CN109971985B - Preparation method of porous titanium - Google Patents
Preparation method of porous titanium Download PDFInfo
- Publication number
- CN109971985B CN109971985B CN201910291568.6A CN201910291568A CN109971985B CN 109971985 B CN109971985 B CN 109971985B CN 201910291568 A CN201910291568 A CN 201910291568A CN 109971985 B CN109971985 B CN 109971985B
- Authority
- CN
- China
- Prior art keywords
- porous titanium
- titanium
- cerium
- rare earth
- earth cerium
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/08—Alloys with open or closed pores
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/08—Alloys with open or closed pores
- C22C1/081—Casting porous metals into porous preform skeleton without foaming
- C22C1/082—Casting porous metals into porous preform skeleton without foaming with removal of the preform
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/30—Acidic compositions for etching other metallic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
Abstract
The invention discloses a preparation method of porous titanium, which is characterized in that metal titanium and rare earth cerium are mixed according to different mass ratios, after vacuum melting, corrosive liquid is corroded to remove cerium for a period of time, cleaning liquid is used for repeatedly washing, and vacuum drying is carried out to prepare the porous titanium. The method is characterized in that a smelting method is adopted to prepare the cerium-containing titanium alloy, the porous titanium is prepared by utilizing the characteristics that titanium and cerium are completely mutually soluble in a liquid phase and the solid phase solubility is extremely low, the content of added rare earth cerium is controlled, so that the porosity is controlled, impurities are prevented from entering the porous titanium forming process, and the porous titanium forming process can be effectively controlled.
Description
Technical Field
The invention relates to the field of porous titanium or titanium alloy, in particular to a preparation method of porous titanium.
Background
As a titanium material with a large number of pores, the porous titanium not only has excellent physicochemical properties of compact titanium, such as high specific strength, good biocompatibility and excellent corrosion resistance, but also brings a plurality of special functional characteristics, such as ultralow density, good fluid permeability and relatively large specific surface area, due to the existence of the pores, the porous titanium has the characteristic of structure and function integration, and is widely applied to military departments such as aviation and aerospace and civil departments such as chemical industry, metallurgy and medicine. In the most widely used medical field, titanium and titanium alloys have been widely used in hard tissue repair due to their excellent "organophilic" properties, and compared to dense titanium, porous titanium is mechanically compatible with hard tissue, its through-hole structure provides a larger space for tissue ingrowth and provides a channel for fluid flow and nutrient exchange, and is beneficial for surrounding cell ingrowth and new bone growth, enhancing biological fixation with bone tissue.
The preparation methods of the porous titanium mainly comprise a slurry foaming method, a powder metallurgy method, a casting method, a self-propagating high-temperature synthesis method and the like at present, and the Y.W.Gu et al uses TiH2Is prepared by adopting a powder metallurgy method for a pore-forming agent and an activating agentThe porous titanium alloy has the pore diameter range of 90-190 mu m and the opening rate of 43-59 percent. Guobo Yang et al use calcium vapor to reduce Ti2O3The porous titanium with the porosity of 62-82% is prepared, and the opening rate is more than 90%.
How to prepare porous titanium by adopting a simpler and more feasible method is always an object explored by various scholars.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides a preparation method of porous titanium, which is based on the principle that two metals of titanium and cerium are respectively distributed in independent and uniform phases after vacuum melting to form a pseudo-alloy phase, a Ce phase is separated through acid corrosion, the porous titanium formed after cleaning and drying does not contain other impurities, and the forming process of the porous titanium can be effectively controlled by controlling the addition amount of Ce.
In order to realize the purpose of the invention, the technical scheme is that the preparation method of the porous titanium is designed, and comprises the following steps:
1) taking the rare earth cerium out of the kerosene, leaching the rare earth cerium with an ethanol solution, and drying the leached rare earth cerium with cold air by using a blower for later use;
2) mixing metal titanium and the rare earth cerium dried for later use in the step 1) according to different mass ratios to form a master alloy for later use;
3) smelting the master alloy prepared in the step 2) under a vacuum condition, and keeping the titanium and the cerium to be uniformly mixed in the smelting process;
4) soaking the mother alloy smelted in the step 3) for a period of time by using a corrosive liquid until no bubbles emerge, and performing corrosion and cerium removal to form a porous titanium stock;
5) cleaning the porous titanium prepared material in the step 4);
6) and (5) carrying out vacuum drying on the porous titanium prepared material cleaned in the step (5) to prepare the porous titanium.
Preferably, the purity of the metal titanium is more than or equal to 99.6 percent, and the purity of the rare earth cerium is more than or equal to 99.9 percent.
Preferably, the step 1) is performed 10 minutes before the step 3) is started, in order to prevent the rare earth cerium from being rapidly oxidized in the air.
Preferably, the mass ratio range of the metal titanium to the rare earth cerium in the step 2) is (21:4) - (10: 15).
Preferably, the smelting device in the step 3) is a vacuum arc smelting furnace, and the vacuum degree of the vacuum arc smelting furnace is less than or equal to 3 multiplied by 10-3Pa。
Preferably, the etching solution in the step 4) is a hydrochloric acid, sulfuric acid or nitric acid solution with the concentration of 5 mol/L-10 mol/L.
Preferably, the etching time in the step 4) is 2-10 h.
Preferably, the cleaning solution used in the step 5) is deionized water and an ethanol solution, and the cleaning step in the step 5) further comprises the step of placing the porous titanium stock in a beaker filled with the ethanol solution and cleaning the porous titanium stock for 20min by using an ultrasonic oscillator.
Preferably, the purity of the ethanol solution is more than or equal to 99.7 percent.
Compared with the prior art, the dealloying method adopted by the invention for preparing the porous titanium has simple and feasible process and simple and convenient operation. The method is characterized in that a smelting method is adopted to prepare the cerium-containing titanium alloy, the porous titanium is prepared by utilizing the characteristics that titanium and cerium are completely mutually soluble in a liquid phase and the solid phase solubility is extremely low, the content of added rare earth cerium is controlled, so that the porosity is controlled, impurities are prevented from entering the porous titanium forming process, and the porous titanium forming process can be effectively controlled.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a scanning electron micrograph of the porous titanium prepared in example 1.
Fig. 2 is an XRD diffraction pattern of the porous titanium prepared in example 1.
FIG. 3 is a scanning electron micrograph of the porous titanium prepared in example 3.
FIG. 4 is a scanning electron micrograph of the porous titanium prepared in example 2.
Detailed Description
The present invention will be described in further detail with reference to the following detailed description and accompanying drawings.
The raw materials and equipment used in the embodiment of the present invention are known products and obtained by purchasing commercially available products.
The invention provides a method for preparing a porous titanium material by taking titanium and cerium as main raw materials and adopting a dealloying method.
Example 1
Taking out rare earth cerium from kerosene, spraying and washing for three times by using ethanol solution, drying by using a blower with cold air, mixing according to the mass ratio of titanium to cerium of 21:4, putting into a vacuum arc melting furnace, and putting into a vacuum degree of less than or equal to 3 multiplied by 10-3Pa and current of 250A, smelting, turning over the solidified sample by using a manipulator in order to keep the titanium and the cerium uniformly mixed in the smelting process, and then smelting, and repeating the steps for two to three times.
And after the smelting is finished, putting the master alloy into hydrochloric acid with the concentration of 5mol/L for corrosion for 5 hours until no bubbles emerge. And taking out the corrosion sample, repeatedly washing with deionized water and an ethanol solution respectively, placing the washed sample into a beaker filled with the ethanol solution, washing the sample for 20min by using an ultrasonic oscillator, and placing the washed sample into a vacuum drying oven to dry the sample for 2h at the temperature of 120 ℃. The purity of the metal titanium used in the steps is more than or equal to 99.6 percent, the purity of the rare earth cerium is more than or equal to 99.9 percent, and the purity of the ethanol solution is more than or equal to 99.7 percent. In order to prevent the rare earth cerium from being rapidly oxidized in the air, the rare earth cerium is taken out of kerosene ten minutes before the beginning of a smelting experiment, cleaned and dried.
Referring to fig. 1 and fig. 2, the obtained porous titanium has a particle size distribution of 0.60-2.62 μm, an average particle size of 1.63 μm, a porosity of 25.40%, and a micro vickers hardness of 250HV of the pore wall.
Example 2
Taking out rare earth cerium from kerosene, spraying and washing for three times by using ethanol solution, drying by using a blower with cold air, mixing according to the mass ratio of titanium to cerium of 18:7, putting into a vacuum arc melting furnace, and putting into a vacuum degree of less than or equal to 3 multiplied by 10-3Pa and current of 250A, smelting, turning over the solidified sample by using a manipulator in order to keep the titanium and the cerium uniformly mixed in the smelting process, and then smelting, and repeating the steps for two to three times.
And after the smelting is finished, putting the master alloy into hydrochloric acid with the concentration of 5mol/L for corrosion for 5 hours until no bubbles emerge. And taking out the corrosion sample, repeatedly washing with deionized water and ethanol solution respectively, placing the washed sample into a beaker filled with the ethanol solution, washing the sample for 20min by using an ultrasonic oscillator, and placing the washed sample into a vacuum drying oven to dry the sample for 2h at 120 ℃. The purity of the metal titanium used in the steps is more than or equal to 99.6 percent, the purity of the rare earth cerium is more than or equal to 99.9 percent, and the purity of the ethanol solution is more than or equal to 99.7 percent. In order to prevent the rare earth cerium from being rapidly oxidized in the air, the rare earth cerium is taken out of kerosene ten minutes before the beginning of a smelting experiment, cleaned and dried.
Referring to FIG. 4, the obtained porous titanium has a particle size distribution of 1.10-4.70 μm, an average particle size of 2.16 μm, a porosity of 35.48%, and a microvicker hardness of 184 HV.
Example 3
Taking out rare earth cerium from kerosene, spraying and washing for three times by using ethanol solution, drying by using a blower with cold air, mixing according to the mass ratio of titanium to cerium of 17:8, putting into a vacuum arc melting furnace, and putting into a vacuum degree of less than or equal to 3 multiplied by 10-3Pa and current of 250A, smelting, turning over the solidified sample by using a manipulator in order to keep the titanium and the cerium uniformly mixed in the smelting process, and then smelting, and repeating the steps for two to three times.
And after the smelting is finished, putting the master alloy into hydrochloric acid with the concentration of 5mol/L for corrosion for 5 hours until no bubbles emerge. And taking out the corrosion sample, repeatedly washing with deionized water and ethanol solution respectively, placing the washed sample into a beaker filled with the ethanol solution, washing the sample for 20min by using an ultrasonic oscillator, and placing the washed sample into a vacuum drying oven to dry the sample for 2h at 120 ℃. The purity of the metal titanium used in the steps is more than or equal to 99.6 percent, the purity of the rare earth cerium is more than or equal to 99.9 percent, and the purity of the ethanol solution is more than or equal to 99.7 percent. In order to prevent the rare earth cerium from being rapidly oxidized in the air, the rare earth cerium is taken out of kerosene ten minutes before the beginning of a smelting experiment, cleaned and dried.
Referring to FIG. 3, the obtained porous titanium has a particle size distribution of 0.60-3.67 μm, an average particle size of 1.91 μm, a porosity of 57.87%, and a microvicker hardness of 213 HV.
Example 4
Extracting rare earth cerium from keroseneTaking out, spraying and washing for three times by using ethanol solution, drying by using a blower with cold air, mixing according to the mass ratio of titanium to cerium of 10:15, putting into a vacuum arc melting furnace, and keeping the vacuum degree to be less than or equal to 3 multiplied by 10-3Pa and current of 250A, smelting, turning over the solidified sample by using a manipulator in order to keep the titanium and the cerium uniformly mixed in the smelting process, and then smelting, and repeating the steps for two to three times.
And after the smelting is finished, putting the master alloy into hydrochloric acid with the concentration of 5mol/L for corrosion for 5 hours until no bubbles emerge. And taking out the corrosion sample, repeatedly washing with deionized water and ethanol solution respectively, placing the washed sample into a beaker filled with the ethanol solution, washing the sample for 20min by using an ultrasonic oscillator, and placing the washed sample into a vacuum drying oven to dry the sample for 2h at 120 ℃. The purity of the metal titanium used in the steps is more than or equal to 99.6 percent, the purity of the rare earth cerium is more than or equal to 99.9 percent, and the purity of the ethanol solution is more than or equal to 99.7 percent. In order to prevent the rare earth cerium from being rapidly oxidized in the air, the rare earth cerium is taken out of kerosene ten minutes before the beginning of a smelting experiment, cleaned and dried.
The particle size distribution of the obtained porous titanium is 0.26-3.43 mu m, the average particle size is 1.73 mu m, the porosity is 10.93 percent, and the micro Vickers hardness of the pore wall is 240 HV.
The following table shows the performance analysis of the porous titanium obtained by different titanium cerium mass ratios:
| mTi:mCe | particle size distribution/. mu.m | Average particle diameter/. mu.m | Porosity/% | Vickers hardness/HV |
| 21:4 | 0.60-2.62 | 1.63 | 25.40 | 250 |
| 18:7 | 1.10-4.70 | 2.16 | 35.48 | 184 |
| 17:8 | 0.60-3.67 | 1.91 | 57.87 | 213 |
| 15:10 | 0.88-3.63 | 1.72 | 39.22 | 219 |
| 14:11 | 0.36-5.29 | 1.55 | 29.57 | 226 |
| 13:12 | 1.03-3.63 | 2.45 | 17.63 | 213 |
| 10:15 | 0.26-3.43 | 1.73 | 10.93 | 240 |
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" or the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is a more detailed description of the present invention that is presented in conjunction with specific embodiments, and the practice of the invention is not to be considered limited to those descriptions. It will be apparent to those skilled in the art that a number of simple derivations or substitutions can be made without departing from the inventive concept.
Claims (9)
1. The preparation method of the porous titanium is characterized by comprising the following steps:
1) taking the rare earth cerium out of the kerosene, leaching the rare earth cerium with an ethanol solution, and drying the leached rare earth cerium with cold air by using a blower for later use;
2) mixing metal titanium and the rare earth cerium dried for later use in the step 1) according to different mass ratios to form a master alloy for later use;
3) smelting the master alloy prepared in the step 2) under a vacuum condition, and keeping the titanium and the cerium to be uniformly mixed in the smelting process;
4) soaking the mother alloy smelted in the step 3) for a period of time by using a corrosive liquid until no bubbles emerge, and performing corrosion and cerium removal to form a porous titanium stock;
5) cleaning the porous titanium prepared material in the step 4);
6) and (5) carrying out vacuum drying on the porous titanium prepared material cleaned in the step (5) to prepare the porous titanium.
2. The method for preparing porous titanium according to claim 1, wherein the purity of the metal titanium is not less than 99.6%, and the purity of the rare earth cerium is not less than 99.9%.
3. The method of claim 1, wherein the step 1) is performed 10 minutes before the step 3) is performed to prevent rapid oxidation of the rare earth cerium in air.
4. The method for preparing porous titanium according to claim 1, wherein the mass ratio of the metal titanium to the rare earth cerium in the step 2) is (21:4) - (10: 15).
5. The method for preparing porous titanium according to claim 1, wherein the smelting device in step 3) is a vacuum arc smelting furnace with a vacuum degree of 3 x 10 or less-3Pa。
6. The method for preparing porous titanium according to claim 1, wherein the etching solution in the step 4) is a hydrochloric acid, sulfuric acid or nitric acid solution with a concentration of 5mol/L to 10 mol/L.
7. The method for preparing porous titanium according to claim 1, wherein the etching time in step 4) is 2-10 h.
8. The method for preparing porous titanium according to claim 1, wherein the cleaning solution used in step 5) is deionized water and an ethanol solution, and the cleaning step in step 5) further comprises placing the porous titanium stock in a beaker filled with the ethanol solution and cleaning the porous titanium stock for 20min by using an ultrasonic oscillator.
9. The method for preparing porous titanium according to claim 8, wherein the purity of the ethanol solution is not less than 99.7%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910291568.6A CN109971985B (en) | 2019-04-11 | 2019-04-11 | Preparation method of porous titanium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910291568.6A CN109971985B (en) | 2019-04-11 | 2019-04-11 | Preparation method of porous titanium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109971985A CN109971985A (en) | 2019-07-05 |
| CN109971985B true CN109971985B (en) | 2020-06-16 |
Family
ID=67084174
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910291568.6A Active CN109971985B (en) | 2019-04-11 | 2019-04-11 | Preparation method of porous titanium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109971985B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112871125B (en) * | 2021-01-05 | 2023-07-07 | 南京华东电子真空材料有限公司 | Preparation method of flake-shaped getter without particle falling risk |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07258766A (en) * | 1994-03-18 | 1995-10-09 | Mitsubishi Materials Corp | Production of molded goods of ti3al intermetallic compound |
| JP2006083444A (en) * | 2004-09-17 | 2006-03-30 | National Institute For Materials Science | Porous titanium alloy |
| KR20150063880A (en) * | 2013-12-02 | 2015-06-10 | 자동차부품연구원 | Hybrid porous body and method of fabricating the same |
| CN104831104B (en) * | 2015-04-03 | 2017-01-25 | 东南大学 | Preparation method of three dimensional nanometer porous titanium and alloy thereof |
| CN105149607B (en) * | 2015-09-16 | 2018-07-06 | 哈尔滨工业大学 | The preparation method of nanoporous titanium valve |
| CN105568029A (en) * | 2015-11-30 | 2016-05-11 | 陕西高新能源发展有限公司 | Method for preparing porous titanium |
-
2019
- 2019-04-11 CN CN201910291568.6A patent/CN109971985B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109971985A (en) | 2019-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105039771B (en) | A kind of preparation method and its usage of three-dimensional connected porous mg-based material | |
| Atwater et al. | Solid state porous metal production: a review of the capabilities, characteristics, and challenges | |
| Čapek et al. | Properties of porous magnesium prepared by powder metallurgy | |
| EP1964629A2 (en) | Porous metal foam structures | |
| JPS62120403A (en) | Titanium composite body having porous surface and its manufacture | |
| Gülsoy et al. | Particle morphology influence on mechanical and biocompatibility properties of injection molded Ti alloy powder | |
| CN111235429B (en) | Gradient medical material and preparation method thereof | |
| KR20140087714A (en) | Manufacturing method of metal foam and metal foam manufactured thereby | |
| CN109971985B (en) | Preparation method of porous titanium | |
| CN112048635A (en) | Micro-nano graded porous copper and preparation method thereof | |
| Ng et al. | Characterization and corrosion study of NiTi laser surface alloyed with Nb or Co | |
| ES2687658T3 (en) | Improved method for metal production | |
| Wang et al. | Influence of anions in phosphate and tetraborate electrolytes on growth kinetics of microarc oxidation coatings on Ti6Al4V alloy | |
| Cicek et al. | Investigation of microstructural evolution of gas-assisted metal injection molded and sintered Mg-0.5 Ca alloy | |
| Yang et al. | Cerium-activated non-basal slip improves ductility of magnesium alloy | |
| Bütev et al. | Characterization of Ti6Al7Nb alloy foams surface treated in aqueous NaOH and CaCl2 solutions | |
| Wang et al. | Pore structure and compression behavior of porous TiAl alloys by freeze casting | |
| Xu et al. | A primary study of the corrosion behavior and superior structure stability of Mg–Ti composites fabricated by high-pressure solid-state sintering | |
| CN107385429A (en) | A kind of medical titanium alloy porous surface titanium coating and preparation method thereof | |
| JP2022515736A (en) | Large area copper nanofoam with a hierarchical structure for use as an electrode | |
| Fukuzumi et al. | Surface improvement for biocompatibility of Ti-6Al-4V by dealloying in metallic melt | |
| Salvo et al. | The effect of alumina particles on the microstructural and mechanical properties of copper foams fabricated by space-holder method | |
| Johnson et al. | Mechanical properties and corrosion resistance of MIM Ni-based superalloys | |
| Bi et al. | Porous Ti-6Al-4V alloy prepared by a press-and-sinter process | |
| Mutlu | Production and characterization of highly porous biodegradable Mg alloy scaffolds containing Ca, Zn and Co |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |