CN112692287A - Preparation method of ordered porous titanium in three-dimensional communicated latticed distribution - Google Patents

Preparation method of ordered porous titanium in three-dimensional communicated latticed distribution Download PDF

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CN112692287A
CN112692287A CN202110050478.5A CN202110050478A CN112692287A CN 112692287 A CN112692287 A CN 112692287A CN 202110050478 A CN202110050478 A CN 202110050478A CN 112692287 A CN112692287 A CN 112692287A
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porous titanium
ordered porous
preparation
sintering
grid
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CN112692287B (en
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张家敏
彭玉青
甘国友
潘志成
严继康
杜景红
高雄
张登
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10Sintering only
    • B22F3/11Making porous workpieces or articles
    • B22F3/1121Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10Sintering only
    • B22F3/11Making porous workpieces or articles
    • B22F3/1103Making porous workpieces or articles with particular physical characteristics
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00Obtaining refractory metals
    • C22B34/10Obtaining titanium, zirconium or hafnium
    • C22B34/12Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/129Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds by dissociation, e.g. thermic dissociation of titanium tetraiodide, or by electrolysis or with the use of an electric arc

Abstract

The invention discloses a preparation method of ordered porous titanium in three-dimensional communicated latticed distribution, and belongs to the technical field of porous titanium preparation by a powder metallurgy method. The invention prepares ordered porous titanium by utilizing TiH2 powder and an organic grid template. Preparing TiH2 powder into slurry, uniformly filling the slurry into an organic grid template, stacking layer by layer, drying, putting a sample into a vacuum furnace for sintering, thermally decomposing an organic grid, and sintering at high temperature to obtain porous titanium pores which are in grid distribution in a three-dimensional space and have through holes with uniform pore sizes; the TiH2 powder is used as a raw material, so that the powder slurry can be conveniently prepared in the early stage without being oxidized, and hydrogen separated out in the sintering process can promote sintering and prevent titanium from being oxidized at high temperature; the invention has low cost and simple preparation process, and the prepared ordered porous titanium has adjustable porosity and pore size and high strength of the titanium skeleton.

Description

Preparation method of ordered porous titanium in three-dimensional communicated latticed distribution
Technical Field
The invention relates to a preparation method of ordered porous titanium with three-dimensional communicated latticed distribution, belonging to the technical field of porous titanium preparation by a powder metallurgy method.
Background
The porous titanium has the advantages of low density, good biocompatibility, strong corrosion resistance and the like, and can be used as a human implant, an electrode, an air suction and sound absorption material, a separation filter material and the like. The application range of the porous titanium is wide, and the research in recent years is more and more, and the development is rapid.
The porous titanium is prepared by a powder metallurgy method, the pore size is from submicron to millimeter, and the porosity can reach 90%. At present, a closed cavity and a blind hole can only be formed in porous titanium which is mostly prepared, the direction is not controllable, the positions of open holes and closed holes cannot be controlled, and through holes which are orderly arranged and communicated are more difficult to form. The ordered porous titanium has the characteristics of ordered pore canal arrangement, low flow resistance, strong height ratio, long service life and the like, and has more advantages in the aspects of biomedical materials, medical filtration, heat insulation members, sound absorption materials and function integration materials. Ordered porous titanium can be prepared by a fiber sintering method, a laser sintering method, 3D printing and the like, but the process is complex, the cost is high, and the development of the ordered porous titanium is limited.
Compared with the method for preparing porous titanium by adopting pure titanium powder at the front end, the method uses TiH2The powder can not only reduce the cost, but also can be TiH in the preparation process2The powder is not easy to be oxidized, and the dehydrogenation process can purify the surface of the material and promote the sintering.
Disclosure of Invention
The invention aims to provide a preparation method of ordered porous titanium with three-dimensional communicated latticed distribution, pores are orderly latticed distribution in a three-dimensional space, and are provided with through holes with uniform pore diameters, and the pore diameter and the porosity of the porous titanium can be adjusted by selecting different grid stacking layer numbers and grid sizes, so that the porous titanium can be suitable for different use conditions; the method specifically comprises the following steps:
(1) mix TiH2Adding deionized water, a binder and a dispersant into the powder, and ball-milling to prepare slurry.
(2) And (2) uniformly filling the slurry prepared in the step (1) into an organic grid template, and controlling the size of a forming blank according to the number of grid stacking layers and the size of the grids.
(3) And (3) drying the formed sample in the step (2), then putting the dried sample into a vacuum sintering furnace, firstly thermally decomposing the organic grid under the high vacuum condition, and then sintering at high temperature to obtain the ordered porous titanium with three-dimensional grid-shaped pore distribution and uniform pore diameter.
Preferably, said TiH is used in step (1) of the present invention2The powder has a mesh number of 300-400 meshes, and impurity content is less than 0.2%; the binder is a polyvinyl alcohol aqueous solution with the mass percentage concentration of 6-10 wt.%; the dispersing agent is a polyethylene glycol aqueous solution with the mass percentage concentration of 30-40 wt.%; TiH2The mass ratio of the powder to the deionized water to the binder to the dispersant is 100:30:10: 3-100: 40:12: 4.
Preferably, in the step (1), the ball milling speed is 300-500 r/min, and the ball milling time is 2-4 h.
Preferably, in step (2) of the present invention, the organic lattice template is one of a PC net, a nylon net, and a polyethylene net.
Preferably, in the step (2), the aperture of the organic grid template is 20-200 meshes, and the diameter of the grid line is 0.02-0.40 mm.
Preferably, in the step (3), the drying temperature is 30-60 ℃ and the time is 6-12 h.
Preferably, the vacuum sintering conditions in step (3) of the present invention are: the temperature of the organic grid in the thermal decomposition process is 400-450 ℃, and the temperature is kept for 10-30 min; the temperature of the sintering process is 1000-1100 ℃, and the sintering time is 90-180 min; the vacuum degree reaches 5 multiplied by 10 in the sintering process-2Pa or above.
Preferably, the porosity of the ordered porous titanium prepared in the step (3) is 40-60%, and the pore size is 20-400 μm.
The invention has the beneficial effects that:
(1) the method has the advantages of simple raw materials, low cost and simple preparation process, and can flexibly design the ordered porous titanium with different pore characteristics according to different use conditions.
(2) In the invention, the organic grid template is adopted, so that impurities cannot be generated after thermal decomposition; using TiH2The porous titanium prepared by the powder can promote sintering, and the dehydrogenation process can protect the titanium from being oxidized, clean the surface of a sample, and simultaneously, TiH2The skeleton is dehydrogenated to form secondary pore creating effect and form micropores.
(3) The ordered porous titanium pores obtained by the method are in latticed distribution in a three-dimensional space, have through holes with uniform pore size, and have adjustable porosity and pore size and high strength of a titanium framework.
Drawings
FIG. 1 is a schematic view of a sample stack according to the present invention;
FIG. 2 is a process flow diagram of the present invention;
FIG. 3 SEM microtopography of sample of example 1;
FIG. 4 EDS profile of a sample of example 1;
FIG. 5 graph of sintering T-T of example 1.
Detailed Description
The present invention is further described in detail with reference to the following specific examples, but the scope of the present invention is not limited to the above description.
Example 1
A preparation method of ordered porous titanium in three-dimensional communicated latticed distribution specifically comprises the following steps:
(1) mix 400 mesh TiH2Adding deionized water and a binder into the powder to prepare slurry, uniformly filling the slurry into an 80-mesh nylon grid template, leveling, and stacking layer by layer.
(2) And (3) putting the sample into an electric heating drying box, and drying for 6h at 40 ℃.
(3) Putting the sample into a vacuum sintering furnace, heating at the heating rate of 10 ℃/min, and carrying out thermal decomposition treatment at 400 ℃ for 15 min; the sintering temperature is 1050 ℃, and the sintering time is 90 min; the vacuum degree reaches 5 multiplied by 10 in the sintering process-2Pa or above.
The density of the prepared ordered porous titanium is tested by adopting an Archimedes drainage method, and the density of the porous titanium is calculated to be 1.79 g/cm3Porosity of 60.47 percent; the pore size was 160 μm. The EDS test result shows that the sample component is titanium and has no obvious impurities; the obtained porous titanium pores are in latticed distribution in a three-dimensional space and have through holes with uniform pore diameters.
Performing SEM test on the sample of example 1, wherein the obtained porous titanium pores are in grid distribution in a three-dimensional space and have through holes with uniform pore size, the sample has small deformation degree, and the sample is silver white in a macroscopic view as shown in FIG. 3; TiH2The powder particles are basically sintered and fused, and the shape of the ordered porous titanium skeleton is kept intact; the EDS test is carried out on the sample of the example 1, and as shown in figure 4, the main component of the sintered sample is Ti without obvious impurities; the method proves that the organic raw materials are completely pyrolyzed under the vacuum condition, and the obtained porous titanium is pure titanium and is free of oxidation and carbonization; and use of TiH2The powder is taken as a raw material, so that the powder slurry can be conveniently prepared in the early stage without being oxidized, and hydrogen separated out in the sintering process can promote sintering and prevent titanium from being oxidized at high temperature.
Example 2
A preparation method of ordered porous titanium in three-dimensional communicated latticed distribution specifically comprises the following steps:
(1) mix 400 mesh TiH2Adding deionized water and a binder into the powder to prepare slurry, uniformly filling the slurry into an 80-mesh nylon grid template, leveling, and stacking layer by layer.
(2) And (3) putting the sample into an electric heating drying box, and drying for 12h at 30 ℃.
(3) Putting the sample into a vacuum sintering furnace, heating at the heating rate of 10 ℃/min, and carrying out thermal decomposition treatment at 450 ℃ for 10 min; the sintering temperature is 1100 ℃, and the sintering time is 90 min; the vacuum degree reaches 5 multiplied by 10 in the sintering process-2Pa or above.
The density of the prepared ordered porous titanium is tested by adopting an Archimedes drainage method, and the density of the porous titanium is calculated to be 1.76 g/cm3Porosity 60.9%; the pore size was 160 μm. The EDS test result shows that the sample component is titanium and has no obvious impurities; the obtained porous titanium pores are in latticed distribution in a three-dimensional space and have through holes with uniform pore diameters
Example 3
A preparation method of ordered porous titanium in three-dimensional communicated latticed distribution specifically comprises the following steps:
(1) mix 300 mesh TiH2Adding deionized water and a binder into the powder to prepare slurry, uniformly filling the slurry into a 40-mesh polyethylene grid template, leveling, and stacking layer by layer.
(2) And (3) putting the sample into an electric heating drying box, and drying for 6h at 40 ℃.
(3) Putting the sample into a vacuum sintering furnace, heating at the heating rate of 10 ℃/min, and carrying out thermal decomposition treatment at 400 ℃ for 15 min; the sintering temperature is 1050 ℃, and the sintering time is 120 min; the vacuum degree reaches 5 multiplied by 10 in the sintering process-2Pa。
The density of the prepared ordered porous titanium is tested by adopting an Archimedes drainage method, and the density of the porous titanium is calculated to be 1.69 g/cm3The porosity is 62.62%; the pore size is 240 μm; the EDS test result shows that the sample component is titanium and has no obvious impurities; the obtained porous titanium pores are in latticed distribution in a three-dimensional space and have through holes with uniform pore diameters.
Example 4
A preparation method of ordered porous titanium in three-dimensional communicated latticed distribution specifically comprises the following steps:
(1) mix 400 mesh TiH2Adding deionized water and a binder into the powder to prepare slurry, uniformly filling the slurry into a 20-mesh nylon grid template, leveling, and stacking layer by layer.
(2) And (3) putting the sample into an electric heating drying box, and drying for 6h at 40 ℃.
(3) Putting the sample into a vacuum sintering furnace, heating at the heating rate of 10 ℃/min, and carrying out thermal decomposition treatment at 400 ℃ for 15 min; the sintering temperature is 1050 ℃, and the sintering time is 120 min; the vacuum degree reaches 5 multiplied by 10 in the sintering process-2Pa。
The density of the prepared ordered porous titanium is tested by adopting an Archimedes drainage method, and the density of the porous titanium is calculated to be 1.67 g/cm3The porosity is 62.97%; the pore size is 400 mu m; the EDS test result shows that the sample component is titanium and has no obvious impurities; the obtained porous titanium pores are in latticed distribution in a three-dimensional space and have uniform pore diametersUniform through holes.
Example 5
A preparation method of ordered porous titanium in three-dimensional communicated latticed distribution specifically comprises the following steps:
(1) mix 400 mesh TiH2Adding deionized water and a binder into the powder to prepare slurry, uniformly filling the slurry into a 200-mesh PC grid template, leveling and stacking layer by layer.
(2) And (3) putting the sample into an electric heating drying box, and drying for 6h at 60 ℃.
(3) Putting the sample into a vacuum sintering furnace, heating at the heating rate of 10 ℃/min, and carrying out thermal decomposition treatment at the temperature of 410 ℃ for 15 min; the sintering temperature is 1000 ℃, and the sintering time is 180 min; the vacuum degree reaches 5 multiplied by 10 in the sintering process-2Pa。
The density of the prepared ordered porous titanium is tested by adopting an Archimedes drainage method, and the density of the porous titanium is calculated to be 2.70g/cm3The porosity is 40.13%; the pore size is 50 μm; the EDS test result shows that the sample component is titanium and has no obvious impurities; the obtained porous titanium pores are in latticed distribution in a three-dimensional space and have through holes with uniform pore diameters.
SEM test and EDS test were performed on the samples obtained in examples 2 to 5, and the results were similar to those of example 1.

Claims (8)

1. A preparation method of ordered porous titanium in three-dimensional communicated latticed distribution is characterized by comprising the following steps:
(1) adding TiH2 powder into deionized water, a binder and a dispersant, and ball-milling to prepare slurry;
(2) uniformly filling the slurry prepared in the step (1) into an organic grid template, and controlling the size of a forming blank according to the number of grid stacking layers and the size of grids;
(3) and (3) drying the formed sample in the step (2), then putting the dried sample into a vacuum sintering furnace, firstly thermally decomposing the organic grid under the high vacuum condition, and then sintering at high temperature to obtain the ordered porous titanium with three-dimensional grid-shaped pore distribution and uniform pore diameter.
2. The preparation method of the ordered porous titanium with three-dimensional connected latticed distribution as claimed in claim 1, wherein: in the step (1), the mesh number of the TiH2 powder is 300-400 meshes, and the impurity content is lower than 0.2%; the binder is a polyvinyl alcohol aqueous solution with the mass percentage concentration of 6-10 wt.%; the dispersing agent is a polyethylene glycol aqueous solution with the mass percentage concentration of 30-40 wt.%; the mass ratio of the TiH2 powder to the deionized water to the binder to the dispersant is 100:30:10: 3-100: 40:12: 4.
3. The preparation method of the ordered porous titanium with three-dimensional connected latticed distribution according to claim 1 or 2, characterized in that: in the step (1), the ball milling speed is 300-500 r/min, and the ball milling time is 2-4 h.
4. The preparation method of the ordered porous titanium with three-dimensional connected latticed distribution as claimed in claim 1, wherein: the organic grid template in the step (2) is one of a PC net, a nylon net and a polyethylene net.
5. The preparation method of the ordered porous titanium with three-dimensional connected latticed distribution as claimed in claim 1 or 4, wherein: in the step (2), the aperture of the organic grid template is 20-200 meshes, and the diameter of the grid line is 0.02-0.40 mm.
6. The preparation method of the ordered porous titanium with three-dimensional connected latticed distribution as claimed in claim 1, wherein: in the step (3), the drying temperature is 30-60 ℃, and the time is 6-12 h.
7. The preparation method of the ordered porous titanium with three-dimensional connected latticed distribution as claimed in claim 1, wherein: the vacuum sintering conditions in the step (3) are as follows: the temperature of the organic grid in the thermal decomposition process is 400-450 ℃, and the temperature is kept for 10-30 min; the temperature of the sintering process is 1000-1100 ℃, and the sintering time is 90-180 min; the vacuum degree in the sintering process reaches more than 5 multiplied by 10 < -2 > Pa.
8. The preparation method of the ordered porous titanium with three-dimensional connected latticed distribution as claimed in claim 1, wherein: the porosity of the ordered porous titanium prepared in the step (3) is 40% -60%, and the pore size is 20-400 microns.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113665188A (en) * 2021-08-26 2021-11-19 昆明理工大学 Titanium-carbon fiber-titanium sandwich composite material and preparation method thereof
CN115403365A (en) * 2022-08-30 2022-11-29 昆明理工大学 Preparation method of ordered cordierite ceramic with macroscopic pore canal combined with microscopic pore
KR20230083923A (en) * 2021-12-03 2023-06-12 동아대학교 산학협력단 Ti-soluble polymer complex pellet for 3D printer

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CN102864322A (en) * 2012-09-10 2013-01-09 西安工程大学 Method for preparing high-porosity material by formed knitting technology
CN103789566A (en) * 2013-12-27 2014-05-14 中南大学 Preparation method of pore-controllable porous nickel-titanium shape memory alloy
CN108359828A (en) * 2018-03-06 2018-08-03 昆明理工大学 A kind of preparation method of ordered porous TC4 alloys
CN111056857A (en) * 2019-12-04 2020-04-24 西安工业大学 3D printing method for porous ceramic with regular pore structure
CN111375758A (en) * 2020-04-23 2020-07-07 王伟东 Sintering method of titanium or titanium alloy powder

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WO2003092933A1 (en) * 2002-05-03 2003-11-13 Stichting Energieonderzoek Centrum Nederland Method for producing a porous titanium material article
WO2009152481A1 (en) * 2008-06-12 2009-12-17 Avery Dennison Corporation Material and method for producing the same
CN102864322A (en) * 2012-09-10 2013-01-09 西安工程大学 Method for preparing high-porosity material by formed knitting technology
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Publication number Priority date Publication date Assignee Title
CN113665188A (en) * 2021-08-26 2021-11-19 昆明理工大学 Titanium-carbon fiber-titanium sandwich composite material and preparation method thereof
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CN115403365A (en) * 2022-08-30 2022-11-29 昆明理工大学 Preparation method of ordered cordierite ceramic with macroscopic pore canal combined with microscopic pore
CN115403365B (en) * 2022-08-30 2023-09-26 昆明理工大学 Preparation method of ordered cordierite ceramic with macroscopic pore channels combined with microscopic pores

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