drawing etc., and total deformation is 85%, and every time deflection of wire drawing is about between 12～20%.At timeliness
Reason temperature is 350 DEG C, and temperature retention time is 180min.Process the plate of the silk material, bar and thickness 2mm of diameter 0.2～3.5mm
Material.Process the correction circular dental arch filament for manufacturing gear division orthopedic instruments, the specification of circular dental arch filament is 0.51mm.Dental arch filament
Performance see attached list 1, superlastic curve is shown in Fig. 1（a）Shown.
Embodiment 2
With titanium sponge, electrolytic nickel, fine copper plate, tungsten-titanium alloy, tungsten nickel as raw material, gross weight is 27 kilograms, each group
The designing quality divided is respectively：Tungsten（W）：0.432 kilogram, Cu：0.095 kilogram, nickel（Ni）：14.973 kilogram, titanium（Ti）：
11.500 kilograms.The electrode of 2.3 kilograms of compacting, becomes cylinder ingot casting through vacuum induction melting, melting useful vacuum degree is not
More than 7Pa.Ingot casting test chemical composition after melting, actual measurement tungsten percentage by weight is 1.7%, and weight of copper percentage is 0.4%, nickel weight
Amount percentage is 55.5%, and oxygen percentage by weight is 0.043%, and carbon weight percentage is 0.027%, and silicon percentage by weight is
0.028%, iron percentage by weight is 0.03%, and other elements percentage by weight is less than 0.025%.Titanium percentage by weight is surplus.Casting
Ingot after 850 DEG C of homogenization insulation 240min, in 950 DEG C of temperature hammer coggings, through 950 DEG C of rollings, 850 DEG C swage, 700
Silk material, bar are processed in DEG C wire drawing etc., and total deformation is 80%, and every time deflection is about between 15～30%.Ageing Treatment temperature
Spend for 600 DEG C, temperature retention time is 5min.Process the sheet material of the silk material, bar and thickness 3mm of diameter 0.2～3.5mm.Processing
Go out for manufacturing gear division orthopedic instruments correction circular dental arch filament, the specification of circular dental arch filament is 0.31mm.The performance of dental arch filament is shown in
Subordinate list 1, superlastic curve is shown in Fig. 1（b）Shown.
Embodiment 3
With titanium sponge, pure nickel plate, tungsten-titanium alloy, fine copper plate, tungsten nickel as raw material, gross weight is 27 kilograms, each group
The designing quality divided is respectively：Tungsten（W）：0.189 kilogram, Cu：0.257 kilogram, nickel（Ni）：14.782 kilogram, titanium（Ti）：
11.772 kilograms.The electrode of 2.3 kilograms of compacting, becomes cylinder ingot casting through vacuum induction melting, melting useful vacuum degree is not
More than 7Pa.Ingot casting test chemical composition after melting, actual measurement tungsten percentage by weight is 0.66%, and weight of copper percentage is 0.95%, nickel
Percentage by weight is 54.8%, and oxygen percentage by weight is 0.04%, and carbon weight percentage is 0.027%, and silicon percentage by weight is
0.028%, iron percentage by weight is 0.03%, and other elements percentage by weight is less than 0.025%.Titanium percentage by weight is surplus.Casting
Ingot after 950 DEG C of homogenization insulation 120min, in 1000 DEG C of temperature hammer coggings, through 950 DEG C of rollings, 850 DEG C swage,
Silk material, bar are processed in 700 DEG C of wire drawings etc., and total deformation is 90%, and every time deflection is about between 15～25%.Ageing Treatment
Temperature is 450 DEG C, and temperature retention time is 30min.Process silk material, diameter 0.2～0.8mm.Process orthopedic for manufacturing gear division
Bend dental arch filament for apparatus correction side, and the specification of side's bow dental arch filament is 0.41mm*0.41mm.The performance of dental arch filament sees attached list 1, and superlastic is bent
Fig. 1 is shown in by line（c）Shown.
Embodiment 4
With Titanium board, pure nickel plate, tungsten-titanium alloy, fine copper plate, tungsten nickel as raw material, gross weight is 27 kilograms, each group
The designing quality divided is respectively：Tungsten（W）：0.148 kilogram, Cu：0.081 nickel（Ni）：14.903 kilogram, titanium（Ti）：11.868 thousand
Gram.The electrode of 2.3 kilograms of compacting, becomes cylinder ingot casting through vacuum induction melting, melting useful vacuum degree is all not more than 7Pa.
Ingot casting test chemical composition after melting, actual measurement tungsten percentage by weight is 0.55%, and weight of copper percentage is 0.3%, nickel weight percent
For 55.2%, oxygen percentage by weight is 0.037% to ratio, and carbon weight percentage is 0.029%, and silicon percentage by weight is 0.026%, iron weight
Amount percentage is 0.034%, and other elements percentage by weight is less than 0.025%.Titanium percentage by weight is surplus.Ingot casting is through 850
After DEG C homogenization insulation 120min, in 850 DEG C of temperature hammer coggings, through 850 DEG C of rollings, 750 DEG C swage, 680 DEG C of wire drawings etc.
It is processed into silk material, bar, total deformation is 95%, and every time deflection is about between 15～25%.Aging temperature is 400
DEG C, temperature retention time is 30min.The product processing includes silk material, diameter 0.2～0.9mm.Process orthopedic for manufacturing gear division
Bend dental arch filament for apparatus correction side, and the specification of side's bow dental arch filament is 0.51mm*0.61mm.The performance of dental arch filament sees attached list 1, and superlastic is bent
Fig. 1 is shown in by line（d）Shown.
The mechanical property such as following table of the dental arch filament prepared for material with NiTiWCu quaternary alloy of the present invention：
Table 1 embodiment 1-4 alloy dental arch filament surveys mechanical property
Claims (8)
1. a kind of preparation method of the flexible narrow delayed NiTiWCu quaternary alloy of moderate strength is it is characterised in that described quaternary is closed
In gold, each composition and its percentage by weight are：W：0.55%～10.5%, Cu：0.3%～0.95%, balance of Ni, Ti, wherein
The atomicity of Ni, Ti is than for 1.024～1.072；
Concrete preparation method comprises the steps：Raw material containing Ni, Ti, W, Cu is pressed into electrode, melts through vaccum sensitive stove
It is smelt ingot casting；By ingot casting in 850～1000 DEG C of Homogenization Treatments 60～240min；Then carry out hot-working, described hot worked
Technique includes：Hammer cogging, roll, swage, drawing step；The temperature of hammer cogging is 850-1000 DEG C, and the temperature of rolling is
850-950 DEG C, the temperature swaged is 750-850 DEG C, and the temperature of wire drawing is 680-700 DEG C, every time deflection of wire drawing is 10～
30%, total deformation is 80～95%；Finally in 350 DEG C～600 DEG C Ageing Treatment 5～180min.
2. the preparation method of the flexible narrow delayed NiTiWCu quaternary alloy of moderate strength according to claim 1, its feature
It is, the raw material of described nickel is pure nickel plate, electrolytic nickel or tungsten nickel；The raw material of described titanium is Titanium board, titanium sponge or tungsten titanium
Alloy；The raw material of described copper is fine copper plate；The raw material of described tungsten is tungsten-titanium alloy or tungsten nickel.
3. the flexible narrow delayed NiTiWCu quaternary alloy of a kind of moderate strength based on preparation method described in claim 1, it is special
Levy and be, in this alloy, each composition and its percentage by weight are：W：0.55%～10.5%, Cu：0.3%～0.95%, surplus
For Ni, Ti, wherein the atomicity of Ni, Ti is than for 1.024～1.072.
4. according to claim 3 a kind of flexible narrow delayed NiTiWCu quaternary alloy of moderate strength it is characterised in that institute
State the inevitable impurity that quaternary alloy also includes following percentage by weight：Fe：0.01-0.04%；Si：0.01-0.03%；
C：0.005-0.03%；O：0.02-0.05%.
5. the flexible narrow delayed NiTiWCu quaternary alloy of the moderate strength described in claim 3 answering in preparing medicine equipment
With.
6. application according to claim 5 is it is characterised in that described medicine equipment is gear division orthopedic instruments, super-elasticity people
Body implantation support or orthopaedics implantation instrument.
7. application according to claim 6 is it is characterised in that described gear division orthopedic instruments is dental arch filament.
8. according to claim 7 application it is characterised in that described dental arch filament be circular dental arch filament or side bow dental arch filament,
Circular dental arch filament specification is 0.31～0.51mm, and side's bow dental arch filament specification is 0.41mm*0.41mm～0.51mm*0.61mm.
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| CN110983147B (en) * | 2019-12-20 | 2021-05-11 | 有研亿金新材料有限公司 | High-strength palladium-based weak electrical contact material and preparation method thereof |
| CN113559333B (en) * | 2021-06-07 | 2022-11-08 | 中国科学院金属研究所 | Medical nickel-titanium alloy with high anticoagulation function without surface treatment |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4144057A (en) * | 1976-08-26 | 1979-03-13 | Bbc Brown, Boveri & Company, Limited | Shape memory alloys |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS59150069A (en) * | 1983-02-15 | 1984-08-28 | Hitachi Metals Ltd | Manufacture of shape memory alloy |
| JPH0441640A (en) * | 1990-06-07 | 1992-02-12 | Furukawa Electric Co Ltd:The | Superelastic alloy wire rod for catheter guide wire and its manufacture |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4144057A (en) * | 1976-08-26 | 1979-03-13 | Bbc Brown, Boveri & Company, Limited | Shape memory alloys |
Non-Patent Citations (1)
| Title |
|---|
| Transformation sequence and second phases in ternary Ti-Ni-W shape memory alloys with less than 2 at.%W;S.F.Hsieh et al.;《Journal of Alloy and Compounds》;20051231;第122页左栏 * |
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