CN101805843B - NbTi/TiNi memory alloy composite material and preparation method thereof - Google Patents
NbTi/TiNi memory alloy composite material and preparation method thereof Download PDFInfo
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- CN101805843B CN101805843B CN2010101506120A CN201010150612A CN101805843B CN 101805843 B CN101805843 B CN 101805843B CN 2010101506120 A CN2010101506120 A CN 2010101506120A CN 201010150612 A CN201010150612 A CN 201010150612A CN 101805843 B CN101805843 B CN 101805843B
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Abstract
The invention relates to an NbTi/TiNi memory alloy composite material and a preparation method thereof. The memory alloy composite material comprises the following components calculated by the total weight of the memory alloy composite material: Nb element with the atomic percentage of 18-22%, and Ti element and Ni element with the atomic rate of 0.3: 1-1.5: 1, wherein the sum of the atomic percentage of the three elements of Ti, Ni and Nb is 100%. The memory alloy composite material has the special functional features of high yield strength, strain soft mode, linear super-elasticity, double-stress platform and the like. The invention further relates to the preparation method of the NbTi/TiNi memory alloy composite material, which comprises the following steps: selecting elementary substances of niobium, titanium and nickel with the purity of above 99.0% by weight according to the mixture ratio of the components of the NbTi/TiNi memory alloy composite material, placing the elementary substances of niobium, titanium and nickel into a smelting furnace with the vacuum degree of being higher than 10-1Pa or inert gas protection, and smelting for forming the NbTi/TiNi memory alloy composite material.
Description
Technical field
The present invention relates to a kind of NbTi/TiNi memory alloy composite material and preparation method thereof, relating in particular to a kind of is wild phase with NbTi mutually, is matrix mutually with TiNi, has memory alloy composite material of the ultra-fine eutectic structure of as cast condition in-situ authigenic and preparation method thereof.
Background technology
TiNi base marmem (SMA) is as a kind of novel metal functional materials, and because of having characteristics such as shape memory effect, high damping, super-elasticity, it has obtained widespread use in fields such as aerospace, medical treatment, industry, lives.Yet the TiNi memorial alloy generally is martensitic state when having excellent damping capacity, and yield strength has only 100-200MPa, so low yield strength limited greatly its under the high-load environment as Applicaltion of damping material.In addition, the micro drives device that utilizes TiNi memorial alloy super-elasticity to make has also limited its being extensive use of as intelligent material because yield strength is hanged down.
200580036111.7 number Chinese patent application discloses the fibre-reinforced matrix material of a kind of memorial alloy, it is to add shape-memory alloy wire in fiber reinforced polymer composites, to improve the shock resistance of matrix material; Because millimetre-sized TiNi silk specific surface area is little, under the effect of phase transformation restoring force, there is big shear-stress in the interface of itself and matrix, viscous deformation or exoneration take place easily, so people catch at specific surface area is big, interface bond strength is high micron or nano level TiNi memorial alloy in-situ authigenic matrix material.
Bao Dao TiNi memorial alloy/aluminium, polymer and cement composite material in the past, be millimeter level TiNi silk to be compound in make matrix material have excellent properties in the body material, but because millimeter level TiNi silk specific surface area is little, viscous deformation or exoneration take place in interface easily between itself and matrix under the effect of phase transformation recovery stress, and adopt to add TiNi silk composite algorithm and be difficult to the homogeneity that guarantees that TiNi distributes in matrix, influence the functional performance (in being subjected to thermal process, easily bending) of matrix material as sample.These shortcomings all may cause the shape memory effect of TiNi alloy, super-elasticity fully to be coupled with matrix, other functional performances of the cognitive memory alloy composite material of restriction people.Therefore how to obtain that a kind of TiNi sheet is tiny, specific surface area big, be evenly distributed, make it both possess the attribute that the memorial alloy intelligent composite is had with the high memory alloy composite material of substrate combinating strength, can solve the shortcoming of memory alloy composite material existence in the past again, has simultaneously higher intensity again, especially higher yield strength, can satisfy the memory alloy composite material of the requirement of high-load Working environment, be still one of present problem demanding prompt solution in this area.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of NbTi/TiNi memory alloy composite material, enhancing by the relative TiNi matrix of NbTi, obtain a kind of memory alloy composite material with the ultra-fine eutectic structure of as cast condition in-situ authigenic, this matrix material has functional performances such as higher yield strength, strain soft mode, linear super bullet, two stress plateaus.
The present invention also aims to provide the preparation method of above-mentioned NbTi/TiNi memory alloy composite material, prepare the NbTi/TiNi memory alloy composite material by metal simple-substance is carried out melting.
For achieving the above object, the present invention at first provides a kind of NbTi/TiNi memory alloy composite material, total amount in this memory alloy composite material, it comprises following composition: atomic percent is the Nb element of 18-22% (being preferably 20at%), and atomic ratio is 0.3: 1-1.5: 1 Ti element and Ni element, three kinds of elements atomic percentage sums of Ti, Ni and Nb are 100%.
NbTi/TiNi memory alloy composite material provided by the invention is to be wild phase mutually, to be the memory alloy composite material of matrix mutually with TiNi with NbTi, NbTi contains minor N i in mutually, TiNi contains minor N b in mutually, wherein, NbTi can be present in the TiNi matrix with forms such as spherical, fibrous (wire) or sheets mutually, and, the size of NbTi phase can reach Nano grade, therefore, can be called be that a kind of NbTi nanophase strengthens the TiNi memory alloy composite material to NbTi/TiNi memory alloy composite material provided by the invention.In concrete technical scheme of the present invention, the NbTi/TiNi memory alloy composite material is to be raw material with Ti, Ni, Nb metal simple-substance, prepare by melting, in fusion process, the mode that NbTi meets with in-situ authigenic is formed in the TiNi matrix, form the ultra-fine eutectic structure of as cast condition in-situ authigenic, the two-phase interface combination is good mutually with TiNi mutually for NbTi, has very high interface bond strength.
Do not produce Ti in the NbTi/TiNi memory alloy composite material in order to make
2Ni, Ni
3Fragility phases such as Ti, has simultaneously higher cold deformation working ability again, the Ti of this memory alloy composite material and the atomic ratio of Ni may be controlled to 0.3: 1-1.5: 1, preferably Ti element and Ni atoms of elements ratio can be controlled to be 0.8: 1-1.2: 1, all the other are the Nb element, and Ti, Ni, three kinds of elements atomic percentage sums of Nb are 100%.
The concrete technical scheme according to the present invention, NbTi/TiNi memory alloy composite material can be different forms, can be the ingot castings of direct pouring moulding, also can be that ingot casting is processed the section bar that obtains through the method for further plastic working, for example sheet material and silk material etc.Preferably, when above-mentioned matrix material is ingot casting (when being cast alloy in other words), it is spherical that NbTi is mutually, and its diameter is about 0.5-1 micron; When matrix material was the silk material, NbTi was fibrous (wire) mutually, and its diameter is about 20-100 nanometer; When matrix material is sheet material, NbTi mutually in the form of sheets, its thickness is about 30-100 nanometer.
The present invention also provides the preparation method of above-mentioned NbTi/TiNi memory alloy composite material, and it may further comprise the steps:
Choose simple substance niobium, titanium, the nickel of purity more than 99.0wt.% according to the composition proportion of NbTi/TiNi memory alloy composite material;
Simple substance niobium, titanium, nickel are put into vacuum tightness be higher than 10
-1In the smelting furnace of Pa or protection of inert gas, be smelted into the NbTi/TiNi memory alloy composite material.
The ingot casting that casting obtains after the melting can further be processed the section bar that obtains having certain physical dimension.For improving the ingot structure state and being beneficial to following process, can carry out homogenizing annealing to ingot casting, the temperature of homogenizing annealing may be controlled to 800-1000 ℃, and annealing time may be controlled to 5-60 hour.Therefore, the preparation method of NbTi/TiNi memory alloy composite material provided by the invention can also may further comprise the steps:
Be higher than 10 in vacuum tightness
-1In the vacuum of Pa or in the protection of inert gas ingot casting is carried out homogenizing annealing;
With the ingot casting hot-forging forming after the annealing;
Ingot casting to hot-forging forming carries out plastic working, obtains section bar.
For improving the performance of hot-forging forming ingot casting (or claiming material that hot-forging forming obtains afterwards) afterwards, the hot forging temperature of ingot casting can be controlled at 800-1000 ℃.
In the matrix material after the forge hot of the present invention, NbTi is particulate state (or spherical) mutually, carries out plastic working by the ingot casting to hot-forging forming, and granular NbTi phase pattern is changed.For example the matrix material after the forge hot (ingot casting) is through hot drawing or cold-drawing technology, and can obtain with wire NbTi phase (NbTi nanofiber line) is the TiNi base memorial alloy matrix material silk material of wild phase; Matrix material after the forge hot (ingot casting) is through repeatedly process annealing and cold-rolling process, and can obtain with sheet NbTi is the TiNi base memorial alloy composite board of wild phase mutually.
In above-mentioned silk material and the sheet material, the size of NbTi phase can reach nano level, and is uniformly distributed in the TiNi matrix, and the specific surface area of NbTi phase is big, and has very high bonding strength between matrix.There is tangible reversible martensitic transformation in this memory alloy composite material.Simultaneously, because alloy TiNi has in mutually a large amount of twin-plane boundaries to exist, and the existence of interface and TiNi and NbTi interphase interface between martensite and parent phase, will make material have good damping characteristic.In addition, because the wire NbTi phase (NbTi single) of nanoscale itself has very high intensity, the existence of NbTi and TiNi phase interface has simultaneously hindered matrix material generation of defects such as dislocation in plastic history, makes this memory alloy composite material have very high yield strength.
In specific embodiments of the present invention,, can carry out different plastic workings to the ingot casting of NbTi/TiNi memory alloy composite material according to the difference of the section bar that will prepare.Plastic working of the present invention comprises following several concrete technology:
1, cold rolling: as the ingot casting behind the hot-forging forming to be carried out cold rolling and recrystallization annealing, can obtain sheet material.Wherein, the thickness of sheet material can be controlled by adjusting processing parameters such as cold rolling number of times and deflection as required.In cold-rolled process, generally be difficult to just obtain satisfactory sheet material by once cold rolling, therefore, the size and the performance of the sheet material that obtains for making meet the demands, and can repeat cold rolling and annealing, up to the sheet material that obtains to meet the demands.
2, cold-drawn: the ingot casting behind the hot-forging forming is carried out cold-drawn and recrystallization annealing, can obtain a material.
3, hot rolling: the ingot casting behind the hot-forging forming is carried out hot rolling, can obtain sheet material.
4, hot drawing (drawing): the ingot casting behind the hot-forging forming is carried out hot drawing, can obtain a material; The diameter of this memory alloy composite material silk material can be controlled as required.
Wherein, in above-mentioned plastic working, various device that is adopted and processing method all are plastic working field equipment and methods commonly used; For obtaining different section bars various adjustment and control that processing parameter and processing step etc. carries out all can be carried out according to the process program that adopt usually this area.
NbTi/TiNi memory alloy composite material provided by the invention can obtain having wire or the fibrous nano NbTi matrix material silk material of (NbTi nano wire or NbTi nanofiber) mutually after through processing such as forge hot and hot drawings; Through forge hot, repeatedly annealing, can obtain having the composite board of NbTi nanometer sheet layer tissue after cold rolling.The NbTi phase size all reaches nano level, and specific surface area is bigger, and is very high with the interface bond strength of matrix.The yield strength of NbTi/TiNi memory alloy composite material provided by the invention under the martensite attitude can reach more than the 1000MPa, and breaking tenacity can reach more than the 1500MPa.After the annealed processing, under the parent phase state, the yield strength of memory alloy composite material can reach more than the 1400MPa, and breaking tenacity can reach more than the 1500MPa.This shows the yield strength the when yield strength when NbTi/TiNi memory alloy composite material provided by the invention has high damping properties has high damping properties far above TiNi and NiTiNb memorial alloy.
Simultaneously, NbTi/TiNi memory alloy composite material provided by the invention has tangible strain soft mode effect, promptly presents low elastic modulus after the distortion; It is linear that the recoverable deformation of this matrix material when the strain soft mode almost is, and after circuit training repeatedly, can reach the super bullet distortion of linearity about 5.4%, and cyclic deformation reduces linear super bullet hysteresis loop area gradually.In addition, NbTi/TiNi memory alloy composite material provided by the invention is after prestrain, and stretching once more presents two stress plateau phenomenons.Through the DSC test, there is tangible reversible martensitic transformation in memory alloy composite material provided by the invention.
In sum, NbTi/TiNi memory alloy composite material provided by the invention has unique functional performances such as high-yield strength, strain soft mode, linear super bullet, two stress plateaus.
In addition, the plasticity of NbTi/TiNi memory alloy composite material provided by the present invention and toughness are also better, the thickness of the sheet material that plastic working obtains can reach below the 0.5mm, and the diameter minimum of silk material can reach below the 0.1mm, can satisfy the demand of different field to memory alloy composite material.
Description of drawings
Fig. 1 is the Nb that embodiment 1 provides
20Ti
42Ni
38The vertical section transmission electron microscope photo of memory alloy composite material;
Fig. 2 and Fig. 3 are the Nb that embodiment 1 provides
20Ti
42Ni
38The memory alloy composite material wire drawing is to diameter 0.62mm, through the SEM picture behind 850 ℃, 20min anneal;
Fig. 4 is the Nb that embodiment 1 provides
20Ti
42Ni
38The stress-strain curves of memory alloy composite material under the room temperature martensitic state;
Fig. 5 is the Nb that embodiment 1 provides
20Ti
42Ni
38The stress-strain curves of memory alloy composite material under the parent phase state;
Fig. 6 is the Nb that embodiment 1 provides
20Ti
42Ni
38Memory alloy composite material silk material carries out the stress-strain curves after the repeatedly circuit training after through 350 ℃, 20 minutes anneal;
Fig. 7 is the Nb that embodiment 1 provides
20Ti
42Ni
38Memory alloy composite material is through after 350 ℃, 20 minutes anneal, the stress strain curve under 90 ℃;
Fig. 8 is the Nb that embodiment 1 provides
20Ti
42Ni
38Memory alloy composite material is after through 350 ℃ of anneal, at the Young's modulus-strain curve of 90 ℃ of following cyclic tensions;
Fig. 9 is the Nb that embodiment 1 provides
20Ti
42Ni
38Memory alloy composite material silk material is after through 350 ℃, 20 minutes anneal, in the curves of stress-strain relationship of 90 ℃ of following cyclic tensions;
Figure 10 and Figure 11 are respectively the Nb that embodiment 2 provides
20Ti
37Ni
43Memory alloy composite material through forge hot after cold rolling cross section and the stereoscan photograph of vertical section;
Figure 12 is the Nb that embodiment 2 provides
20Ti
37Ni
43The XRD figure spectrum of memory alloy composite material;
Figure 13 is the Nb that embodiment 1 provides
20Ti
42Ni
38The SEM back scattering photo of memory alloy composite material ingot casting;
Figure 14 is the Nb that embodiment 1 provides
20Ti
42Ni
38The Nb that memory alloy composite material and embodiment 2 provide
20Ti
37Ni
43The DSC curve comparison diagram of the ingot casting of memory alloy composite material before and after homogenizing annealing;
Figure 15 is the Nb that embodiment 2 provides
20Ti
37Ni
43The stress-strain(ed) curve of memory alloy composite material sheet material.
Embodiment
Below by specific embodiment NbTi/TiNi memory alloy composite material provided by the invention and preparation method thereof is further detailed, but but can not be interpreted as the qualification that practical range of the present invention is done.
The preparation method of NbTi/TiNi memory alloy composite material provided by the invention can comprise following concrete steps:
(1) choose the niobium that purity is 99.0wt.%-99.9wt.% by the composite material compositions proportioning, purity is the titanium of 99.0wt.%-99.9wt.%, and purity is the nickel of 99.0wt.%-99.9wt.%;
(2) above-mentioned composite material compositions is put into smelting furnace, melting obtains the NbTi/TiNi memory alloy composite material, and it is cast into ingot casting;
(3) (final vacuum is 6.7 * 10 in vacuum oven
-4Pa), the homogenizing annealing that under 950 ℃ ingot casting was carried out 10 hours is handled;
(4) ingot casting after will annealing becomes club-shaped material (bar-shaped cast ingot) or pie material (pie ingot casting) 850 ℃ of forge hots;
(5) club-shaped material or the pie material that forge hot is obtained repeats plastic working, up to obtaining needed section bar.
Embodiment 1:Nb
20Ti
42Ni
38Memory alloy composite material
(1) press Nb content 20at.%, Ti and 21: 19 proportioning of Ni atomic ratio are chosen the niobium that purity is 99.9wt.%, and purity is the titanium of 99.9wt.%, and purity is the nickel of 99.9wt.%, and wherein, the atomic percent sum of Nb, Ti and Ni is 100%;
(2) above-mentioned alloy compositions is put into vacuum melting furnace, under the argon shield of-0.05MPa, be smelted into ingot casting;
(3) in vacuum oven, the homogenizing annealing that under 950 ℃ ingot casting was carried out 10 hours is handled;
(4) under 850 ℃, the ingot casting forge hot after the annealing is become club-shaped material (bar-shaped cast ingot);
(5) under 600 ℃, the club-shaped material that forge hot is obtained carries out the silk material that hot drawing obtains diameter 1mm;
(6) resulting silk material in the step (5) is carried out 3 minutes anneal under 750 ℃;
(7) resulting silk material in the step (6) is carried out cold-drawn till can not pulling out, in Cold Drawing Process, should note avoiding making a material to be broken because of diameter is meticulous;
(8) resulting silk material in the step (7) is carried out 3 minutes anneal under 750 ℃; The operation of step (7) and step (8) can be carried out according to the method that adopt usually this area;
(9) repeating step (7) and step (8) up to obtaining the silk material that diameter is 0.5mm, are carried out 20 minutes anneal at 350 ℃ to this material then, finally obtain the Nb of diameter 0.5mm
20Ti
42Ni
38Memory alloy composite material silk material.
The silk material that obtains from step (9) downcuts the long silk of 100mm, use the transmission electron microscope observing microstructure, microstructure image as shown in Figure 1, as can be seen from Figure 1 matrix material is still by TiNi phase and NbTi phase composite behind the wire drawing process, and discontinuous NbTi nanophase is uniformly distributed in the TiNi matrix.The Nb that Figure 13 provides for present embodiment
20Ti
42Ni
38The SEM back scattering photo of memory alloy composite material ingot casting, it is the microstructure of as cast condition memory alloy composite material alloy, wherein, black region is a TiNi matrix phase, and white is the NbTi phase, as can be seen from the figure, NbTi phase in-situ authigenic in TiNi mutually in, and the size of NbTi phase has formed the ultra-fine eutectic structure of as cast condition in-situ authigenic near Nano grade in this matrix material.By to the contrast of Fig. 1 and Figure 13 as can be seen, after handling through wire drawing process, the TiNi in the matrix material is littler with NbTi size mutually mutually, can reach tens nanometers, and this illustrates the Nb that present embodiment provides
20Ti
42Ni
38Memory alloy composite material silk material is a NbTi nanofiber line enhanced TiNi base memorial alloy matrix material.
Fig. 2 and shown in Figure 3 be the Nb that present embodiment provides
20Ti
42Ni
38The memory alloy composite material wire drawing is to diameter 0.62mm, and through the SEM picture behind 850 ℃, 20min anneal, wherein, Fig. 2 is the cross section picture, and Fig. 3 is the vertical section picture.As can be seen from Figures 2 and 3, the silk material through 850 ℃ of anneal after TiNi still evenly distribute alternately mutually mutually with NbTi.
Adopt WDT type electronic universal tensile testing machine to reach the mechanical property of the memory alloy composite material that the test present embodiment provides under the parent phase state down in room temperature (martensitic state), yield strength under its martensitic state can reach 1104MPa, deformation rate can reach 11.5%, stress strain curve as shown in Figure 4, yield strength under the parent phase state can reach 1500MPa, and stress strain curve as shown in Figure 5.The Nb that present embodiment provides
20Ti
42Ni
38The yield strength of memory alloy composite material under martensitic state is greatly improved than existing TiNi memorial alloy, can use as damping material under the high-load environment.
Fig. 6 is above-mentioned Nb
20Ti
42Ni
38Memory alloy composite material silk material carries out the stress-strain curves after the repeatedly circuit training after through 350 ℃, 20 minutes anneal.As seen from Figure 6, the linear elasticity of matrix material is up to 5.4%, and the above-mentioned matrix material that this explanation present embodiment provides has the functional performance of linear super bullet.
Fig. 7 is above-mentioned Nb
20Ti
42Ni
38Memory alloy composite material through 350 ℃ of thermal treatments after, the stress strain curve under 90 ℃, wherein, digital 1-10 represents respectively is the curve that loads, is offloaded to for the first time the tenth loading, unloads.Fig. 8 is above-mentioned Nb
20Ti
42Ni
38Memory alloy composite material through 350 ℃ of thermal treatments after, at the Young's modulus-strain curve of 90 ℃ of following cyclic tensions.By the content of Fig. 7 and Fig. 8, can learn that the memory alloy composite material that present embodiment provides has tangible strain soft mode effect.
Fig. 9 is the Nb that present embodiment provides
20Ti
42Ni
38Memory alloy composite material silk material is after through 350 ℃, 20 minutes thermal treatment, in the curves of stress-strain relationship of 90 ℃ of following cyclic tensions.Usually only there is a stress-induced martensite phase transformation platform in the TiNi memorial alloy, but as can be seen by the curve among Fig. 9, after the TiNi/NbTi matrix material that present embodiment provides plays prestrain through puppet, stretch once more and present two stress-induced martensite phase transformation platforms, CD shown in Fig. 9 and EF section.
Embodiment 2:Nb
20Ti
37Ni
43Memory alloy composite material
(1) press Nb content 20at.%, Ti and 37: 43 proportioning of Ni atomic ratio are chosen the niobium that purity is 99.9wt.%, and purity is the titanium of 99.9wt.%, and purity is the nickel of 99.9wt.%, and wherein, the atomic percent sum of Nb, Ti and Ni is 100%;
(2) above-mentioned alloy compositions is put into smelting furnace, melting and be cast into button shape ingot casting under-0.5MPa argon shield;
(3) in vacuum oven, the homogenizing annealing that under 950 ℃ ingot casting was carried out 10 hours is handled;
(4) under 850 ℃, with annealing after button shape ingot casting radially forge hot become the thick pie material of 10mm (pie ingot casting);
(5) the pie material that forge hot is obtained carries out cold rollingly, and cold rolling reduction is 50%-60%;
(6) material after cold rolling is carried out 20 minutes anneal under 800 ℃;
(7) repeating step (5) and step (6) are up to obtaining the thick sheet material of 0.5mm.
It is wide that the sheet material that obtains from step (7) downcuts 2mm, and the silk that 100mm is long after 20 minutes, with its microstructure of scanning electron microscopic observation, is measured its The Nomenclature Composition and Structure of Complexes with X-ray diffractometer 400 ℃ of following anneal.
The Nb that present embodiment provides
20Ti
37Ni
43The cross section of sheet material and the microstructure image of vertical section are as shown in Figure 10 and Figure 11.White (light color) part among Figure 10 and Figure 11 be sheet NbTi mutually, black (dark color) part is the TiNi phase, NbTi be distributed in mutually TiNi mutually in, can play the enhanced effect, the NbTi/TiNi memory alloy composite material that present embodiment is provided has very high yield strength.
The Nb that present embodiment provides
20Ti
37Ni
43The result of the XRD of memory alloy composite material test as shown in figure 12, by test result as can be seen: this alloy has obtained the NbTi/TiNi memory alloy composite material through forge hot after cold rolling.
Figure 15 is the Nb that present embodiment provides
20Ti
37Ni
43The stress-strain(ed) curve of memory alloy composite material sheet material, as seen from Figure 15, the yield strength of this composite board can reach 455MPa, far above existing TiNi memorial alloy.
Figure 14 is the Nb that embodiment 1 provides
20Ti
42Ni
38The Nb that memory alloy composite material and embodiment 2 provide
20Ti
37Ni
43The DSC curve comparison diagram of the ingot casting of memory alloy composite material before and after homogenizing annealing, as can be seen from the figure, after homogenizing annealing is handled, martensite reverse transformation peak is offset to high-temperature area in heat-processed, narrow down between the phase change zone simultaneously, it is more sharp-pointed that the peak becomes, this may be because the process of cooling of melting is very fast, and the homogenizing annealing postcooling is slower, make (Nb behind the homogenizing annealing, Ti) the Ni content in the sosoloid increases relatively to some extent, and the Ni content of memorial alloy in mutually reduces relatively, thereby transformation temperature just raises to some extent.
As calculated, the martensite reverse transformation enthalpy of the preceding two kinds of alloys of homogenizing annealing is respectively 2.849J/g, 12.32J/g, rises to 9.649J/g, 14.833J/g behind the homogenizing annealing respectively.Learn thus, after passing through the anneal of in vacuum oven, carrying out 950 ℃, 10 hours, the TiNi of the reversible martensitic transformation of participation increases before comparing annealing to some extent in the memory alloy composite material, this explanation is handled by homogenizing annealing, eliminated the uneven situation of composition profiles of the TiNi phase that has reversible martensitic transformation in the memory alloy composite material, made the composition of memory alloy composite material more even.
Above embodiment only is used to illustrate technical scheme of the present invention and is unrestricted, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement technical scheme of the present invention, and not break away from the spirit and scope of technical solution of the present invention.
Claims (6)
1. NbTi/TiNi memory alloy composite material, total amount in this memory alloy composite material, it comprises following composition: atomic percent is the Nb element of 18-22%, and atomic ratio is 0.3: 1-1.5: 1 Ti element and Ni element, and three kinds of elements atomic percentage sums of Ti, Ni and Nb are 100%;
Wherein, described NbTi is wild phase mutually, and described TiNi is matrix mutually, and described NbTi contains minor N i in mutually, and described TiNi contains minor N b in mutually, and this memory alloy composite material is an ingot casting, and described NbTi is spherical mutually, and its diameter is the 0.5-1 micron; Perhaps, this memory alloy composite material is the silk material, and described NbTi is fibrous mutually, and its diameter is the 20-100 nanometer; Perhaps, this memory alloy composite material is a sheet material, and described NbTi is sheet mutually, and its thickness is the 30-100 nanometer.
2. the preparation method of NbTi/TiNi memory alloy composite material as claimed in claim 1, it may further comprise the steps:
Choose simple substance niobium, titanium, the nickel of purity more than 99.0wt.% according to the composition proportion of NbTi/TiNi memory alloy composite material;
Simple substance niobium, titanium, nickel are put into vacuum tightness be higher than 10
-1In the smelting furnace of Pa or protection of inert gas, be smelted into the NbTi/TiNi memory alloy composite material.
3. preparation method as claimed in claim 2, wherein, this preparation method also comprises:
The NbTi/TiNi memory alloy composite material that melting is obtained is cast into ingot casting.
4. preparation method as claimed in claim 3, wherein, this preparation method also comprises:
Be higher than 10 in vacuum tightness
-1In the vacuum of Pa or in the protection of inert gas ingot casting is carried out homogenizing annealing;
With the ingot casting hot-forging forming after the annealing;
Ingot casting to hot-forging forming carries out plastic working, obtains section bar.
5. preparation method as claimed in claim 4, wherein, described plastic working comprises:
Ingot casting to hot-forging forming repeats cold rolling and recrystallization annealing, obtains sheet material; Perhaps
Ingot casting to hot-forging forming carries out hot rolling, obtains sheet material.
6. preparation method as claimed in claim 4, wherein, described plastic working comprises that the ingot casting to hot-forging forming repeats cold-drawn and recrystallization annealing, obtains a material; Perhaps
Ingot casting to hot-forging forming carries out hot drawing, obtains a material.
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| CN103658205A (en) * | 2012-09-04 | 2014-03-26 | 西安思维金属材料有限公司 | Method for processing titanium-nickel base shape memory alloy profiled bar |
| CN104480348B (en) * | 2014-12-06 | 2017-07-21 | 康伏香 | NiTi shape memory alloy materials and preparation method thereof, using and fire-fighting automatic alarm detecting instrument |
| CN104532035B (en) * | 2015-01-08 | 2017-05-17 | 中国石油大学(北京) | Metal nanocomposite material with linear superelasticity and high strength and preparation method thereof |
| CN104946931B (en) * | 2015-05-18 | 2017-01-18 | 中国石油大学(北京) | Nb nanobelt/martensitic NiTi memory alloy matrix composite filament and production method thereof |
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| CN1528930A (en) * | 2003-10-16 | 2004-09-15 | 上海交通大学 | Micro fine-grained titanium-nickel-niobium shape memory alloy block material preparing method |
| CN1661124A (en) * | 2004-02-17 | 2005-08-31 | 爱发科股份有限公司 | Multiple phase alloys and membranes thereof for hydrogen separation-purification and their method of preparation |
| CN101270424A (en) * | 2008-03-25 | 2008-09-24 | 厦门大学 | Nickel titanium niobium negative thermal expansion alloy and method of producing the same |
| CN101654753A (en) * | 2008-08-22 | 2010-02-24 | 中国石油大学(北京) | TiNiNb/NbTi memory alloy composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1528930A (en) * | 2003-10-16 | 2004-09-15 | 上海交通大学 | Micro fine-grained titanium-nickel-niobium shape memory alloy block material preparing method |
| CN1661124A (en) * | 2004-02-17 | 2005-08-31 | 爱发科股份有限公司 | Multiple phase alloys and membranes thereof for hydrogen separation-purification and their method of preparation |
| CN101270424A (en) * | 2008-03-25 | 2008-09-24 | 厦门大学 | Nickel titanium niobium negative thermal expansion alloy and method of producing the same |
| CN101654753A (en) * | 2008-08-22 | 2010-02-24 | 中国石油大学(北京) | TiNiNb/NbTi memory alloy composite material and preparation method thereof |
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