CN102876908B - Method for improving density of foam titanium - Google Patents
Method for improving density of foam titanium Download PDFInfo
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- CN102876908B CN102876908B CN201210368564.1A CN201210368564A CN102876908B CN 102876908 B CN102876908 B CN 102876908B CN 201210368564 A CN201210368564 A CN 201210368564A CN 102876908 B CN102876908 B CN 102876908B
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- rare earth
- density
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- titanium foam
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Abstract
The invention provides a method for improving density of foam titanium. In a process that the foam titanium is prepared by a traditional powder metallurgy blended elemental method, not more than 0.75wt% of rare earth Er2O3 powder is added, and the high-density foam titanium is obtained by means of raw material mixing, compression molding and desorption and vacuum sintering of pore-forming agents. The rare earth Er2O3 of an appropriate quantity is added, and a liquid phase is generated during sintering to improve the density of the materials, so that the quantity of microcosmic pores is effectively decreased to improve the density of the foam titanium, microstructures and mechanical properties of the foam titanium are further improved, and the technical problem unsolved for a long time is solved. The method is simple in technology and high in operability.
Description
Technical field
The present invention relates to titanium foam material technology field, be specifically related to a kind of method that improves titanium foam density.
Background technology
Porous material is the virgin material system growing up in 20th century, has become a kind of novel structure and the functional materials of present material circle.For dense material, porous material is because the existence of pore structure has some unique performances, as low in relative density, specific tenacity is high, large specific surface area, lightweight, sound insulation, heat insulation, good penetrating quality etc., be widely used in the fields such as space flight and aviation, chemical industry, building materials, metallurgy.Titanium is the metal that a kind of performance is very superior, has that specific tenacity is high, a feature such as light specific gravity, high temperature resistant, erosion resistance and good biocompatibility, is widely used in industries such as national defence, chemical industry, metallurgy, medical treatment.Therefore, titanium foam has merged the characteristic of vesicular structure and metal titanium, have the features such as outstanding mechanical property, low density, erosion resistance and biocompatibility, it is in space flight and aviation, bathyscaph and submarine, automobile, chemical industry catalysis, filtration and separate, the field such as sports equipment, biomedical engineering has a wide range of applications.
The preparation general less employing liquid condition shaping of titanium foam (as foamed aluminium), this is the fusing point higher (approaching 1670 ℃) due to titanium because of one side; Because the gas in titanium and atmosphere has extreme chemical affinity (as oxygen and nitrogen), exceed in the liquid or solid-state titanium of 400 ℃ of left and right in temperature on the other hand, the dissolution rate of these gases is very fast, and this has reduced the ductility of titanium greatly; In addition, titanium liquid also has very high reactive behavior with most moulding stock, has further increased the difficulty of flux foaming.In numerous potential can preparing in titanium foam technology, powder metallurgic method can make titanium foam at lower temperature and under looser chemical reaction constraint condition, particularly in conjunction with pore-forming material technology.Pore-forming material is wherein as the material that can remove, as urea, MAGNESIUM METAL or sodium-chlor.
Before the applicant, adopt complex element powder metallurgic method, take urea as pore-forming material, titanium foam and the alloy thereof of different porosities, different pore size are successfully prepared, the porosity of sample is 55%-75%, mean pore size is 600 μ m, pore wall thickness is 100-200 μ m, plateau stress and Young's modulus are respectively 4.5-24.7MPa and 1.38-6.90GPa, basically formed based on complex element powder sintering and prepared technology prototype prepared by titanium foam and alloy thereof, achievement in research has been delivered the some pieces of writing of relevant academic paper.The titanium foam preparing contains two pore structures on yardstick: come from the microcosmic aperture that pore-forming material removes and produce due to the incomplete sintering of powder on macroscopical macropore of staying and hole wall.The quantity that how effectively to reduce microcosmic aperture improves the density of titanium foam, further improves microtexture and the mechanical property of titanium foam, is current those skilled in the art's problem demanding prompt solution.
Summary of the invention
For prior art above shortcomings, the quantity that the object of the invention is to reduce microcosmic aperture improves the density of titanium foam, and a kind of method that improves titanium foam density is provided.
Realize above-mentioned purpose, the present invention adopts following technical scheme: a kind of method that improves titanium foam density, it is characterized in that, and adopt prior powder metallurgy blended elemental to prepare in titanium foam process, add rare earth Er
2o
3powder, rare earth Er
2o
3addition be 0.25 wt%～0.75wt%.
Further, the method for described raising titanium foam density, is characterized in that, specifically comprises the steps:
1) mixing of raw material: first, by load weighted titanium valve and rare earth Er
2o
3powder carries out ground and mixed, after it mixes, then packs in V-type mixer and mixes 30min with urea granules; Rare earth Er
2o
3the addition of powder is 0.25 wt%～0.75wt%;
2) compression moulding: to be mixedly pour in mould after evenly, then use hydraulic single column press compression moulding, pressure used is about 200 Mp, and the dwell time is made as fixed value 1～5min, obtains giving birth to pressed compact;
3) removing and vacuum sintering of pore-forming material: raw pressed compact is carried out to sintering in the vacuum carbon tube furnace having under argon shield atmosphere, and vacuum keep is in 10-3 level; Within the scope of 0～450 ℃, slowly heating is to remove pore-forming material, and temperature rise rate is 2 ℃/min, and within the scope of 450～1250 ℃, temperature rise rate is 10 ℃/min, in the time that temperature is raised to 1250 ℃ of sintering temperatures, be incubated 3 h, then cool to room temperature with the furnace, obtain the titanium foam that density is higher.
Compared to existing technology, the present invention has following beneficial effect:
1, the present invention by adding appropriate rare earth Er in raw material
2o
3powder, improve the density of material by producing liquid phase in sintering process, the quantity that effectively reduces microcosmic aperture on hole wall improves the density of titanium foam, further improves microtexture and the mechanical property of titanium foam, solves the long-term unsolved technical barrier in this area.
2, by add appropriate rare earth Er in raw material
2o
3powder combines with the rare earth element of trace in skeleton, has not only effectively improved the density of titanium foam titanium skeleton, and mechanical property also improves thereupon, has further enriched the method that improves titanium foam mechanical property.
The Young's modulus of the Young's modulus of the titanium foam that 3, the present invention prepares and human body cortex bone tissue matches, be conducive to the fusion of implant and body bone tissue, there will not be stress shielding, increased patient's adaptability, titanium foam is existed in human body for a long time as implant material.
4, technique of the present invention is simple, has stronger operability.
Accompanying drawing explanation
Fig. 1 is the process flow sheet that powder metallurgy blended elemental is prepared titanium foam;
Fig. 2 is the titanium foam sample that the present invention prepares;
Fig. 3 is different Er
2o
3the stereoscan photograph of microscopic appearance on the titanium foam hole wall of content.
Fig. 4 is the fracture apperance of titanium foam sample.
Embodiment
Below in conjunction with specific embodiments and the drawings, the present invention is described in further detail.
(1) improve the method for titanium foam density, adopt prior powder metallurgy blended elemental to prepare in titanium foam process, add rare earth Er
2o
3powder, rare earth Er
2o
3addition be 0.25 wt%～0.75wt%.Specific embodiment is as follows:
With HDH titanium valve, (purity>=99%, Li Du≤50 μ m) and rare earth Er
2o
3powder (purity>=99.95%, Li Du≤10 μ is m) raw material, urea granules (particle diameter is between 700-1000 μ m), as pore-forming material, adopts prior powder metallurgy blended elemental to prepare titanium foam.Experiment is 70% according to porosity, and specimen size is that φ 12mm × 10 mm designs, rare earth Er
2o
3the addition of powder is set to 6 level: 0,0.25,0.50,0.75,1.0,2.0wt%, as shown in table 1.
The Er2O3 content that the different samples of table 1 are corresponding
As shown in Figure 1, the main processes that prepared by sample comprises: the removing and vacuum sintering of the mixing of raw material, compression moulding, pore-forming material.First, by load weighted titanium valve and rare earth Er
2o
3powder carries out the about 5min of ground and mixed in mortar, after it tentatively mixes, pack in V-type mixer and mix 30min with urea granules again, rotating speed is about 86 revs/min, to be mixedly pours in mould after evenly, die size is φ 12mm × 20 mm, then use hydraulic single column press compression moulding, pressure used is about 200 Mp, and the dwell time is made as fixed value 1min, the raw compact specimen diameter obtaining is 12mm, highly approaches 10mm.Raw pressed compact is carried out to sintering in the vacuum carbon tube furnace having under argon shield atmosphere, and (vacuum keep is 10
-3level), within the scope of 0～450 ℃, slowly heat to remove pore-forming material, temperature rise rate is 2 ℃/min, within the scope of 450～1250 ℃, temperature rise rate is 10 ℃/min, in the time that temperature is raised to 1250 ℃ of sintering temperatures, be incubated 3 h, then cool to room temperature with the furnace, obtained adding the titanium foam sample of different content rare earth Er 2O3.
The volume ratio of titanium valve and urea granules is 6～7:3～6, as 7:3 is advisable; Titanium valve and rare earth Er
2o
3the weight ratio of powder is that 95:5 is advisable.
(2) performance test and the analysis of the titanium foam sample that contains rare earth Er 2O3.
Adopt drainage to measure the density of titanium foam sample.Porosity ε=the 1-of titanium foam
ρ/ ρ
0, the density that wherein ρ is actual samples, ρ
0for the density (ρ of titanium skeleton
0=4.51g/cm
3).The porosity key of mensuration material is the mensuration of porous material and solid material density, and this experiment selects drainage to measure the density of titanium foam.Before measuring, with Vaseline, titanium foam is carried out to sealing of hole processing.Measuring method is as follows: i sample obtains M through cleaning except weighing in air after oil drying
empty; Ii sample, after suitable liquid infiltration processing or surface-coated, is again weighed and is obtained M in air
, empty; Iii is suspended from said sample in water, measures the weight M of sample in water
water; The density of iv institute test specimens is calculated as follows:
For reducing error, the measurement of every inferior quality is all surveyed three times and is averaged.M
, emptymeasurement the most key, this experimental water is as medium, thus experiment should be soaked two hours applying after Vaseline in water, after load-bearing three times in air, average.
Due to the weak inductive of metal titanium, sample carries out metal spraying processing, with surface topography and the cross-section morphology of scanning electron microscopic observation titanium foam.Compression experiment adopts newly thinks carefully universal electrical experimental machine.Before experiment, first check whether cylindrical sample bottom surface is plane, and whether two bottom surfaces are parallel, proofread and correct otherwise need to tie sample; After all are appropriate, the performance of material being detected, is mainly Young's modulus, plateau stress, appearance of fracture etc.
Adopt powder metallurgy blended elemental successfully to prepare the interpolation different content rare earth Er of porosity between 64 %～73% in conjunction with pore-forming material technology
2o
3titanium foam.
Fig. 2 is the prepared titanium foam sample out of experiment, and as can be seen from the figure, even pore distribution, physically well develops.Porosity is the of paramount importance feature of porous material.But experimental result is found porosity and the Er of titanium foam sample
2o
3between addition, there is no dependency.Occur that this phenomenon mainly gives the credit to pore-forming material and removes left macropore and make sintering process become more complicated, cause being difficult to assess Er
2o
3on the impact of porosity.In addition, the volumetric shrinkage that sintering process occurs will have influence on the shape of macropore, causes the shared volume difference of macropore of various sample.Therefore,, from the angle of porosity, be difficult to investigate rare earth Er by quantitative analysis
2o
3on the impact of titanium foam density.
Fig. 3 is the stereoscan photograph of microscopic appearance on the titanium foam hole wall of different Er2O3 content.As can be seen from the figure, remove by pore-forming material the impact that left macroscopical macropore is added by rare earth Er 2O3 hardly, and microcosmic aperture on hole wall there is obvious variation.In the time that rare earth addition is less than 0.75%, along with the increase of content of rare earth, the number of the microcosmic aperture on its hole wall reduces to some extent, and the size of aperture also reduces to some extent.Continuing increases content of rare earth, and the quantity of microcosmic aperture starts to increase, and the size of micropore increases slightly to some extent, the density reduction of hole wall.
Fig. 3 has disclosed in the time that addition is less than 0.75wt%, has added different rare earth Ers
2o
3the density of the titanium foam of content is more and more finer and close.But, excessive Er
2o
3cause density to decline.From the angle of qualitative analysis, work as rare earth Er
2o
3when addition is 0.5wt%, the density of titanium foam skeleton is the highest.
Fig. 4 is the fracture apperance of titanium foam sample.Fig. 4 (a) has shown and has not added Er
2o
3the fracture apperance sintering of pure foam titanium incomplete, can observe significantly and on hole wall, contain a large amount of micropores and significantly tiny crack, sintering neck ateliosis and have discontinuous phase constitution structure.And when adding rare earth Er
2o
3when content is 0.5wt%, the microcosmic aperture on titanium foam sample hole wall reduces greatly, and weave construction is more fine and close, mainly complete owing to sintering, as shown in Fig. 4 (b).In addition, the good and size distribution of grain growth is evenly as Fig. 4 (d).But rare earth Er is worked as in Fig. 4 (c) demonstration
2o
3although can crystal grain further be grown up by continuing acceleration of sintering when addition is increased to 2.0wt%, make the pore size on hole wall become large, this is mainly the result of assembling in sintering diffusion process due to hole.
To sum up, appropriate rare earth Er
2o
3improve the density of material by producing liquid phase in sintering process.But, excessive Er
2o
3but the density that has reduced titanium skeleton when having promoted sintering on the one hand, causes the decline of titanium foam sample performance.Relation between the density of titanium foam sample and rare earth addition can be analyzed from angle qualitatively, and the density that addition of 0～0.75wt% can improve titanium foam sample exceedes 0.75wt% and reduced density.
The mechanical property that adopts compression testing to test titanium foam sample.Young's modulus and yield strength are the of paramount importance performances of porous material.The mechanical property of titanium foam sample and Er
2o
3relation between addition is as shown in Fig. 2.
The mechanical property of table 2 titanium foam sample
With do not add Er
2o
3sample compare, the Young's modulus of titanium foam and yield strength are along with Er
2o
3the increase of addition presents the trend of first increases and then decreases.Especially, work as Er
2o
3when addition is 0.5wt%, the Young's modulus of titanium foam and yield strength reach a maximum value, are respectively 11.56GPa and 24.21MPa.From table, can be clear that rare earth Er
2o
3can effectively improve the mechanical property of titanium foam sample, and rare earth Er
2o
3optimum addition should be 0.5wt%.
The present invention by adding the rare earth Er of different content in raw material
2o
3, adopt powder metallurgy blended elemental successfully to prepare porosity between 64%～73% closed-cell foam titanium in conjunction with pore-forming material technology.
When rare earth Er 2O3 addition is during between 0.25～0.75wt%, along with the increase of addition, the quantity of the microcosmic aperture on the matrix skeleton of titanium foam sample reduces, size reduction, causes skeleton density to increase, and prepared sample performance is also better; And in the time that addition exceedes 0.75wt%, titanium skeleton density declines to some extent, corresponding is the deterioration of the mechanical property of material.Therefore, rare earth Er
2o
3affect the final mechanical property of material by the weave construction that changes titanium foam sample.
Experiment shows, in the time that rare earth addition is 0. 5wt%, and performance the best of prepared titanium foam sample out, its Young's modulus and yield strength are respectively 11.56GPa and 24.21MPa.
Finally explanation is, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can modify or be equal to replacement technical scheme of the present invention, and not departing from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of claim scope of the present invention.
Claims (2)
1. a method that improves titanium foam density, is characterized in that, adopts prior powder metallurgy blended elemental to prepare in titanium foam process, adds rare earth Er 2O3 powder, and the addition of rare earth Er 2O3 is 0.25 wt%～0.75wt%;
Specifically comprise the steps:
1) mixing of raw material: first, load weighted titanium valve and rare earth Er 2O3 powder are carried out to ground and mixed, after it mixes, then pack in V-type mixer and mix 30min with urea granules; The addition of rare earth Er 2O3 powder is 0.25 wt%～0.75wt%;
2) compression moulding: to be mixedly pour in mould after evenly, then use hydraulic single column press compression moulding, pressure used is about 200 MPa, and the dwell time is made as fixed value 1～5min, obtains giving birth to pressed compact;
3) removing and vacuum sintering of pore-forming material: raw pressed compact is carried out to sintering in the vacuum carbon tube furnace having under argon shield atmosphere, and vacuum keep is 10
-3level; Within the scope of 0～450 ℃, slowly heating is to remove pore-forming material, and temperature rise rate is 2 ℃/min, and within the scope of 450～1250 ℃, temperature rise rate is 10 ℃/min, in the time that temperature is raised to 1250 ℃ of sintering temperatures, be incubated 3 h, then cool to room temperature with the furnace, obtain the titanium foam that density is higher.
2. the method that improves according to claim 1 titanium foam density, is characterized in that, the addition of rare earth Er 2O3 powder is 0.5wt%.
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| CN103205592B (en) * | 2013-04-12 | 2015-06-03 | 重庆大学 | Preparation method of titanium foams for cancellous bone |
| CN103447533B (en) * | 2013-09-28 | 2015-04-01 | 重庆大学 | Method for preparing open-cell foam titanium |
| CN103614587A (en) * | 2013-12-05 | 2014-03-05 | 北京师范大学 | Cell-shaped foam titanium of spherical hole structure |
| CN103785831B (en) * | 2014-02-26 | 2015-11-04 | 重庆大学 | A kind of method judging the change of titanium foam sintering process macroscopic view macropore volume |
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Non-Patent Citations (2)
| Title |
|---|
| 朱亚平等.稀土CeO2增强型多孔钛的制备与性能.《稀有金属材料工程》.2011,第40卷(第3期),第511-514页. |
| 稀土CeO2增强型多孔钛的制备与性能;朱亚平等;《稀有金属材料工程》;20110331;第40卷(第3期);第511-514页 * |
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