CN104357700B - A kind of POROUS TITANIUM and preparation method thereof - Google Patents
A kind of POROUS TITANIUM and preparation method thereof Download PDFInfo
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Abstract
A kind of POROUS TITANIUM and preparation method thereof, belongs to field of material technology, and POROUS TITANIUM is through hole skeleton structure, and framework ingredient is Titanium, and grand hole hole wall is dispersed with micropore, and grand hole pore diameter range is 200 ~ 1000 μm, and micropore size scope is 5 ~ 55 μm, porosity 35 ~ 85%.Preparation method is: with titanium valve as raw material, with magnesium granules, magnesium powder as pore creating material, with absolute ethyl alcohol as dispersant with binding agent, first magnesium powder and titanium valve are mixed, then magnesium granules fully soaks with absolute ethyl alcohol and pours into the homogeneous mixture of magnesium powder, titanium valve, again mix, then the prefabricated blank vacuum distillation of compacting is removed magnesium metal, then POROUS TITANIUM presoma is carried out vacuum-sintering.The method that the present invention uses does not produces oxide in course of reaction, and pore creating material can all reclaim；Preparation POROUS TITANIUM even structure, pore structure is adjustable, porosity is high, impurity is few, mechanical property is good.
Description
Technical field
The invention belongs to field of material technology, particularly to a kind of POROUS TITANIUM and preparation method thereof.
Background technology
POROUS TITANIUM is a kind of porous material having structural and functional feature concurrently, show as light weight, anticorrosive endurance, ductility good, and high specific strength specific stiffness, energy-absorbing damping and there is permeance property etc., energy absorbing material can be used as in damper and buffer, it is used as filter element or catalyst carrier in the filter, it is used as electrode material in a fuel cell, is used as body implanting material etc. at medical field.But, under the high-melting-point of titanium and the condition of high temperature, easily with the feature such as oxygen reaction, preparation POROUS TITANIUM be there be difficulties involved when.The preparation method of POROUS TITANIUM mainly has powder sintering, sedimentation, slurry foaming, self-propagating high-temperature synthesis, gel moldings formed therefrom method at present.Wherein: the hole of POROUS TITANIUM prepared by powder direct sintering is affected by arch bridge phenomenon between titanium valve particle size, particle, it is impossible to prepare the POROUS TITANIUM of high porosity；And the pore-forming material that mixed-powder sintering process is selected easily pollutes parent metal, and it is not easy to remove totally；Sedimentation is typically higher to equipment requirement, and technological operation is more complicated；Slip foaming equally exists the removal problem of pore-forming material, and the structural homogeneity of POROUS TITANIUM prepared by self-propagating high-temperature synthesis is relatively poor；The subject matter of gel moldings formed therefrom method is that technical process is loaded down with trivial details, and preparation cost is higher.Therefore, among the preparation method of POROUS TITANIUM is constantly in and constantly explores and improve.
CN101948964A discloses the preparation method of a kind of bio-medical porous titanium and titanium alloy material; the method with the magnesium powder of 100 ~ 400 μm as pore creating material; the titanium valve of magnesium powder with granularity≤50 μm mixes and is pressed into the green compact of definite shape, then under the conditions of argon shield, green compact is incubated 1 ~ 2 hour to remove magnesium metal between 650 ~ 750 DEG C；It is further continued for being warming up between 1150 ~ 1250 DEG C be incubated 3 ~ 7 hours to sinter POROUS TITANIUM into；This hole only formed with magnesium powder occupy-place is unfavorable for the regulation of pore structure, and then affects the permeance property of POROUS TITANIUM；And the method used during removing demagging powder easily forms the mechanical properties such as oxide, and then the ductility of reduction POROUS TITANIUM in sintered body.Document " Processing of titanium foams using
magnesium spacer particles》、《Processing of
Porous TiNi alloys using magnesium as space holder " and " Characterization of Ti 6Al 4V alloy foams
Synthesized by space holder technique " disclose a kind of magnesium and prepare POROUS TITANIUM, porous titanium nickel alloy and the method for POROUS TITANIUM six aluminium four vanadium alloy as pore creating material；Wherein preparing the titanium valve using average grain diameter to be 74 μm in the document of POROUS TITANIUM is raw material; with magnesium powder that granularity is 425 ~ 600 μm as pore creating material; preparation process include using as binding agent 5% polyvinyl alcohol join among titanium valve and magnesium powder and mix 30 minutes; then mixture is colded pressing under 500MPa, under argon shield, be finally heated to 1200 DEG C sinter 1 hour；The method is binding agent owing to using polyvinyl alcohol water solution, and magnesium powder easily reacts with water, and polyvinyl alcohol its residue after sintering easily pollutes POROUS TITANIUM；Meanwhile, the oxygen that magnesium powder, titanium valve are easily remaining with argon gas in sintering process reacts and generates oxide, and then the mechanical property of reduction POROUS TITANIUM；And, use the method going demagging in document, be unfavorable for the recovery of magnesium.
Summary of the invention
For existing POROUS TITANIUM in the problems referred to above present on technology of preparing, the present invention provides a kind of POROUS TITANIUM and preparation method thereof, by with magnesium granules and magnesium powder as pore creating material, with absolute ethyl alcohol as binding agent with dispersant, prefabricated blank is obtained by twice mixing and compacting, then vacuum distillation, sintering, make that impurity is few, mechanical property good, porosity much higher hole titanium.
The POROUS TITANIUM of the present invention is through hole skeleton structure, and framework ingredient is Titanium, and grand hole hole wall is dispersed with micropore, and grand hole pore diameter range is 200 ~ 1000 μm, and micropore size scope is 5 ~ 55 μm, and the porosity ranges of POROUS TITANIUM is 35 ~ 85%.
Compression strength 9 ~ the 145MPa of above-mentioned POROUS TITANIUM, elastic modelling quantity 0.4 ~ 11.8GPa.
The preparation method of the POROUS TITANIUM of the present invention is:
1, prepare granularity be the titanium valve of 50 ~ 150 μm, granularity be that the magnesium granules of 400 ~ 1000 μm and magnesium powder that granularity is 20 ~ 60 μm are as raw material, titanium valve accounts for the 20 ~ 70% of whole raw material cumulative volume, magnesium granules accounts for the 20 ~ 60% of whole raw material cumulative volume, and magnesium powder accounts for the 10 ~ 20% of whole raw material cumulative volume；
2, batch mixer is used to mix 0.5 ~ 1.5 hour in magnesium powder and titanium valve, it is thus achieved that mixed once powder；
3, magnesium granules is placed in absolute ethyl alcohol it is sufficiently humidified so as to, make absolute ethyl alcohol be coated on magnesium granules surface；Wetted magnesium granules is taken out, then mixed once powder is joined in wetted magnesium granules, use batch mixer to mix 0.5 ~ 1.5 hour, it is thus achieved that secondary mixed powder；
4, using the mode of single shaft, twin shaft or isostatic pressed to suppress secondary mixed powder, pressing pressure is 300 ~ 500MPa, and the dwell time is 5 ~ 15 minutes, makes prefabricated blank；
5, demagging powder and magnesium granules are removed in prefabricated blank vacuum distillation；
6, by the prefabricated blank after vacuum distillation at 1100 ~ 1300 DEG C and pressure 1 ~ 1 × 10-2Carrying out vacuum-sintering under the conditions of Pa, the time is 2 ~ 4 hours, makes POROUS TITANIUM.
In said method, the vacuum distillation in step 5 is to carry out under the conditions of temperature 650 ~ 1050 DEG C and pressure 10 ~ 90Pa, and distillation time is 1.5 ~ 3.5 hours.
In said method, the magnesium vapor crystallizer volatilized in step 5 reclaims.
The good effect that the present invention produces is:
1, the present invention is with magnesium metal particle, magnesium powder as pore creating material, and pore-forming material can reclaim in vacuum distillation process completely, will not pollute parent metal.
2, the present invention forms grand hole with magnesium granules occupy-place in POROUS TITANIUM, forms micropore with magnesium powder on hole wall, and hole is interconnected, and pore structure is adjustable, can widen the application of POROUS TITANIUM.
3, the present invention uses vacuum distillation, sintering preparation POROUS TITANIUM, does not results in the secondary oxidation of material, can be used for preparing the goods of big specification in preparation process.
4, the present invention made POROUS TITANIUM pore structure is uniform, and porosity is high, and impurity content is few, and mechanical property is good.
Accompanying drawing explanation
Fig. 1 is the preparation method process chart of the POROUS TITANIUM of the present invention；
Fig. 2 is the POROUS TITANIUM morphology figure in the embodiment of the present invention, in figure, and 1, micropore on hole wall, 2, grand hole in POROUS TITANIUM.
Detailed description of the invention
The titanium valve used in the embodiment of the present invention is commercial, purity 98.49%；Magnesium granules is commercial products, purity >=98%；Magnesium powder is commercial AR.
The absolute ethyl alcohol used in the embodiment of the present invention is commercial AR.
The equipment observing the employing of POROUS TITANIUM microstructure in the embodiment of the present invention is SSX-550 ESEM.
The equipment that in the embodiment of the present invention, mixed material uses is drum mixer, rotating speed 80rpm.
The equipment suppressing prefabricated blank employing in the embodiment of the present invention is digital display type forcing press, maximum pressure 200t.
The equipment that in the embodiment of the present invention, vacuum distillation and vacuum-sintering use is vacuum sintering furnace, final vacuum 1 × 10-3Pa。
In the embodiment of the present invention, vacuum distillation is under the conditions of pressure 10 ~ 90Pa, prefabricated blank is heated to 650 ~ 1050 DEG C and distills, and programming rate is 10 DEG C/min.
In the embodiment of the present invention, by Stress control 1 ~ 1 × 10 after vacuum distillation-2Under the conditions of Pa, continue to be warming up to 1100 ~ 1300 DEG C with the speed of 10 DEG C/min and carry out vacuum-sintering.
Embodiment 1
Prepare granularity be the titanium valve of 150 μm, granularity be the magnesium granules of 1000 μm and magnesium powder that granularity is 60 μm as raw material, titanium valve accounts for the 70% of whole raw material cumulative volume, and magnesium granules accounts for the 20% of whole raw material cumulative volume, and magnesium powder accounts for the 10% of whole raw material cumulative volume；
Batch mixer is used to mix 1.5 hours in magnesium powder and titanium valve, it is thus achieved that mixed once powder；
Magnesium granules is placed in absolute ethyl alcohol and is sufficiently humidified so as to, make absolute ethyl alcohol be coated on magnesium granules surface；Wetted magnesium granules is taken out, then mixed once powder is joined in wetted magnesium granules, use batch mixer to mix 0.5 hour, it is thus achieved that secondary mixed powder；
The mode that secondary mixed powder uses isostatic cool pressing being suppressed, pressing pressure is 500MPa, and the dwell time is 15 minutes, makes prefabricated blank；
Demagging powder and magnesium granules are removed in prefabricated blank vacuum distillation；The temperature of vacuum distillation 1050 DEG C, pressure 10Pa, distillation time is 1.5 hours；The magnesium vapor crystallizer volatilized reclaims；
By the prefabricated blank after vacuum distillation at 1300 DEG C and pressure 1 × 10-2Carrying out vacuum-sintering under the conditions of Pa, the time is 2 hours, makes POROUS TITANIUM；POROUS TITANIUM has through hole skeleton structure, and framework ingredient is Titanium, and grand hole hole wall is dispersed with micropore, and grand hole average pore size is 850 μm, and micropore average pore size scope is 50 μm, and the porosity of POROUS TITANIUM is 35%, compression strength 145MPa, elastic modelling quantity 11.8GPa.
Embodiment 2
Prepare granularity be the titanium valve of 100 μm, granularity be the magnesium granules of 700 μm and magnesium powder that granularity is 40 μm as raw material, wherein titanium valve accounts for the 50% of whole raw material cumulative volume, and magnesium granules accounts for the 35% of whole raw material cumulative volume, and magnesium powder accounts for the 15% of whole raw material cumulative volume；
Batch mixer is used to mix 1 hour in magnesium powder and titanium valve, it is thus achieved that mixed once powder；
Magnesium granules is placed in absolute ethyl alcohol and is sufficiently humidified so as to, make absolute ethyl alcohol be coated on magnesium granules surface；Wetted magnesium granules is taken out, then mixed once powder is joined in wetted magnesium granules, use batch mixer to mix 1 hour, it is thus achieved that secondary mixed powder；
Secondary mixed powder uses the most double pressure head suppress, and pressing pressure is 400MPa, and the dwell time is 10 minutes, makes prefabricated blank；
Demagging powder and magnesium granules are removed in prefabricated blank vacuum distillation；The temperature of vacuum distillation 850 DEG C, pressure 50Pa, distillation time is 2.5 hours；The magnesium vapor crystallizer volatilized reclaims；
By the prefabricated blank after vacuum distillation at 1200 DEG C and pressure 1 × 10-1Carrying out vacuum-sintering under the conditions of Pa, the time is 3 hours, makes POROUS TITANIUM；POROUS TITANIUM has through hole skeleton structure, and framework ingredient is Titanium, and grand hole hole wall is dispersed with micropore, and grand hole average pore size is 600 μm, and micropore average pore size scope is 30 μm, and the porosity of POROUS TITANIUM is 55%, compression strength 93MPa, elastic modelling quantity 4.4GPa.
Embodiment 3
Prepare granularity be the titanium valve of 50 μm, granularity be the magnesium granules of 400 μm and magnesium powder that granularity is 20 μm as raw material, wherein titanium valve accounts for the 20% of whole raw material cumulative volume, and magnesium granules accounts for the 60% of whole raw material cumulative volume, and magnesium powder accounts for the 20% of whole raw material cumulative volume；
Batch mixer is used to mix 0.5 hour in magnesium powder and titanium valve, it is thus achieved that mixed once powder；
Magnesium granules is placed in absolute ethyl alcohol and is sufficiently humidified so as to, make absolute ethyl alcohol be coated on magnesium granules surface；Wetted magnesium granules is taken out, then mixed once powder is joined in wetted magnesium granules, use batch mixer to mix 1.5 hours, it is thus achieved that secondary mixed powder；
Secondary mixed powder uses the most single pressure head suppress, and pressing pressure is 300MPa, and the dwell time is 5 minutes, makes prefabricated blank；
Demagging powder and magnesium granules are removed in prefabricated blank vacuum distillation；The temperature of vacuum distillation 650 DEG C, pressure 90Pa, distillation time is 3.5 hours；The magnesium vapor crystallizer volatilized reclaims；
Under the conditions of 1100 DEG C and pressure 1Pa, the prefabricated blank after vacuum distillation is carried out vacuum-sintering, and the time is 4 hours, makes POROUS TITANIUM；POROUS TITANIUM has through hole skeleton structure, and framework ingredient is Titanium, and grand hole hole wall is dispersed with micropore, and grand hole average pore size is 250 μm, and micropore average pore size scope is 15 μm, and the porosity of POROUS TITANIUM is 85%, compression strength 9MPa, elastic modelling quantity 0.4GPa.
Claims (4)
1. the preparation method of a POROUS TITANIUM, it is characterised in that sequentially include the following steps:
(1) prepare granularity be the titanium valve of 50 ~ 150 μm, granularity be that the magnesium granules of 400 ~ 1000 μm and magnesium powder that granularity is 20 ~ 60 μm are as raw material, titanium valve accounts for the 20 ~ 70% of whole raw material cumulative volume, magnesium granules accounts for the 20 ~ 60% of whole raw material cumulative volume, and magnesium powder accounts for the 10 ~ 20% of whole raw material cumulative volume；
(2) batch mixer is used to mix 0.5 ~ 1.5 hour in magnesium powder and titanium valve, it is thus achieved that mixed once powder；
(3) magnesium granules is placed in absolute ethyl alcohol it is sufficiently humidified so as to, make absolute ethyl alcohol be coated on magnesium granules surface；Wetted magnesium granules is taken out, then mixed once powder is joined in wetted magnesium granules, use batch mixer to mix 0.5 ~ 1.5 hour, it is thus achieved that secondary mixed powder；
(4) using the mode of single shaft, twin shaft or isostatic pressed to suppress secondary mixed powder, pressing pressure is 300 ~ 500MPa, and the dwell time is 5 ~ 15 minutes, makes prefabricated blank；
(5) demagging powder and magnesium granules are removed in prefabricated blank vacuum distillation；
(6) by the prefabricated blank after vacuum distillation at 1100 ~ 1300 DEG C and pressure 1 ~ 1 × 10-2Carrying out vacuum-sintering under the conditions of Pa, the time is 2 ~ 4 hours, makes POROUS TITANIUM；Described POROUS TITANIUM is through hole skeleton structure, and framework ingredient is Titanium, and grand hole hole wall is dispersed with micropore, and grand hole pore diameter range is 200 ~ 1000 μm, and micropore size scope is 5 ~ 55 μm, and the porosity ranges of POROUS TITANIUM is 35 ~ 85%.
The preparation method of POROUS TITANIUM the most according to claim 1, it is characterised in that the vacuum distillation in step (5) is carried out under the conditions of temperature 650 ~ 1050 DEG C and pressure 10 ~ 90Pa, and distillation time is 1.5 ~ 3.5 hours.
The preparation method of POROUS TITANIUM the most according to claim 1, it is characterised in that the magnesium vapor crystallizer volatilized in step (5) reclaims.
The preparation method of POROUS TITANIUM the most according to claim 1, it is characterised in that the compression strength 9 ~ 145MPa of described POROUS TITANIUM, elastic modelling quantity 0.4 ~ 11.8GPa.
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| JPWO2016170805A1 (en) * | 2015-04-24 | 2018-02-15 | 住友電気工業株式会社 | Composite material and manufacturing method thereof |
| CN106466494B (en) * | 2015-08-18 | 2020-09-15 | 重庆润泽医药有限公司 | Porous material and preparation method thereof |
| CN106693047A (en) * | 2015-08-18 | 2017-05-24 | 重庆润泽医药有限公司 | Porous material |
| CN106466493A (en) * | 2015-08-19 | 2017-03-01 | 重庆润泽医药有限公司 | A kind of multilevel hole material |
| CN106474554B (en) * | 2015-08-31 | 2020-09-15 | 重庆润泽医药有限公司 | Porous metal material and preparation method thereof |
| CN105063400B (en) * | 2015-09-16 | 2017-10-03 | 哈尔滨工业大学 | It is a kind of to use the Ti/TiO with nano-porous structure2The method that composite prepares ultracapacitor |
| CN105568032B (en) * | 2016-03-04 | 2017-07-07 | 佛山市海科云筹信息技术有限公司 | A kind of injection molding through-hole foamed metal and preparation method thereof |
| CN106521219B (en) * | 2017-01-05 | 2018-07-03 | 重庆大学 | A kind of preparation method of TiC granule intensified titaniums based porous materials |
| CN107824784B (en) * | 2017-11-10 | 2019-12-10 | 南昌航空大学 | preparation method of light high-strength high-damping porous nickel-titanium shape memory alloy |
| CN108677050A (en) * | 2018-05-25 | 2018-10-19 | 哈尔滨工程大学 | A kind of preparation method of porous magnetic memorial alloy |
| CN110923490B (en) * | 2019-12-09 | 2020-11-10 | 武汉理工大学 | Method for preparing high-strength micron porous metal titanium block by dealloying titanium-molybdenum alloy |
| CN114505481B (en) * | 2020-11-16 | 2023-11-10 | 鞍钢股份有限公司 | Production process of foam steel |
| CN114505480A (en) * | 2020-11-16 | 2022-05-17 | 鞍钢股份有限公司 | Method for preparing foam steel |
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| CN101948964A (en) * | 2010-09-16 | 2011-01-19 | 大连理工大学 | Method for preparing biomedical porous titanium and titanium alloy material |
| CN104070164B (en) * | 2014-07-16 | 2016-08-24 | 哈尔滨工业大学 | The method of powder sintered synthesizing porous Intermatallic Ti-Al compound |
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