CN116275022A - Ultrahigh-toughness porous Ti-based memory alloy composite material and preparation method thereof - Google Patents
Ultrahigh-toughness porous Ti-based memory alloy composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an ultrahigh-toughness porous Ti-based memory alloy composite material and a preparation method thereof; firstly, ball-milling TiH 2 ‑Nb‑ZrH 2 Mixing the powder with a certain amount of pore-forming agent on a powder mixer, adding superfine Mo fiber, and mixing Mo with the mixture f /TiH 2 ‑Nb‑ZrH 2 Mixing the powder mixture on a powder mixer again uniformly; mo is then added to f /TiH 2 ‑Nb‑ZrH 2 Cold pressing the pore-forming agent mixture under proper pressure to prepare a green body; finally, the green body is put into a tube furnace for high-temperature sintering to obtain Mo-fiber reinforced medical high-porosity Ti-based memory alloy composite material. The prepared high-porosity Ti-based memory alloy composite material has excellent strength and toughness, simple preparation process and low cost, and is easy for industrial production.
Description
Technical Field
The invention relates to a memory alloy composite material, in particular to an ultrahigh-strength and high-toughness porous Ti-based memory alloy composite material and a preparation method thereof.
Background
The medical metal material has higher mechanical properties (including high breaking strength and fatigue resistance) and becomes the bearing implant material with the most wide clinical application. Medical metal implant materials currently used clinically include medical stainless steel, cobalt-based alloys, titanium alloys, pure metals (such as zirconium, niobium, tantalum) and the like. Meanwhile, the bone implant is also required to have good biocompatibility and biomechanical properties so as to ensure the therapeutic effect and long-term safety and reliability of the bone implant.
The recently developed porous beta-phase Ti-based memory alloy (Ti-Nb-based, ti-Mo-based and Ti-Ta-based alloys) not only inherits the good biocompatibility and unique super-elastic characteristics of the compact Ti-based memory alloy, but also can effectively reduce the elastic modulus of the alloy by introducing a pore structure, solve the problem of stress shielding caused by mismatching of the elastic modulus of the implant and human bone, and is beneficial to the growth of bone tissues and the fixation of the implant.
Therefore, the porous beta-phase Ti-based memory alloy becomes a novel hard tissue substitute material with more medical potential. The porosity of human bones (including cortical and cancellous bones) is in the range of 30-90%, however, the porosity of the porous Ti-based memory alloy which can meet the requirement of the compression strength of human bones is not more than 40% at present. The porosity exceeding 40% can greatly reduce the strength of the porous Ti-based memory alloy, is lower than the strength requirement (more than 200 MPa) of the bone implant material, and meanwhile, the toughness is poor, so that the application of the porous Ti-based memory alloy with high porosity as the bone implant material is limited. It is reported that the compressive strength of a porous titanium-based memory alloy with a porosity of 50% is about 150MPa, which is only one seventh of the compressive strength of a dense matrix, and the toughness is reduced by about 17%. Therefore, there is a need to try to improve the strength and toughness of high porosity Ti-based memory alloys, which is a critical problem that medical high porosity Ti-based memory alloys are urgently required to solve.
There are studies reporting that the strength of the porous material can be effectively improved by adding high-strength fibers as reinforcement.
For example, the high-porosity aluminum alloy/aluminum core aluminum oxide fiber composite foam material prepared by a seepage method, wherein 5 percent (volume ratio) of aluminum oxide fibers are added, the yield strength of the composite foam material with the porosity of 82 percent is improved by 448 percent, and the fracture toughness is also obviously improved. The fiber-reinforced bionic artificial bone ceramic composite material with orthogonally distributed fibers, which is manufactured by utilizing the three-dimensional weaving technology, has the porosity of about 64 percent, and the compression strength of 30MPa which is far higher than that of a bionic artificial bone (about 6 MPa) without fibers. It can be seen that the porous material is reinforced with the addition of high-strength fibers to have a remarkable effect.
Currently, mo is used in the aerospace field f A great deal of researches and experiments of successful application of the Ti composite material show that the Mo fiber with high strength and high temperature resistance has obvious improvement effect on the strength and toughness of the compact titanium alloy.
For example Mo prepared by vacuum hot pressing f/ The yield strength of the TiAl composite material at room temperature is as high as 1148MPa, which is improved by nearly 90% compared with that of the matrix, and the fracture toughness of the composite material is improved by nearly one time compared with that of the matrix.
Meanwhile, the Mo element has good biocompatibility. Therefore, the Mo fiber is selected to carry out strengthening and toughening treatment on the medical porous Ti-based memory alloy. So far, no report on the utilization of Mo fiber reinforced porous Ti-based alloy is seen, and a preparation method for utilizing the Mo fiber reinforced high-porosity Ti-based memory alloy composite material is urgently needed to be developed, so that the strength and toughness of the high-porosity Ti-based memory alloy are improved, and the mechanical property requirement of the high-porosity Ti-based memory alloy serving as a human hard tissue repair and replacement material is met.
The invention provides an ultrahigh-strength and toughness porous Ti-based memory alloy composite material and a preparation method thereof, which solve the problems of low strength and poor toughness of the traditional medical high-porosity Ti-based memory alloy.
The compressive strength of the porous Ti-based composite material prepared by the method is up to 700MPa, the compressive strain is increased to more than 60%, the mechanical property is comprehensively and obviously improved, the preparation process is simple, the cost is low, and the industrial production is easy.
The invention is realized by the following technical scheme:
the preparation method of the ultrahigh-toughness porous Ti-based memory alloy composite material is characterized by comprising the following operation steps:
step one: tiH is processed by 2 ，ZrH 2 Performing ball milling treatment on Nb powder, and cutting Mo fibers;
step two: treating the treated TiH 2 ，ZrH 2 And Nb powder and Mo fiber, mixed;
step three: mo/TiH in the second step 2 -Nb-ZrH 2 The mixed powder is mixed with pore-forming agent (ammonium bicarbonate particles) according to a certain weight ratio, and mixed for a period of time on a powder mixer at a certain speed.
Step four: mo/TiH 2 -Nb-ZrH 2 Cold press molding the pore-forming agent mixed powder on a hydraulic press to obtain a green body;
step five: and (5) placing the green blanks into a vacuum sintering furnace for heating and sintering, and cooling along with the furnace.
Step six: the sintered sample was subjected to solution treatment.
In the first step, tiH is calculated in atomic percent 2 ，ZrH 2 And the purity of the Nb powder is more than 99.5 percent; the Mo content in the Mo yarn is more than or equal to 99.3 percent.
In the first step, the processing means: high purity TiH 2 ，ZrH 2 Ball milling Nb powder for more than 8 hours by a plasma discharge ball mill; the Mo fiber length is cut to be less than 12mm.
In the third step, the diameter of the Mo fiber is 30 mu m, and the Mo/TiH 2 -Nb-ZrH 2 The volume ratio of the mixed powder of the pore-forming agent and the powder is not more than 5%; the rotating speed of the powder mixer is not more than 200r/min, and the mixing time is not more than 30min.
In the third step, pore-forming agent and Mo/TiH 2 -Nb-ZrH 2 The weight ratio of the mixed powder is more than 30 percent, the rotating speed of the powder mixer is less than 100r/min, and the mixing time is 5-10 min.
In the fourth step, the cold press molding pressure of the green blank is 300-660 MPa, and the pressure maintaining time is 5-30 min.
Step five, placing the green body into a vacuum sintering furnace for heating and sintering, and cooling along with the furnace, wherein the method specifically comprises the following steps of: turning on vacuum pump at 0-200deg.C and heating at 5 deg.C/min to 10% -3 Rapidly heating under Pa vacuum, closing vacuum pump at 200-800 deg.C, and heating under H 2 At 2 ℃/m under atmosphereSlowly heating to 800 ℃ at the in heating rate, and preserving heat for 1h at 800 ℃; then the vacuum pump is turned on again at 800-1100 ℃ and the heating rate is 10 at 5 ℃/min -3 And (5) quickly heating to 1100 ℃ under Pa vacuum, sintering at 1100 ℃ under vacuum for 5 hours, and cooling along with a furnace.
In the sixth step, the sintered sample is subjected to solution treatment, specifically: and sealing the sintered sample in a glass tube, carrying out solution treatment under the protection of argon, wherein the solution treatment temperature is 900 ℃, the heat preservation time is 1h, and then rapidly cooling in ice water.
Mo prepared by the method f The porosity of the porous Ti-based memory alloy composite material is higher than 50%, and compared with a porous sample without Mo fiber under the same porosity, the compressive strength is improved from 180MPa to 700MPa, the compressive strain is improved by nearly 300%, the compressive strain is improved from 25% to more than 60%, and the mechanical property is comprehensively and obviously improved. Has great application potential as a material for repairing and replacing human hard tissues.
The principle of the invention is as follows: the Mo fiber can organically connect a plurality of independent holes of the high-porosity Ti-based alloy, when the porous alloy is deformed under force, the hole wall can transfer stress to the high-strength Mo fiber, the Mo fiber plays a role in resisting stress and preventing cracks from expanding in a matrix, the stress resisting capacity of the porous alloy hole wall matrix is improved, and the porous alloy is promoted to enter a densification stage, so that the strength of the porous alloy is greatly improved. At the same time, the pulling-out of the fiber and the deflection of the fiber to crack extension have obvious improvement effect on the toughness of the porous alloy.
Compared with the prior art, the invention has the following advantages and effects:
aiming at the problems of low strength and poor toughness of medical high-porosity Ti-based memory alloy, the invention prepares Mo in a powder metallurgy mode f Porous Ti-based memory alloy composite material, mo at 50% porosity compared with non-fiber reinforced porous Ti-based memory alloy f The compressive strength and compressive strain of the porous Ti-based memory alloy composite material are respectively improved by approximately three times or more, the reinforcing and toughening effects are obvious, the preparation method is simple, and the requirement on equipment is low.
By using high purity TiH 2 And ZrH 2 The hydride powder effectively reduces the sintering temperature of the porous titanium alloy, relieves the Mo/Ti interface reaction during high-temperature sintering, obtains excellent Mo/Ti interface combination, and ensures the reinforcing and toughening effects of Mo fibers.
The Mo element is nontoxic element, has better biocompatibility, and is suitable for being used as alloying element of medical titanium alloy.
Drawings
FIG. 1 is an SEM morphology of the near dense Ti-12Nb-18Zr memory alloy of example 1 having a porosity of 7% according to the invention.
FIG. 2 is an SEM morphology of a medical high porosity Ti-12Nb-18Zr memory alloy of example 2 with a porosity of 50.3%.
FIG. 3 is an SEM morphology of a Mo fiber reinforced medical high porosity Ti-12Nb-18Zr memory alloy composite material of example 3 having a porosity of 53.1%.
FIG. 4 is a graph of the near dense Ti-12Nb-18Zr memory alloy, high porosity Ti-12Nb-18Zr memory alloy and Mo prepared in examples 1-3 f Compression fracture curve of the Ti-12Nb-18Zr composite. As can be seen from the figure, the introduction of high porosity leads to a significant decrease in the compressive strength and toughness of the memory alloy, while the addition of Mo fibres leads to Mo f The mechanical property of the Ti-12Nb-18Zr composite material is obviously improved, and the toughness of the composite material is far more than that of a near compact state matrix alloy.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1:
step one: tiH with powder purity greater than 99.5% was processed in a glove box 2 Nb and ZrH 2 The atomic ratio of Ti, nb and Zr of the powder is 70:12:18, weighing the materials in proportion. Putting the weighed powder into a plasma discharge ball mill for ball milling for 8 hours to obtain uniformly mixed TiH 2 -Nb-ZrH 2 A powder;
step two: cold pressing the mixed powder on a hydraulic press to obtain a green blank, wherein the cold press molding pressure is 660MPa (the maximum pressure of the hydraulic press), and the pressure maintaining time is 5min.
Step three: the obtained green compact is put into a vacuum tube furnace for sectional heating and sintering, a vacuum pump is started at the temperature of 0-200 ℃ and the heating rate of 5 ℃/min is 10% -3 Rapidly heating under Pa vacuum, closing vacuum pump at 200-800 deg.C, and heating under H 2 Slowly heating to 800 ℃ at a heating rate of 2 ℃/min under the atmosphere, and preserving heat for 1h at 800 ℃; then the vacuum pump is turned on again at 800-1100 ℃ and the heating rate is 10 at 5 ℃/min -3 And (5) quickly heating to 1100 ℃ under Pa vacuum, sintering at 1100 ℃ under vacuum for 5 hours, and cooling along with a furnace.
Step four: the obtained sintered sample was sealed in a glass tube filled with Ar gas for solution treatment at 900℃for 1 hour, and then the sample was rapidly cooled in ice water.
Example 2:
step one: tiH with powder purity greater than 99.5% was processed in a glove box 2 Nb and ZrH 2 The atomic ratio of Ti, nb and Zr of the powder is 70:12:18, weighing the materials in proportion. Putting the weighed powder into a plasma discharge ball mill for ball milling for 8 hours to obtain uniformly mixed TiH 2 -Nb-ZrH 2 And (3) powder.
Step two: tiH is processed by 2 -Nb-ZrH 2 The mixed powder and the ammonium bicarbonate pore-forming agent are mixed according to the weight ratio of 45% of the pore-forming agent, and then the mixed powder and the ammonium bicarbonate pore-forming agent are placed on a powder mixer to be mixed for 5min at the speed of 100 r/min.
Step three: tiH is processed by 2 -Nb-ZrH 2 And (3) cold pressing the ammonium bicarbonate mixed powder on a hydraulic press to obtain a green body, wherein the cold pressing molding pressure is 300MPa, and the pressure maintaining time is 5min.
Step four: the obtained green compact is put into a vacuum tube furnace for sectional heating and sintering, a vacuum pump is started at the temperature of 0-200 ℃ and the heating rate of 5 ℃/min is 10% -3 Rapidly heating under Pa vacuum, closing vacuum pump at 200-800 deg.C, and heating under H 2 Slowly heating to 800 ℃ at a heating rate of 2 ℃/min under the atmosphere, and preserving heat for 1h at 800 ℃; then the vacuum pump is turned on again at 800-1100 ℃ and the heating rate is 10 at 5 ℃/min -3 Rapid under Pa vacuumAnd when the temperature is raised to 1100 ℃, sintering the mixture for 5 hours at 1100 ℃ in vacuum, and cooling the mixture along with a furnace.
Step five: the obtained sintered sample was sealed in a glass tube filled with Ar gas for solution treatment at 900℃for 1 hour, and then the sample was rapidly cooled in ice water.
Example 3:
step one: tiH with powder purity greater than 99.5% was processed in a glove box 2 Nb and ZrH 2 The atomic ratio of Ti, nb and Zr of the powder is 70:12:18, weighing the materials in proportion. Putting the weighed powder into a plasma discharge ball mill for ball milling for 8 hours to obtain uniformly mixed TiH 2 -Nb-ZrH 2 A powder; mo fibers with a diameter of 30 μm were cut into 8-10mm.
Step two: tiH is processed by 2 -Nb-ZrH 2 The mixed powder and the ammonium bicarbonate pore-forming agent are mixed according to the weight ratio of 45% of the pore-forming agent, and then the mixed powder and the ammonium bicarbonate pore-forming agent are placed on a powder mixer to be mixed for 5min at the speed of 100 r/min.
Step three: tiH is processed by 2 -Nb-ZrH 2 The ammonium bicarbonate mixed powder was mixed with 5vol% of the chopped Mo fibers on a powder mixer at a speed of 250r/min for 15min.
Step four: mo is added with f /TiH 2 -Nb-ZrH 2 And (3) cold pressing the ammonium bicarbonate mixture on a hydraulic press to obtain a green body, wherein the cold pressing molding pressure is 300MPa, and the pressure maintaining time is 5min.
Step five: the obtained green compact is put into a vacuum tube furnace for sectional heating and sintering, a vacuum pump is started at the temperature of 0-200 ℃ and the heating rate of 5 ℃/min is 10% -3 Rapidly heating under Pa vacuum, closing vacuum pump at 200-800 deg.C, and heating under H 2 Slowly heating to 800 ℃ at a heating rate of 2 ℃/min under the atmosphere, and preserving heat for 1h at 800 ℃; then the vacuum pump is turned on again at 800-1100 ℃ and the heating rate is 10 at 5 ℃/min -3 And (5) when the temperature is quickly increased to 1100 ℃ under Pa vacuum, sintering for 5 hours under 1100 ℃ vacuum, and cooling along with a furnace.
Step six: the obtained sintered sample was sealed in a glass tube filled with Ar gas for solution treatment at 900℃for 1 hour, and then the sample was rapidly cooled in ice water.
As described above, the present invention can be preferably realized.
The embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principles of the invention should be made and equivalents should be construed as falling within the scope of the invention.
Claims (10)
1. The preparation method of the ultrahigh-toughness porous Ti-based memory alloy composite material is characterized by comprising the following operation steps:
step one: tiH is processed by 2 ，ZrH 2 Performing ball milling treatment on Nb powder, and cutting Mo fibers;
step two: treating the treated TiH 2 ，ZrH 2 And Nb powder and Mo fiber, mixed;
step three: mo/TiH in the second step 2 -Nb-ZrH 2 Mixing the mixed powder and the pore-forming agent according to the weight ratio, and mixing on a powder mixer;
step four: mo/TiH 2 -Nb-ZrH 2 Cold press molding the pore-forming agent mixed powder on a hydraulic press to obtain a green body;
step five: placing the green blanks into a vacuum sintering furnace for heating and sintering, and cooling along with the furnace;
step six: the sintered sample was subjected to solution treatment.
2. The method for preparing the ultra-high-toughness porous Ti-based memory alloy composite material according to claim 1, wherein the method comprises the following steps: in the first step, tiH is calculated in atomic percent 2 ，ZrH 2 And the purity of the Nb powder is more than 99.5 percent; the Mo content in the Mo yarn is more than or equal to 99.3 percent.
3. The method for preparing the ultra-high-toughness porous Ti-based memory alloy composite material according to claim 1, wherein the method comprises the following steps: in the first step, the processing means: high purity TiH 2 ，ZrH 2 And ball milling Nb powder for more than 8 hours by a plasma discharge ball mill.
4. The method for preparing the ultra-high-toughness porous Ti-based memory alloy composite material according to claim 1, wherein the method comprises the following steps: in the first step, the length of the Mo fiber is cut to be smaller than 12mm.
5. The method for preparing the ultra-high-toughness porous Ti-based memory alloy composite material according to claim 1, wherein the method comprises the following steps: in the third step, the diameter of the Mo fiber is 30 mu m, and the Mo/TiH 2 -Nb-ZrH 2 The volume ratio of the mixed powder of the pore-forming agent and the powder is not more than 5%; the rotating speed of the powder mixer is not more than 200r/min, and the mixing time is not more than 30min.
6. The method for preparing the ultra-high-toughness porous Ti-based memory alloy composite material according to claim 1, wherein the method comprises the following steps: in the third step, pore-forming agent and Mo/TiH 2 -Nb-ZrH 2 The weight ratio of the mixed powder is more than 30 percent, the rotating speed of the powder mixer is less than 100r/min, and the mixing time is 5-10 min.
7. The method for preparing the ultra-high-toughness porous Ti-based memory alloy composite material according to claim 1, wherein the method comprises the following steps: in the fourth step, the cold press molding pressure of the green blank is 300-660 MPa, and the pressure maintaining time is 5-30 min.
8. The method for preparing the ultra-high-toughness porous Ti-based memory alloy composite material according to claim 1, wherein the method comprises the following steps: step five, placing the green body into a vacuum sintering furnace for heating and sintering, and cooling along with the furnace, wherein the method specifically comprises the following steps of: turning on vacuum pump at 0-200deg.C and heating at 5 deg.C/min to 10% -3 Rapidly heating under Pa vacuum, closing vacuum pump at 200-800 deg.C, and heating under H 2 Slowly heating to 800 ℃ at a heating rate of 2 ℃/min under the atmosphere, and preserving heat for 1h at 800 ℃; then the vacuum pump is turned on again at 800-1100 ℃ and the heating rate is 10 at 5 ℃/min -3 And (5) quickly heating to 1100 ℃ under Pa vacuum, sintering at 1100 ℃ under vacuum for 5 hours, and cooling along with a furnace.
9. The method for preparing the ultra-high-toughness porous Ti-based memory alloy composite material according to claim 1, wherein the method comprises the following steps: in the sixth step, the sintered sample is subjected to solution treatment, specifically: and sealing the sintered sample in a glass tube, carrying out solution treatment under the protection of argon, wherein the solution treatment temperature is 900 ℃, the heat preservation time is 1h, and then rapidly cooling in ice water.
10. An ultra-high toughness porous Ti-based memory alloy composite material characterized by being obtained by the preparation method according to any one of claims 1 to 9.
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| CN111876699A (en) * | 2020-06-05 | 2020-11-03 | 华南理工大学 | SiC fiber reinforced high-porosity Ti-based memory alloy composite material and preparation |
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| US6365092B1 (en) * | 1999-06-23 | 2002-04-02 | Abb Lummus Global, Inc. | Method for producing a sintered porous body |
| CN102796972A (en) * | 2012-09-12 | 2012-11-28 | 哈尔滨工业大学 | Continuous Mo fiber reinforcement TiAl base composite material and method for preparing same |
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