CN103014414A - TiNi-base shape memory alloy containing components in graded distribution and preparation method thereof - Google Patents
TiNi-base shape memory alloy containing components in graded distribution and preparation method thereof Download PDFInfo
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- CN103014414A CN103014414A CN2013100008545A CN201310000854A CN103014414A CN 103014414 A CN103014414 A CN 103014414A CN 2013100008545 A CN2013100008545 A CN 2013100008545A CN 201310000854 A CN201310000854 A CN 201310000854A CN 103014414 A CN103014414 A CN 103014414A
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Abstract
The invention provides a TiNi-base shape memory alloy containing components in graded distribution and a preparation method thereof. The preparation method comprises the following steps of: depositing a layer of metal coating on the surface of the TiNi-base shape memory alloy by adopting an electroplating or chemical plating method; and performing diffusion annealing when the vacuum degree is not less than 10<-4> Pa and the temperature is 700 to 900 DEG C to ensure that metallic elements of the metal coating are continuously distributed along the thickness direction of the TiNi-base shape memory alloy, and the TiNi-base shape memory alloy containing the components in graded distribution is formed. The TiNi-base shape memory alloy containing the components in graded distribution has a wide phase-transition temperature range, so that the controllability of a memory alloy driver is improved conveniently. The preparation method has the characteristics of simple process and low requirement on equipment; and the TiNi-base shape memory alloy is suitable for various types of shape memory alloy drivers with different shapes, such as springs and the inner walls of twisty tubes.
Description
Technical field
What the present invention relates to is a kind of TiNi base marmem, specifically a kind of modification TiNi base marmem.The present invention also relates to a kind of preparation method of TiNi base marmem.
Background technology
As a kind of intelligent material that integrates perception, drives, the TiNi shape memory alloy has abundant martensitic transformation phenomenon, good shape memory effect and super-elasticity, good biocompatibility, has been widely used in the fields such as Aeronautics and Astronautics, machinery, the energy, electronics, biomedicine and daily life.The member of TiNi shape memory alloy can be divided into two large classes according to its mechanism: a class is the super-elasticity of utilizing its stress-induced martensite phase transformation and reverse transformation thereof to bring out, is used for permanent elastic body and is connected occasions such as carrying connection; Another kind ofly be based on the shape memory effect that its temperature trigger martensitic transformation and reverse transformation thereof produce, after reaching a certain specific temperature, occur that shape is recovered and externally acting, be used for making various driving mechanisms.At present, the maximum fully recoverable strain of TiNi alloy can reach 8%, and the unit volume output work is up to 10
7MJ/m
3, far above other actuator materials.
The controllability of driving mechanism is to need one of important factor of considering in the practical engineering application, yet the narrower phase transition temperature interval (being about 20 ℃) of TiNi shape memory alloy has greatly limited the controllability of TiNi alloy driver.The transformation temperature alloy composition of TiNi alloy is very responsive, for example, after Ni content surpasses 50.0at.%, the every increase of Ni content 1at.%, transformation temperature descends 100 ℃.In addition, add the larger variation that the 3rd a small amount of constituent element also can cause TiNi alloy phase change temperature.
The investigator has utilized magnetron sputtering technique to deposit layer of metal Ni at the TiNi alloy surface at present, has then obtained to have the TiNi alloy of certain ingredients gradient by diffusion annealing.Yet, the method preparation cycle is long, high to equipment requirements, be not suitable for the alloy components (such as spring, torque tube etc.) of complicated shape, and only be suitable for widening between the phase change zone of alloy. in addition can not deposit thickness surpass the metal Ni of 10 μ m, otherwise Ni coating will peel off from matrix owing to excessive internal stress.The formed component gradient of the method is limited simultaneously, so can not process the larger TiNi alloy of thickness.The problems referred to above cause the application of the method to be subject to certain limitation.
Summary of the invention
The object of the present invention is to provide a kind of TiNi base marmem that contains the Gradient distribution composition with wider phase transition temperature interval.The present invention also aims to provide a kind of preparation method of the TiNi base marmem that contains the Gradient distribution composition of the material that is applicable to process large specification and complicated shape.
The object of the present invention is achieved like this:
The TiNi base marmem that contains the Gradient distribution composition of the present invention is the method deposition layer of metal coating that passes through plating or electroless plating on the surface of TiNi base marmem, is not less than 10 in vacuum tightness
-4Pa, temperature are to carry out diffusion annealing under 700-900 ℃ the condition to process, and make the coated metal element along the TiNi base marmem that contains the Gradient distribution composition of TiNi base marmem thickness direction continuous distribution.
Described coated metal element is Ni, Fe, Cr or its combination.
The preparation method who contains the TiNi base marmem of Gradient distribution composition of the present invention is:
(1) the TiNi base marmem is carried out surperficial mechanical polishing or electrochemical polishing treatment;
(2) the TiNi base marmem with polishing places sulfuric acid and hydrochloric acid mixed solution to soak 10～20 minutes;
(3) utilize plating or chemical plating method at TiNi base marmem surface deposition layer of metal coating;
(4) the TiNi base marmem that deposits metal plating is not less than 10 in vacuum tightness
-4Carry out diffusion annealing under the Pa condition and process, the diffusion annealing treatment temp is 700-900 ℃, namely obtains the coated metal element along the TiNi base marmem that contains the Gradient distribution composition of TiNi base marmem thickness direction continuous distribution.
Described coated metal element is Ni, Fe, Cr or its combination.
Described diffusion annealing treatment temp is 900 ℃.
Described TiNi base marmem is for containing the alloy components of complicated shape of the Ni of 48-51% by atomic percent
The alloy components of described complicated shape is spring or torque tube.
The TiNi base marmem that contains the Gradient distribution composition that the present invention is prepared, the through-thickness continuous distribution Ni that contains or Fe, Cr grade in an imperial examination three compositions.Therefore have wider phase transition temperature interval, thereby be conducive to improve the controllability of memory alloy actuator.Simultaneously, the present invention can further give material more excellent characteristic by selecting suitable alloying element, and the component gradient alloy that for example utilizes the Fe element to make up has more excellent damping characteristic.The component gradient alloy that utilizes the Cr element to make up not only can obtain wider phase transition temperature interval, can also obtain the mechanical characteristics such as the rigidity of through-thickness continuous distribution and yield strength.It is simple that preparation method of the present invention has technique, low for equipment requirements, be applicable to various difform marmens, inwall such as spring and torque tube, can adjust easily by the processing parameter of control plating or chemical plating technology and diffusion annealing the Gradient distribution situation of alloying element, obtain to have the alloy of larger component gradient.
Description of drawings
Fig. 1 is the Cross Section Morphology of plated surface Ni layer that contains the TiNi base marmem of Gradient distribution Ni.
Fig. 2 is that current density and electroplating time are on the impact of Ni thickness of coating.
Fig. 3 is that electroplating temperature is on the impact of Ni thickness of coating.
Fig. 4 contains the Cross Section Morphology of TiNi base marmem of Gradient distribution Ni and the position of energy spectrum analysis.
Fig. 5 is alloying constituent and relation apart from Ni coating and TiNi alloy interface position.
Fig. 6 (a)-Fig. 6 (b) is for containing the TiNi base marmem of Gradient distribution Ni and the DSC curve of homogeneous TiNi alloy.
Fig. 7 contains the TiNi base marmem of Gradient distribution Ni and the comparison of homogeneous TiNi alloy phase change temperature range.
Embodiment
The below does more detailed description to the present invention for example:
Embodiment one:
(1) the TiNi base marmem is ground then mechanical polishing with 240#, 600#, 1000#, 2000#, 4000# abrasive paper for metallograph successively;
(2) the TiNi base marmem of polishing to be placed concentration be 98% sulfuric acid with concentration is 37% hydrochloric acid mixed solution immersion 15 minutes, and the volume ratio of sulfuric acid and hydrochloric acid is 13:7;
(3) utilize electroplating technology at the good TiNi base marmem deposition layer of Ni coating of pre-treatment, the watt type plating Ni liquid of plating bath we selected typical: six hydration nickel sulfate 260～280g/l), nickelous chloride 40～45g/l), boric acid 35～40g/l, sodium lauryl sulphate 0.05～0.1g/l, electroplating technological parameter is: current density is 1.5～3A/dm
2, the pH value is 3～5, and temperature is 30～60 ℃, and the time is 10～60 minutes.Electroplating process is divided into strike plating and thickens plating, and the strike plating current density is 3A/dm
2, thickening the plating current density is 1.5A/dm
2
The TiNi base marmem that (4) will deposit metal plating is enclosed vacuum tightness and is not less than 10
-4In the silica tube of Pa, carry out diffusion annealing and process in the Conventional Heat Treatment stove, the diffusion annealing treatment temp is 900 ℃, and the time is 1～10h, can obtain containing the TiNi base marmem of Gradient distribution Ni.
Adopt the method for spark cutting, cutting length in the TiNi of the covering Ni coating that above-mentioned steps (3) makes is that 10mm, width are that 5mm, thickness are the thin slice of 0.35mm, grind off the cutting vestige with sand paper, with Cross section polishing, observe the interface of coating and matrix, the scanning electron photomicrograph of acquisition is as shown in Figure 1, as seen, thickness of coating is about 50 μ m, and combination is tight between coating and the matrix, and is seamless.The relation of thickness of coating and current density, electroplating time and temperature is respectively shown in Fig. 2 and 3.Cutting length in the component gradient distribution TiNi alloy that above-mentioned steps (4) makes is that 10mm, width are that 5mm, thickness are the thin slice of 0.35mm, grinds off cutting vestige and polishing with sand paper, utilizes the sem observation interface conditions, result such as Fig. 4.Utilize energy spectrum analysis to carry out composition analysis at distance Ni film and TiNi matrix 10 μ m, 76 μ m, 210 μ m, 337 μ m places respectively, particular location is shown in A, B, C, D among Fig. 4, analytical results as shown in Figure 5, show through after the 900 ℃/1h diffusion annealing processing, in alloy, formed component gradient.The content of considering simultaneously Ni in the initial state TiNi alloy is 50.2at.%, can find that component gradient is larger in the TiNi alloy.This mainly is because adopt the Ni coating of electric plating method preparation thicker, and enough Ni atoms can be provided in diffusion annealing.Cutting diameter in mentioned component Gradient distribution TiNi alloy is that 4mm, thickness are the thin slice of 0.35mm, grinds off surface cutting vestige with sand paper, and at its transformation behavior of PerkinElmer Diamond DSC test, the DSC curve of acquisition is shown in Fig. 6 (a).For ease of relatively, also provided the DSC curve of homogeneous TiNi alloy among Fig. 6 (b).Usually definition martensitic transformation starting temperature (Ms) is the positive phase transition temperature interval of martensite with the difference of finishing temperature (Mf), martensitic transformation reverse transformation finishing temperature (Af) is that the martensite Reverse Martensitic Transformation Temperatures is interval with the difference of starting temperature (As), utilize tangent method to determine transformation temperature in the DSC of Fig. 6 curve and calculate the positive phase transition temperature interval of martensite and the Reverse Martensitic Transformation Temperatures interval, the result as shown in Figure 7.As seen, component gradient TiNi alloy just, the Reverse Martensitic Transformation Temperatures interval be respectively 47 ℃ with 60 ℃, the phase transition temperature interval (20 ℃ and 21 ℃) that is higher than homogeneous TiNi alloy far away, this shows that the present invention can increase the phase transition temperature interval of TiNi alloy effectively, thereby improves the controllability of driving mechanism.
Embodiment two: present embodiment and embodiment one difference are that the plating bath that adopts is in the step in the present embodiment (3): iron protochloride 350～400g/l, sodium-chlor 10～20g/l, Manganous chloride tetrahydrate 1～5g/l, boric acid 5～8g/l.Other concrete technology parameters comprise: current density is 15～25A/dm
2, the pH value is 1.0～1.8, and temperature is 30～55 ℃, and the time is 10～60 minutes.
Embodiment three: present embodiment and embodiment one difference are to adopt plating Cr liquid to be in the step in the present embodiment (3): chromic anhydride 150～180g/l, sulfuric acid 1.5～1.8g/l.Other concrete technology parameters comprise: current density is 30～45A/dm
2, the pH value is 3～5, and temperature is 55～60 ℃, and the time is 10～60 minutes.
Embodiment four: present embodiment and embodiment one difference are, the technique that adopts in the step in the present embodiment (3) is Electroless Plating Ni, six hydration nickel sulfate 260g/l), nickelous chloride 40g/l, boric acid 35g/l, sodium lauryl sulphate 0.05g/l plating bath is as follows:, electroplating technological parameter is: current density is 1.5A/dm
2, the pH value is 3.5, and temperature is 55 ℃, and the time is 10～15 minutes.Other is identical with embodiment one.
Embodiment five: present embodiment and embodiment four differences are, the technique that adopts in the step in the present embodiment (3) is electroless plating Fe, plating bath is ferrous sulfate 30g/l, sodium hypophosphite 10g/l, Seignette salt 50g/l, the concrete technology parameter is as follows: the pH value is 8～10, temperature is 77～98 ℃, and the time is 10～15 minutes.Other is identical with embodiment one.
Embodiment six: present embodiment and embodiment four differences are, the technique that adopts in the step in the present embodiment (3) is electroless plating Cr, plating bath is chromium chloride 11g/l, chromic bromide 16g/l, sodium hypophosphite 10g/l, potassium oxalate 4.5g/l, sodium acetate 10g/l, the concrete technology parameter is as follows: the pH value is 4～6, temperature is 75～90 ℃, and the time is 10～15 minutes.Other is identical with embodiment one.
Need to prove that at last the glossing of TiNi alloy also can be electrochemical etching in the step of the present invention (1), can satisfy like this polishing requirement of the TiNi memorial alloy of complicated shape.
Claims (9)
1. a TiNi base marmem that contains the Gradient distribution composition is characterized in that: be the method deposition layer of metal coating that passes through plating or electroless plating on the surface of TiNi base marmem, be not less than 10 in vacuum tightness
-4Pa, temperature are to carry out diffusion annealing under 700-900 ℃ the condition to process, and make the coated metal element along the TiNi base marmem that contains the Gradient distribution composition of TiNi base marmem thickness direction continuous distribution.
2. the TiNi base marmem that contains the Gradient distribution composition according to claim 1, it is characterized in that: described coated metal element is Ni, Fe, Cr or its combination.
3. preparation method who contains the TiNi base marmem of Gradient distribution composition is characterized in that:
(1) the TiNi base marmem is carried out surperficial mechanical polishing or electrochemical polishing treatment;
(2) the TiNi base marmem with polishing places sulfuric acid and hydrochloric acid mixed solution to soak 10～20 minutes;
(3) utilize plating or chemical plating method at TiNi base marmem surface deposition layer of metal coating;
(4) the TiNi base marmem that deposits metal plating is not less than 10 in vacuum tightness
-4Carry out diffusion annealing under the Pa condition and process, the diffusion annealing treatment temp is 700-900 ℃, namely obtains the coated metal element along the TiNi base marmem that contains the Gradient distribution composition of TiNi base marmem thickness direction continuous distribution.
4. the preparation method who contains the TiNi base marmem of Gradient distribution composition according to claim 3, it is characterized in that: described coated metal element is Ni, Fe, Cr or its combination.
5. according to claim 3 or the 4 described preparation methods that contain the TiNi base marmem of Gradient distribution composition, it is characterized in that: described diffusion annealing treatment temp is 900 ℃.
6. it is characterized in that according to claim 3 or the 4 described preparation methods that contain the TiNi base marmem of Gradient distribution composition: described TiNi base marmem is the alloy components of the complicated shape of the Ni that contains 48-51% by atomic percent.
7. the preparation method who contains the TiNi base marmem of Gradient distribution composition according to claim 5 is characterized in that: described TiNi base marmem is the alloy components of the complicated shape of the Ni that contains 48-51% by atomic percent.
8. the preparation method who contains the TiNi base marmem of Gradient distribution composition according to claim 6, it is characterized in that: the alloy components of described complicated shape is spring or torque tube.
9. the preparation method who contains the TiNi base marmem of Gradient distribution composition according to claim 7, it is characterized in that: the alloy components of described complicated shape is spring or torque tube.
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| CN108690967A (en) * | 2018-05-04 | 2018-10-23 | 深圳市中科摩方科技有限公司 | Nitinol medical instrument with face coat and coating production |
| CN110508815A (en) * | 2019-10-09 | 2019-11-29 | 山东大学 | A method of niti-shaped memorial alloy phase transition temperature is regulated and controled based on increasing material manufacturing |
| CN111041421A (en) * | 2019-12-30 | 2020-04-21 | 哈尔滨工业大学 | Shape memory alloy radial gradient film and preparation method thereof |
| CN114540606A (en) * | 2022-03-09 | 2022-05-27 | 西部金属材料股份有限公司 | Preparation method of high-hardness titanium alloy sheet and foil |
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| CN114540606A (en) * | 2022-03-09 | 2022-05-27 | 西部金属材料股份有限公司 | Preparation method of high-hardness titanium alloy sheet and foil |
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