CN101139664A - Method for preparing pore-space feature controlled lightweight high-strength porous nickel titanium memory alloys - Google Patents
Method for preparing pore-space feature controlled lightweight high-strength porous nickel titanium memory alloys Download PDFInfo
- Publication number
- CN101139664A CN101139664A CNA2007100308224A CN200710030822A CN101139664A CN 101139664 A CN101139664 A CN 101139664A CN A2007100308224 A CNA2007100308224 A CN A2007100308224A CN 200710030822 A CN200710030822 A CN 200710030822A CN 101139664 A CN101139664 A CN 101139664A
- Authority
- CN
- China
- Prior art keywords
- titanium
- powder
- nickel
- memory alloy
- pore
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Powder Metallurgy (AREA)
Abstract
The invention discloses a preparation method for light and highly intensive nickel-titanium memory alloy that is of controllable porosities and porous, which comprises of: (1) mixing evenly the pure titanium powder with the pure nickel powder; (2) mixing fully a novel pore forming agent-urea particles with the mixed powder got by step (1),with the mass ratio of 10 to 30 per cent; (3) pressing the powder got in step (2) into a sample blank with original porosity of 30 to 60 per cent and evenly distributed pores; (4) heating the blank to dissolve and remove the pore forming agent-urea; (5) heating in a gradient way to rise and preserve the temperature and then sintering in a gradient way to prepare the porous nickel-titanium memory alloy that is of evenly distributed pores, low density, high strength and super elasticity. The invention has good process adaptability, simple preparation process, easy and simple procedure for removing the pore forming agent; the prepared product has good porosity adjustability, high porosity, high compression strength, stable mechanical properties and excellent linear hyperelastic deformation capability.
Description
Technical Field
The invention relates to preparation of a porous nickel-titanium shape memory alloy, in particular to a preparation method of a porous nickel-titanium shape memory alloy with good controllability of pore characteristics, low density, high strength and stable mechanical properties.
Background
The nickel-titanium shape memory alloy is a novel functional material, and has unique shape memory effect, phase change superelasticity, good biocompatibility, corrosion resistance, wear resistance and high fatigue resistance. The excellent characteristics of the nickel-titanium alloy make the nickel-titanium alloy have unique advantages as a biomedical material. At present, the compact nickel-titanium shape memory alloy is widely applied to the medical fields of oral cavity, orthopaedics, neurosurgery, cardiovascular system, urinary system and the like. With the development of interventional medicine, the nickel-titanium shape memory alloy has wider medical field and wider application prospect. The porous nickel-titanium shape memory alloy has a series of advantages of excellent shape memory effect, super elasticity, corrosion resistance, good biocompatibility and the like, and has great medical value, thereby drawing the attention of scientists all over the world. Only when the research and development of porous nickel-titanium memory alloy in China are emphasized and accelerated, can China strive for a place in the field of biomedical materials in the world.
The current laboratory and industrial methods for preparing porous metals and alloys mainly comprise: melt casting, metal deposition and powder metallurgy. These methods have three disadvantages: firstly, the porosity controllability of the prepared sample is not high, and the randomness of the sample performance is larger; secondly, the porous nickel-titanium alloy with large-size pore structure, uniform pore distribution and high porosity is difficult to obtain; thirdly, as porosity increases, the strength and superelasticity of the sample decreases. The mechanical properties of porous nickel-titanium alloy are greatly influenced by the characteristics of pores (porosity and pore morphology), and sharp irregular pore parts are stress concentration areas, so that the strength of the alloy is reduced to a certain extent. Therefore, reasonably improving the pore characteristics and enabling the pore characteristics to have good controllability are effective methods for improving the strength of the porous nickel-titanium memory alloy. The inventor adds easily decomposed ammonium bicarbonate particles as a pore forming agent into nickel-titanium alloy powder in Chinese patent application with the application number of 200610124394.7 in 2006, 12, 25 and 25, so as to improve the pore characteristics and the porosity and the mechanical property of the porous nickel-titanium alloy, but the improvement range is not very large. Ammonium bicarbonate can be decomposed at a lower temperature, and a large amount of loss of ammonium bicarbonate can be caused in the room-temperature powder mixing and pressing process, so that the mass ratio of nickel-titanium powder to ammonium bicarbonate is usually deviated from the initial design value, the porosity is difficult to accurately control, the performance repeatability of a sample is not ideal, and the mechanical performance stability is not high. In addition, in the processes of mixed powder pressing, pore-forming agent removal and the like, the ammonium bicarbonate can be decomposed at a temperature far lower than the reaction temperature of the nickel-titanium powder. After decomposition, a large number of pores may be preformed in the green body, but some of the pores may be closed during subsequent high temperature sintering, thereby reducing the connectivity of the pores. In addition, most of ammonium bicarbonate powders sold on the market are fine needle-like, and the edges of the pores formed by the decomposition of ammonium bicarbonate are sharp. When the sample is acted by external force, the sample is easy to break at the sharp area of the pore, and the super-elastic behavior controlled by the strength and stress induced phase change of the porous nickel-titanium alloy is influenced. In a word, although the pore characteristics can be improved to a certain extent by adding ammonium bicarbonate as a pore-forming agent, the loss of the pore-forming agent in the preparation process is not easy to be accurately controlled, the performance of the prepared sample is not stable enough, and the process repeatability needs to be improved.
Disclosure of Invention
The invention aims to provide a preparation method of a light high-strength porous nickel-titanium shape memory alloy with controllable pore characteristics aiming at the defects existing when ammonium bicarbonate is used as a pore forming agent, so as to obtain the porous nickel-titanium shape memory alloy with good pore characteristic controllability, low density, high strength and stable superelasticity.
The purpose of the invention is realized by the following technical scheme.
A preparation method of a pore characteristic-controllable light high-strength porous nickel-titanium memory alloy comprises the following steps and process conditions:
(1) Mixing pure nickel powder and pure titanium powder evenly according to the atomic ratio of nickel to titanium of 50-51 percent to 49-50 percent;
(2) Fully mixing spherical or nearly spherical urea powder with the mixed powder obtained in the step (1) according to the proportion of 10-30 percent by mass fraction;
(3) Pressing the powder obtained in the step (2) into a green body with the original porosity of 30-60% and uniformly distributed urea particles at room temperature;
(4) Putting the pressed blank into a heating furnace under the protection of inert gas to preheat for 1-2 hours, controlling the temperature at 200-300 ℃ to decompose and remove the pore-forming agent urea;
(5) Heating up according to a step heating mode, wherein the step heating temperature ranges are respectively as follows: 820-860 ℃ is a first-grade gradient temperature range; the temperature of 950 to 1150 ℃ is a secondary gradient temperature range; heating the blank to a first-grade gradient temperature range at the speed of 10-30 ℃/min, and preserving the temperature for 5-10 minutes; then heating to the second-stage gradient temperature range at the speed of 10-20 ℃/min, and preserving the heat for 1-3 hours to prepare the porous nickel-titanium shape memory alloy with high porosity and high strength.
The porous nickel-titanium shape memory alloy with excellent porosity and mechanical property can be obtained by the method, the porosity range is 31-62%, the average size of pores can be changed between 290-730 mu m according to different treatment processes, and the porosity can reach 90%. The phase transition characteristics and the temperature can be adjusted according to specific use requirements so as to meet the requirements of human hard tissue repair and implantation under different conditions.
The principle of the invention is as follows: the pores are first prefabricated in a cold compact using solid urea granules, and then the following polycondensation reaction is used
2CO(NH 2 ) 2 →NH 2 CONHCONH 2 +NH 3 ↑ (1)
NH 2 CONHCONH 2 +CO(NH 2 ) 2 →NH2CONHCONHCONH 2 +NH 3 ↑(2)
NH 2 CONHCONHCONH 2 →(HCNO) 3 +NH 3 ↑ (3)
And volatilization of decomposition products at high temperatures to completely remove the pore-forming agent(ii) a And then the exothermic reaction of Ni + Ti → NiTi is combined to prepare the porous nickel-titanium alloy with good pore controllability. The residue after urea decomposition as the pore-forming agent is a substance which has little influence on the nickel titanium of the final product. The urea decomposition product has proved to have little influence on the product performance, and only a very small amount of TiN or C is found on the product surface 0.7 N 0.3 Ti is generated, which is derived from the action of trace products after the condensation polymerization of urea and nickel titanium at high temperature, and experiments prove that the related properties of the material are not changed. It is worth pointing out that when the surface modification treatment of nitinol is performed to prevent and reduce Ni ion precipitation, tiN or other nitride layers are often formed on the alloy surface by ion implantation or the like, and TiN or C is obtained as by-products in this process 0.7 N 0.3 Ti may have the same effect of reducing Ni ion precipitation.
Compared with the prior art, the invention has the following advantages:
(1) The product prepared by the invention has high porosity and good controllability. According to the present method, porosity can be controlled by controlling the amount of pore former added. The decomposition temperature of urea (initial decomposition temperature 132.7 ℃ C., severe decomposition temperature 205 ℃ C.) was higher than the decomposition temperature of ammonium bicarbonate (initial decomposition temperature 35 ℃ C., severe decomposition temperature 65 ℃ C.). Compared with ammonium bicarbonate, the urea has less loss in the powder mixing and pressing process, and the mass ratio of the metal powder to the urea can be accurately controlled; meanwhile, the pores formed by the urea can be reserved to a high temperature range and in the subsequent sintering process, so that more through pores are generated. The method is particularly suitable for preparing the porous nickel-titanium alloy with good adjustability of pore characteristics. By the method, a porous nickel-titanium shape memory alloy sample with the porosity of 62% can be prepared.
(2) Can obtain products with high strength and stable mechanical property. The method can adjust the pore characteristics by changing the size of the urea particles of the pore-forming agent, and can also prepare the porous nickel-titanium shape memory alloy with controllable mechanical properties by controlling the content of the urea in the blank. The urea used in the method is spherical or approximately spherical, and the hardness of the urea is higher than that of the ammonium bicarbonate, so that the urea in the alloy powder is better than the ammonium bicarbonate in the aspect of keeping the original shape in the mixed powder pressing process. Most of the pores formed after urea decomposition are nearly spherical, and acute angles are few, so that the stress concentration effect of the nickel-titanium alloy under pressure is reduced. Under the condition of the same porosity, the compressive strength of the sample using urea as the pore-forming agent is better than that of the sample using ammonium bicarbonate as the pore-forming agent. The porous nickel-titanium alloy prepared by the method has stable strength and super elasticity after being subjected to one-time compression training, has small changes in mechanical property and super elasticity after being subjected to multiple times of compression, and is obviously superior to the porous nickel-titanium alloy prepared by other methods.
(3) The process adaptability is good. The method can adopt a hot isostatic pressing sintering mode, and can also adopt a common powder sintering mode and a step heating reaction mode to prepare the ideal porous nickel-titanium shape memory alloy, thereby overcoming the problems of insufficient sample porosity and poor pore size controllability existing when a hot isostatic pressing sintering or powder sintering process is singly adopted.
(4) The density of the porous nickel-titanium alloy prepared by the method of the invention is 1.94-3.87 g/cm 3 Relative to the dense nickel titanium alloy density (6.45 g/cm) 3 ) In addition, the portability is obviously improved, and the advantages of the excellent light biological material can be exerted; meanwhile, the alloy density is 5g/cm 3 The high porosity also lays the foundation for the excellent damping light alloy. (note: metal/alloy Density less than 5 g/cm) 3 Sometimes called light metal/alloy)
(5) The sintering process is simple, and the influence on operators and the environment is small. The method is beneficial to compact forming, the process of removing the pore-forming agent is simple and convenient, and the sintering procedure is less. The urea is not easy to decompose at room temperature, has no special smell, and reduces the influence on operators and the pollution to the surrounding environment.
Drawings
FIG. 1-1 is a macroscopic photograph of the porous nickel titanium shape memory alloy with uniformly distributed pores prepared in example 1. Wherein the particle size of the urea is 600-900 μm, and the content is 20wt%.
FIGS. 1-2 are X-ray diffraction patterns of samples prepared in example 1.
FIGS. 1 to 3 show Ti prepared in example 1 49.2 Ni 50.8 DSC test curve of the sample.
FIG. 2 is an optical microscope photograph of the porous Ni-Ti shape memory alloy prepared in example 2, wherein the pores are uniformly distributed, and the urea has a particle size of 300-450 μm and a content of 30wt%.
FIG. 3-1 shows Ti prepared in example 3 50 Ni 50 DSC curve of the sample.
Fig. 3-2 is a graph of the change in stress and strain of the porous nitinol sample prepared in example 3 when subjected to compression after a single compression training.
Detailed Description
For a better understanding of the present invention, the present invention is further described below with reference to the drawings and examples, but the scope of the present invention is not limited to the examples.
Example 1
Pure titanium powder (the average particle size is 48 mu m) and pure nickel powder (the average particle size is 57 mu m) are fully mixed for 24 hours according to the nickel-titanium atomic ratio of 50.8: 49.2 to obtain the raw material powder A. 20wt% of urea (average particle size of 700 μm, maximum and minimum particle sizes of 600 and 900 μm, respectively) was added to powder A, and mixed for 12 hours to obtain powder B. Powder B was pressed at 50MPa into a cylindrical green compact 16 mm in diameter, 15 mm in length, and 45.76% porosity. And (3) putting the blank into an electric heating tube type sintering furnace, heating to 250 ℃ under the protection of argon with the purity higher than 99.99%, and preserving the heat for 1 hour so as to remove the pore-forming agent urea and activate the blank. Then heating to 840 ℃ at a heating rate of 15 ℃/min, and keeping the temperature for 5 minutes. Finally heating to 1000 ℃ at a heating rate of 10 ℃/min, and preserving heat for 3 hours. Finally obtaining the porous nickel-titanium shape memory alloy with high porosity and macropore characteristics.
FIG. 1-1 is a photomicrograph of a cross-section of a porous nickel titanium shape memory alloy prepared according to example 1, with a porosity of 43.29% and an average pore size of 530 μm. From the macroscopic picture, the pores are uniformly distributed and have good appearance, and most of the pores are nearly spherical. FIGS. 1-2 are porous Nitinol Ni prepared in accordance with example 1 50.8 Ti 49.2 X-ray diffraction pattern of (a). Diffraction analysis results show that the main component of the alloy is NiTi phase, and the alloy contains a very small amount of impurity phase. Differential Scanning Calorimetry (DSC) is an effective method for researching the phase change process of an alloy, and thermodynamic and kinetic information such as phase change temperature, phase change enthalpy and the like of the alloy is directly or indirectly measured by dynamically detecting the heat change of an alloy system in the program control heating process. FIGS. 1 to 3 show Ti prepared according to example 1 49.2 Ni 50.8 DSC curve of the sample, P a Representing the occurrence of an austenitic phase transformation, P m Indicating the occurrence of a martensitic transformation. It can be seen that the sample is austenite phase near the body temperature (36-37 ℃), which ensures that the sample has good super-elasticity and large deformation capability in the human body.
Example 2
Pure titanium powder (average particle size of 48 μm) and pure nickel powder (average particle size of 57 μm) are mixed fully for 24 hours according to the nickel-titanium atomic ratio of 51: 49 to obtain the raw material powder A. 30wt% of urea (average particle size 350 μm, maximum and minimum particle sizes 300 and 450 μm, respectively) was added to the powder A, mixed for 12 hours to prepare a powder B, and the powder B was pressed at 200MPa into a cylindrical green compact having a diameter of 16 mm, a length of 18 mm, and a porosity of 61.59%. The blank is placed in a tubular sintering furnace, heated to 300 ℃ under the protection of argon with the purity higher than 99.99 percent and kept warm for 1 hour. Then heating to 820 ℃ at a heating rate of 30 ℃/min, and preserving heat for 10 minutes. Finally heating to 950 ℃ at a heating rate of 20 ℃/min, and preserving the heat for 3 hours. Finally, the porous nickel-titanium shape memory alloy with evenly distributed pores is synthesized.
FIG. 2 is a photomicrograph of a cross-sectional view of a porous nickel titanium shape memory alloy prepared according to example 2 having a porosity of 61.59%, an average pore size of 470 μm and an open porosity of 90.5%.
Example 3
Pure titanium powder (average particle size of 48 μm) and pure nickel powder (average particle size of 57 μm) were mixed thoroughly for 24 hours according to the nickel-titanium atomic ratio of 50: 50 to obtain raw material powder A. 10wt% of urea (average particle size 500 μm, maximum and minimum particle sizes of 450 and 600 μm, respectively) was added to powder A, and mixed for 12 hours to obtain powder B. Powder B was pressed at 100MPa into a cylindrical green body with a diameter of 16 mm, a length of 20 mm and a porosity of 35.02%. The blank is put into an electric heating tube sintering furnace, heated to 200 ℃ under the protection of argon with the purity higher than 99.99 percent and kept for 2 hours. Then heating to 860 ℃ at a heating rate of 10 ℃/min, and then preserving the heat for 5 minutes. Then heating to 1150 ℃ at the heating rate of 15 ℃/min and then preserving the heat for 1 hour.
FIG. 3-1 is a DSC curve of the prepared sample, P m Representing the occurrence of martensitic transformation, P r Representing the occurrence of R phase transition and its inverse, P a Indicating the occurrence of an austenite phase transition. Tests show that the sample has three phase changes in the processes of temperature reduction and temperature rise, namely R phase change, martensite phase change and austenite phase change. The structure of the sample is that R phase and martensite phase coexist at room temperature, and the temperature for R phase transformation and reverse phase transformation is the same. It is worth pointing out that the R phase transformation of the sample is obvious when the temperature is raised and lowered, and a large amount of R phase can be generated, so that the phase interface in the material is steeply increased. The anelastic migration of the interface absorbs energy and has good damping characteristics, while the high porosity of the sample contributes additionally to damping. Therefore, the sample is also suitable for serving as a high damping material for reducing vibration and noise.
Fig. 3-2 is a graph of the stress-strain change of a porous nitinol alloy coupon prepared according to example 3 when subjected to a compression training. The sample has good mechanical property as a whole, the super elasticity is stable after multiple times of cyclic compression, and the linear super elasticity deformability reaches 3%.
In order to accurately compare the strength of samples with different porosities, the compressive strength of the samples is calculated by adopting the formula (4).
In the formula, σ eq Defined as the equivalent compressive strength, representing the load strength of the matrix material in the sample, excluding the pore area, σ is the experimentally measured nominal compressive strength of the porous sample, and P is the porosity of the sample. Table 1 shows a comparison of the equivalent compressive strength of a sample using urea as the pore former and a sample using ammonium bicarbonate as the pore former, all in accordance with ASTM E9-89 a. And selecting alloy samples with the same sintering temperature and components for comparison. The urea samples in table 1 were prepared according to examples 1, 2 and 3, and the ammonium bicarbonate samples were prepared according to the method described in the chinese patent application No. 200610124394.7.
It can be seen from table 1 that, when the porosity of the urea sample is greater than or close to that of the ammonium bicarbonate sample, the pore morphology formed after the decomposition of the spherical urea is more rounded and has few sharp notches and fillets, so that the stress concentration effect is effectively reduced, the equivalent compressive strength of the urea sample is obviously higher than that of the ammonium bicarbonate sample, and the average increase is 8.7% (for different porosities, the increase range is 3-15%). Meanwhile, the sample taking urea as the pore-forming agent has higher porosity, can ensure the requirement of the ingrowth of histiocytes after the material is implanted into organisms, and can effectively improve the biomechanical compatibility of the implanted material and improve the mechanical property matching.
TABLE 1
| Compression Strain of | Name of pore-forming agent | Increase in strength ** | |||||
| Ammonium bicarbonate | Urea | ||||||
| Porosity factor | Compressive strength /MPa | Equivalent strength /MPa | Porosity factor | Compressive strength /MPa | Equivalent strength
/ |
||
| 5％ | 42.1％ 41.4％ 41.5％ 36.7％ 36.9％ | 148(1000℃ * ) 155(1000℃) 146(1000℃) 195(1000℃) 233(1100℃) | 256 265 249 308 369 | 43.3％ 44.5％ 45.8％ 43.4％ 37.3％ | 161(1000℃) 170(1000℃) 154(1000℃) 196(1000℃) 244(1100℃) | 284 307 284 346 389 | 10.9％ 15.8％ 14.1％ 12.3％ 5.4％ |
| 4％ | 42.1％ 41.4％ 38.4％ 34.3％ 33.1％ | 121(1000℃) 114(1000℃) 176(1100℃) 201(1100℃) 188(1100℃) | 209 195 286 306 281 | 44.5％ 47.7％ 37.3％ 35.0％ 31.2％ | 127(1000℃) 104(1000℃) 189(1100℃) 205(1100℃) 208(1100℃) | 229 199 302 316 302 | 9.6％ 2.1％ 5.6％ 3.3％ 7.5％ |
Note: * represents the sintering temperature; ** this represents an increase in equivalent strength of the sample using urea as a pore-forming agent relative to the equivalent strength of the sample using ammonium bicarbonate as a pore-forming agent, which is 8.7% on average.
Claims (6)
1. A preparation method of a pore-controllable light high-strength porous nickel-titanium memory alloy is characterized by comprising the following steps and process conditions:
(1) Mixing pure nickel powder and pure titanium powder evenly according to the atomic ratio of nickel to titanium of 50-51 percent to 49-50 percent;
(2) Fully mixing urea powder and the mixed powder obtained in the step (1) according to the proportion of 10-30% in terms of mass fraction;
(3) Pressing the powder obtained in the step (2) into a green blank with the original porosity of 30-60% at room temperature;
(4) Putting the pressed green body into a heating furnace under the protection of inert gas to preheat for 1-2 hours, controlling the temperature at 200-300 ℃ to decompose and remove the pore-forming agent urea;
(5) Heating up according to a step heating mode, wherein the step heating temperature ranges are respectively as follows: the temperature of 820-860 ℃ is a first-grade gradient temperature range; the temperature of 950-1150 ℃ is a secondary gradient temperature range; heating the blank to a first-grade gradient temperature range at the speed of 10-30 ℃/min, and preserving the temperature for 5-10 minutes; then heating to the second-stage gradient temperature range at the speed of 10-20 ℃/min, and preserving the heat for 1-3 hours to prepare the porous nickel-titanium shape memory alloy with low density, high strength and stable mechanical property.
2. The method for preparing the lightweight, high-strength and porous nickel-titanium memory alloy with controllable pore characteristics according to claim 1, wherein the average particle size of the pure titanium powder in the step (1) is 48 μm, and the average particle size of the pure nickel powder is 57 μm.
3. The preparation method of the light-weight high-strength porous nickel-titanium memory alloy with controllable pore characteristics according to claim 1, characterized in that the pore-forming agent urea in the step (2) is screened spherical or nearly spherical urea, and the particle size of the urea is 300-450, 450-600 or 600-900 μm.
4. The method for preparing the lightweight high-strength porous nickel titanium memory alloy with controllable pore characteristics according to claim 1, wherein the inert gas in the step (4) is argon gas, and the purity of the argon gas is higher than 99.99%.
5. The method for preparing the lightweight high-strength porous nickel-titanium memory alloy with controllable pore characteristics according to claim 1, wherein the heating furnace is an electrically heated tubular sintering furnace.
6. The method for preparing a lightweight high-strength porous nickel titanium memory alloy with controlled pore characteristics as claimed in claim 1, wherein the green body of step (3) is in the shape of a cylinder or a rectangular parallelepiped.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100308224A CN100513603C (en) | 2007-10-12 | 2007-10-12 | Method for preparing pore-space feature controlled lightweight high-strength porous nickel titanium memory alloys |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100308224A CN100513603C (en) | 2007-10-12 | 2007-10-12 | Method for preparing pore-space feature controlled lightweight high-strength porous nickel titanium memory alloys |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101139664A true CN101139664A (en) | 2008-03-12 |
| CN100513603C CN100513603C (en) | 2009-07-15 |
Family
ID=39191769
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100308224A Expired - Fee Related CN100513603C (en) | 2007-10-12 | 2007-10-12 | Method for preparing pore-space feature controlled lightweight high-strength porous nickel titanium memory alloys |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100513603C (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100588379C (en) * | 2008-06-26 | 2010-02-10 | 上海交通大学 | Preparation of artificial joint prosthesis with partially controllable porous structure |
| CN102337419A (en) * | 2011-04-15 | 2012-02-01 | 中南大学 | Method for preparing pore structure parameter controlled porous TiNi shape memory alloy |
| CN102528039A (en) * | 2010-11-09 | 2012-07-04 | 德固萨有限责任公司 | Method for the manufacture of a shaped body as well as green compact |
| CN103290248A (en) * | 2013-05-31 | 2013-09-11 | 西华大学 | Preparation method of particle-reinforced wearable porous titanium |
| CN103447533A (en) * | 2013-09-28 | 2013-12-18 | 重庆大学 | Method for preparing open-cell foam titanium |
| CN106402133A (en) * | 2016-11-10 | 2017-02-15 | 无锡市明盛强力风机有限公司 | Automatic load averaging method for cylinder head bolts |
| CN107008905A (en) * | 2017-02-25 | 2017-08-04 | 河北工业大学 | The preparation method of TiNiCu marmem based damping composite materials |
| CN109304463A (en) * | 2018-10-09 | 2019-02-05 | 中国科学院合肥物质科学研究院 | A kind of aperture, the adjustable high porosity Mn-Cu base high-damping alloy of pass production method |
| CN110947969A (en) * | 2019-12-18 | 2020-04-03 | 西安西工大超晶科技发展有限责任公司 | Preparation method of metallic nickel porous material with controllable main pore diameter value gradient distribution |
| CN112872354A (en) * | 2021-01-11 | 2021-06-01 | 上海交通大学 | Gradient porous metal material and preparation method thereof |
| CN115229186A (en) * | 2021-10-28 | 2022-10-25 | 南京尚吉增材制造研究院有限公司 | Preparation method of porous nickel or nickel alloy with controllable pores |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100451144C (en) * | 2006-12-25 | 2009-01-14 | 华南理工大学 | Method for preparing shape memory nickel titanium alloy with gradient porosity |
-
2007
- 2007-10-12 CN CNB2007100308224A patent/CN100513603C/en not_active Expired - Fee Related
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100588379C (en) * | 2008-06-26 | 2010-02-10 | 上海交通大学 | Preparation of artificial joint prosthesis with partially controllable porous structure |
| CN102528039B (en) * | 2010-11-09 | 2016-01-27 | 德固萨有限责任公司 | Formed body manufacture method and green compact |
| CN102528039A (en) * | 2010-11-09 | 2012-07-04 | 德固萨有限责任公司 | Method for the manufacture of a shaped body as well as green compact |
| US9393088B2 (en) | 2010-11-09 | 2016-07-19 | Degudent Gmbh | Method for the manufacture of a shaped body as well as a green compact |
| CN102337419A (en) * | 2011-04-15 | 2012-02-01 | 中南大学 | Method for preparing pore structure parameter controlled porous TiNi shape memory alloy |
| CN103290248A (en) * | 2013-05-31 | 2013-09-11 | 西华大学 | Preparation method of particle-reinforced wearable porous titanium |
| CN103290248B (en) * | 2013-05-31 | 2015-12-02 | 西华大学 | A kind of particle reinforce abradable porous titanium preparation method |
| CN103447533A (en) * | 2013-09-28 | 2013-12-18 | 重庆大学 | Method for preparing open-cell foam titanium |
| CN103447533B (en) * | 2013-09-28 | 2015-04-01 | 重庆大学 | Method for preparing open-cell foam titanium |
| CN106402133A (en) * | 2016-11-10 | 2017-02-15 | 无锡市明盛强力风机有限公司 | Automatic load averaging method for cylinder head bolts |
| CN107008905A (en) * | 2017-02-25 | 2017-08-04 | 河北工业大学 | The preparation method of TiNiCu marmem based damping composite materials |
| CN107008905B (en) * | 2017-02-25 | 2018-08-17 | 河北工业大学 | The preparation method of TiNiCu marmem based damping composite materials |
| CN109304463A (en) * | 2018-10-09 | 2019-02-05 | 中国科学院合肥物质科学研究院 | A kind of aperture, the adjustable high porosity Mn-Cu base high-damping alloy of pass production method |
| CN110947969A (en) * | 2019-12-18 | 2020-04-03 | 西安西工大超晶科技发展有限责任公司 | Preparation method of metallic nickel porous material with controllable main pore diameter value gradient distribution |
| CN112872354A (en) * | 2021-01-11 | 2021-06-01 | 上海交通大学 | Gradient porous metal material and preparation method thereof |
| CN112872354B (en) * | 2021-01-11 | 2022-05-31 | 上海交通大学 | Gradient porous metal material and preparation method thereof |
| CN115229186A (en) * | 2021-10-28 | 2022-10-25 | 南京尚吉增材制造研究院有限公司 | Preparation method of porous nickel or nickel alloy with controllable pores |
| CN115229186B (en) * | 2021-10-28 | 2023-08-01 | 南京尚吉增材制造研究院有限公司 | Preparation method of porous nickel or nickel alloy with controllable pores |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100513603C (en) | 2009-07-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101139664A (en) | Method for preparing pore-space feature controlled lightweight high-strength porous nickel titanium memory alloys | |
| Li et al. | Space-holder engineered porous NiTi shape memory alloys with improved pore characteristics and mechanical properties | |
| Chu et al. | Effects of heat treatment on characteristics of porous Ni-rich NiTi SMA prepared by SHS technique | |
| Sadrnezhaad et al. | Fabrication of porous NiTi-shape memory alloy objects by partially hydrided titanium powder for biomedical applications | |
| CN100451144C (en) | Method for preparing shape memory nickel titanium alloy with gradient porosity | |
| Wen et al. | Porous shape memory alloy scaffolds for biomedical applications: a review | |
| Aydog et al. | Superelasticity and compression behavior of porous TiNi alloys produced using Mg spacers | |
| Chen et al. | Using an agar-based binder to produce porous NiTi alloys by metal injection moulding | |
| Li et al. | High porosity and high-strength porous NiTi shape memory alloys with controllable pore characteristics | |
| Yuan et al. | A comparative study of the porous TiNi shape-memory alloys fabricated by three different processes | |
| CN111893348B (en) | Preparation method of nickel-titanium alloy material | |
| Lou et al. | Effects of high O contents on the microstructure, phase-transformation behaviour, and shape-recovery properties of porous NiTi-based shape-memory alloys | |
| Kazior et al. | Properties of precipitation hardening 17-4 PH stainless steel manufactured by powder metallurgy technology | |
| Dawood et al. | Fabrication of porous NiTi shape memory alloy objects by powder metallurgy for biomedical applications | |
| Ma et al. | Properties of porous TiNbZr shape memory alloy fabricated by mechanical alloying and hot isostatic pressing | |
| Lu et al. | Microstructure and mechanical properties of spark plasma sintered Ti-Mo alloys for dental applications | |
| Yuan et al. | Control of porosity and superelasticity of porous NiTi shape memory alloys prepared by hot isostatic pressing | |
| Li et al. | Microstructure and superelasticity of porous NiTi alloy | |
| CN106939395A (en) | A kind of medical high nitrogen and nickel-less austenitic stainless steel and preparation method thereof | |
| Annur et al. | Powder metallurgy preparation of Mg-Ca alloy for biodegradable implant application | |
| Kim et al. | Shape memory characteristics of Ti–Ni–Mo alloys sintered by sparks plasma sintering | |
| US20070123976A1 (en) | Pseudoelastic porous shape memory materials for biomedical and engineering applications | |
| Hosseini et al. | Phase transformation behavior of porous NiTi alloy fabricated by powder metallurgical method | |
| Wu et al. | Wear properties of porous NiTi orthopedic shape memory alloy | |
| Sago et al. | METAL INJECTION MOLDING OF ALLOYS FOR IMPLANTABLE MEDICAL DEVICES. |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090715 Termination date: 20111012 |