CN103938051B - The preparation method of the corrosion of resistance to aluminium high desnity metal ceramic material - Google Patents
The preparation method of the corrosion of resistance to aluminium high desnity metal ceramic material Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of the corrosion of resistance to aluminium high desnity metal ceramic material, the corrosion of resistance to aluminium high desnity metal ceramic material comprises Ti powder, Ni powder, AlN and Al2O3 powder, percentage by weight is 12-28 ﹪ Ti powder, 3-7 ﹪ Ni powder, 13-35 ﹪ AlN powder and 30-60 ﹪ Al2O3 powder, weight ratio=the 4:1 of Ti powder and Ni powder, described preparation method comprises the following steps: the mixing and ball milling of (1) preparing burden, (2) pulverize dry, (3) compressing, (4) sintering, after sintering with stove coolingly come out of the stove, the demoulding. This material structure densification, has higher decay resistance, the especially corrosion of resistance to aluminium performance, and the decay resistance in aluminium liquid has very important engineering using value; This preparation method simplifies, production cost is low.
Description
Technical field:
The present invention relates to the corrosion of resistance to aluminium Material Field, relate in particular to a kind of cermet material and preparation method thereof.
Background technology:
Along with the increase of aluminum products demand; cause the waste of the use material such as container, liquid aluminium conveyance conduit and thermometric protective casing of dress metal aluminium liquid, aluminum alloy melt to increase, the material that obtains the better corrosion of resistance to aluminium has very important engineering using value thereupon. Liquid aluminium and aluminium alloy, due to its strong corrosivity, are had higher requirement to the corrosion resistance of the materials such as dress aluminum alloy melt, aluminum alloy melt conveyance conduit and survey aluminium liquid thermocouple protective casing.
Aluminium oxide is a kind of research ceramic material early, composite ceramic material taking aluminium oxide as matrix has high rigidity, the excellent properties such as high temperature resistant, wear-resistant, corrosion-resistant, is therefore widely used in the fields such as metallurgy, chemical industry, machinery, electronics and Aero-Space; But pure alumina fragility is large, toughness is low, how solving this defect also becomes the focus that numerous domestic and international researchers study always. Investigation of materials person is by adding metal in alumina substrate material, make the fragility problem of alumina substrate obtain improving significantly, large quantity research report shows, in improving alumina material toughness, tend to follow the raising of its cost, the preparation cost that therefore how to reduce material also becomes the critical problem of people's research. China national Department of Intellectual Property discloses the preparation method of 201110094542.6 1 kinds of alumina ceramic composite materials, taking Al-Ti-B intermediate alloy, rare metal as toughened and reinforced interpolation phase, preparation by the following method: (1) in common intermediate frequency furnace 1000～1300 DEG C, titanium valve and boron powder are added to aluminium liquid, be incubated 5～10 minutes, prepare Al-Ti-B intermediate alloy; Al-Ti-B intermediate alloy consists of by weight percentage, boron 0.5～2.0%, and titanium 3.0～7.0%, aluminium is surplus; (2) using aluminium oxide ceramics as matrix material, taking Al-Ti-B intermediate alloy, rare metal as toughened and reinforced interpolation phase, take raw material according to the mass percent of aluminium oxide 86%～95%, Al-Ti-B intermediate alloy 3%～8%, rare metal 2%～6%; (3) the raw material weighing up is mixed, taking ethanol as medium Intensive ball mill is after 100～120 hours, place vacuum drying chamber and be dried and cross 200 mesh sieves, make even mixed powder; (4) adopt hot-pressing sintering technique, using nitrogen as sintering atmosphere, 1480～1580 DEG C of sintering temperatures, sintering pressure 28～35MPa, temperature retention time 25～35 minutes, can prepare high tenacity, high-intensity alumina ceramic composite material.
Ceramic-metal composites feature be by ceramic advantage as high temperature resistant, high strength and non-oxidizability etc. with the advantage of metal as good toughness and bending strength etc. combine, obtain a kind of material with good combination property, in addition, Metal Phase add sintering character and the fragility that can also improve ceramic phase. be used for preparing the most frequently used pottery of ceramic-metal composite material and have resistant to elevated temperatures oxide, silicide, boride, carbide and nitride etc., wherein, boron carbide, because having excellent combination property, is more and more subject to the extensive concern of Chinese scholars. boron carbide has ultrahigh hardness, low-density characteristic. mostly the pure B4C potsherd of current closely knit sintering is to adopt the mode of high-temperature pressurizing sintering at 2300 DEG C to obtain. because ceramic densification process is more difficult, thus the ceramic material that the material density finally obtaining in 95% left and right, wants to obtain high-compactness (> 98%) to equipment and process require high. the B4C pottery compression strength that can make is at present generally between 1.7GPa～2.8GPa, and HV can reach 1220～1250, and bending strength is between 280MPa～400MPa. because the performance of boron carbide is relevant to ceramic density, density with sintering temperature, temperature retention time and moulding pressure are closely related, therefore to obtain high performance dense ceramic material owing to all requiring very high to former and technical process, cause product cost too high, and the product of final molding cannot carry out normal machining because of the restriction of ceramic high rigidity, and therefore, the application of its product is also greatly limited. require highly for pottery preparation, fragility is large and be difficult for mach shortcoming and developed B4C/Al cermet material technology prepared by pressure-free impregnation. adopt lower sintering temperature (2000 DEG C of left and right) with respect to closely knit sintering to prepare ceramic skeleton, reduced the requirement to equipment, reduced preparation time, and adding of metallic aluminium can improve ceramic toughness. select metallic aluminium to be because the density of boron carbide and aluminium is close, and the ductility of fine aluminium, more flowability, can infiltrate in the space of boron carbide skeleton by capillary attraction automatic infiltration at a certain temperature, without additionally pressurization again. and adding of aluminium makes the cermet product of final molding have electric conductivity, can utilize wire cutting machine to be processed into any required form. at present obtaining larger progress for the research of B4C/Al is to have reduced ceramic sintering temperature (sintering between 1900 DEG C～2000 DEG C), adding of aluminium brought up to the bending strength of ceramic material between 300GPa～600GPa, fracture toughness also improves, the bending strength of B4C/Al composite prepared by the people such as domestic Li Qing reaches 601MPa, fracture toughness is 9.2MPam1/2, but its hardness (between HV900～1050) and compression strength (1.2GPa～1.5GPa) are but reduced accordingly, and performance is subject to large (the wherein porosity of ceramic skeleton of the impact of metallic aluminium amount, the fluidity determining of metallic aluminium the number of metallic aluminium amount). China national Department of Intellectual Property discloses the preparation method of 201110453215.5 1 kinds of low-density ceramic-metal composites of high compressive strength, step is as follows: (1) granulating and forming: taking doped silicon carbide ceramic powders and boron carbide powder as ceramic material, the doped silicon carbide ceramic powders that is 5～50% by mass percent and surplus boron carbide powder add three-dimensional planetary mixed powder machine to mix powder, in ceramic material after mixing, adding mass concentration is 4% binding agent PVA mixing granulation, and the addition of binding agent PVA is 2～10% of ceramic material gross mass, after granulation, then adopt 24～60 order sieve, leave standstill and again institute's granulation is placed in to cast iron die extrusion forming after 12 hours, obtain prefabricated blank, molding pressure is 50～120MPa, pressurize 30～150s, (2) pressureless sintering: prefabricated blank is placed in to vacuum sintering furnace, vacuumize, vacuum is 10-2Pa, be warming up to 1600～1900 DEG C of sintering with 5～10 DEG C/min speed, insulation 0.5～2h, obtain B4C-SiC Quito hole pre-burning body, (3) pressure-free impregnation: aluminium block is placed on B4C-SiC Quito hole pre-burning body, and be jointly placed in vacuum sintering furnace and be warming up to 1000～1200 DEG C, insulation 0.5～2h, obtain ceramet, (4) heat treatment: ceramet is placed in heat-treatment furnace, and be heated to 650～900 DEG C of temperature, after insulation 8～24h, take out, and be placed in water and do Quenching Treatment.
The heterogeneous composite material that cermet material is made up of one or more ceramic phases and metal or alloy. Can be divided into heat resistant type, wear-resisting type and corrosion resistant type etc. by performance and purposes. China national Department of Intellectual Property discloses CN200610053348.2 metal/metal ceramic composite, it is that composite cermet forms on low-alloy steel base material, described cermet is Metal Substrate titanium carbide, and it comprises Binder Phase metal and is dispersed in the hard particles phase titanium carbide in Binder Phase metal; Between described low-alloy steel and cermet, be metallurgical binding, between the Binder Phase metal at combination interface place and described low-alloy steel, exist and spread the district of dissolving each other, spread the gradient transitional lay that has hard particles phase in the district of dissolving each other; Described Binder Phase metal is nickel-based self-fluxing alloy, and the self propagating high temperature synthetic reaction that described titanium carbide is caused in the time casting described low-alloy steel by the titanium in self propagating high temperature synthetic reaction system and carbon generates; It consists of described self propagating high temperature synthetic reaction system by percentage to the quality: nickel-based self-fluxing alloy 35～45%, titanium Ti44～52%, carbon C11～13%.
Sialon ceramics has good toughness, very high hardness and wearability, and very high high-temperature oxidation resistance. The initial material of preparing Sialon ceramics is Si3N4, Al2O3, AlN, Y2O3 and other metal oxides, when sintering, easily reaches densified by liquid phase around knot, and preparation technology can adopt pressureless sintering, hot pressed sintering or gas pressure sintering. Have the very strong corrosion of resistance to aluminium ability although match the grand ceramic material that waits, its fragility is large, especially very easily ftractures and has limited its use at the working condition of hot and cold alternation. Metal and ceramic composite can effectively improve the fragility of single ceramic material, and strong, the toughness of entirety are improved, and the material that had not only had excellent strength-toughness but also had the high corrosion of a resistance to aluminium performance for preparation has improved condition.
Summary of the invention:
The object of the present invention is to provide a kind of preparation process simple, material structure densification, there is good toughness, hardness, wearability and high-temperature oxidation resistance, especially there is the corrosion of resistance to aluminium high desnity metal ceramic material of the corrosion of resistance to aluminium performance and preparation method thereof.
The present invention is achieved by the following technical solution:
The corrosion of resistance to aluminium high desnity metal ceramic material, comprise Ti powder, Ni powder, AlN and Al2O3 powder, percentage by weight is 12-28 ﹪ Ti powder, 3-7 ﹪ Ni powder, 13-35 ﹪ AlN powder and 30-60 ﹪ Al2O3 powder, weight ratio=the 4:1 of Ti powder and Ni powder, described Ti powder, Ni powder, AlN powder and Al2O3 powder form through mixing and ball milling, compacting, electric field-activate hot pressing auxiliary combustion stove sintering.
The corrosion of resistance to aluminium high desnity metal ceramic material also comprises TiN, and its percentage by weight is 5-10 ﹪.
The corrosion of resistance to aluminium high desnity metal ceramic material also comprises Y2O3, and its percentage by weight is 2-10 ﹪.
Described Ti powder and the purity > 97.8% of Ni powder, 20 microns of granularity <.
The purity > 97.8% of described AlN, TiN, Y2O3 and Al2O3 powder, 50 microns of granularity <.
The preparation method of the described corrosion of resistance to aluminium high desnity metal ceramic material comprises the following steps:
(1) the mixing and ball milling of preparing burden: according to percentage by weight batching mixing and ball milling, ball-milling medium is ethanol, and Ball-milling Time is 10-16 hour;
(2) pulverize dry: the powder mixing after ball milling is pulverized, is dried;
(3) compressing: the blank that above-mentioned mixed-powder is packed into mould and is pressed into required form;
(4) sintering: above-mentioned blank is carried out to electric field-activate hot pressing assisted sintering; the vacuum-sintering under argon shield atmosphere of described sintering; described vacuum < 10Pa; sintering temperature is 1150 DEG C-1250 DEG C; temperature retention time is 5～10 minutes, after sintering with stove coolingly come out of the stove, the demoulding.
Described step (1) in mixing and ball milling according to powder mixture: ball: the mode that the weight ratio of ethanol is 1:2:1 is carried out.
The mould of described step in is (3) graphite jig.
Described step (4) in heating, be 55-65MPa to the auxiliary pressure applying of blank electric field-activate hot pressing in insulating process.
The present invention compared with prior art has following row beneficial effect:
The present invention is low-temperature sintering ceramic-metal composite, simplify production technology, reduced production costs, greatly improved the compactness of ceramic-metal composite, there is good toughness, hardness, wearability and high-temperature oxidation resistance, thereby improve the decay resistance of ceramic-metal composite, improved the service life of cermet material, the decay resistance of this material in aluminium liquid has very important engineering using value simultaneously.
Brief description of the drawings:
Fig. 1 is the embodiment of the present invention one corrosion of resistance to aluminium high desnity metal ceramic material scanning electron micrograph;
Fig. 2 is the XRD diffracting spectrum of the embodiment of the present invention one corrosion of resistance to aluminium high desnity metal ceramic material.
Detailed description of the invention:
Below in conjunction with the drawings and specific embodiments, the invention will be further described:
Embodiment mono-: referring to Fig. 1 and Fig. 2, a kind of corrosion of resistance to aluminium high desnity metal ceramic material, comprise Ti powder, Ni powder, AlN powder, TiN powder, Y2O3 powder and Al2O3 powder, percentage by weight is 16 ﹪ Ti powder, 4 ﹪ Ni powder, 17 ﹪ AlN powder, 8 ﹪ TiN powder, 5 ﹪ Y2O3 powder and 50 ﹪ Al2O3 powder, and described Ti powder, Ni powder, AlN powder, TiN powder, Y2O3 powder and Al2O3 powder form through mixing and ball milling, compacting, electric field-activate hot pressing auxiliary combustion stove sintering, its preparation method comprises the following steps: the mixing and ball milling of (1) preparing burden: with Ti powder, Ni powder, AlN powder, TiN powder, Y2O3 powder and Al2O3 powder are raw material, the purity > 99.8% of AlN and Al2O3 powder, 1 micron of granularity, TiN powder, Y2O3 powder, the purity > 99.8% of Ti and Ni powder, 0.5 micron of granularity, pack ball mill into according to percentage by weight, ball-milling medium is ethanol, according to powder mixture: ball: the weight ratio of ethanol is 1:2:1 batching, start ball milling, Ball-milling Time is 16 hours, ball milling adopts clearance-type ball milling, it is ball milling 1 hour, shut down half an hour, (2) pulverize dry: after ball milling completes, the powder mixing is taken out, and at 120 DEG C, dry, grind, (3) compressing: above-mentioned mixed-powder to be filled to graphite jig, to be put on baby press, be pressed into the pressed compact of required form, (4) sintering: the graphite jig that finally this is pressed to pressed compact is put into electric field-activate hot pressing auxiliary combustion stove and carried out sintering, sintering is to carry out under argon shield atmosphere, in heating, insulating process, pressed compact is applied to 60MPa pressure, in stove, vacuum maintains below 10Pa, sintering temperature is 1250 DEG C, temperature retention time is 5～10 minutes, is together cooled to 100 DEG C comes out of the stove when following after sintering with combustion furnace, then from combustion furnace, takes out, the demoulding.
Mechanical milling process Main Function of the present invention is make bonded metal Ti, the refinement of Ni powder and evenly wrap up AlN powder, TiN powder, Y2O3 powder, Al2O3 powder particle. The present invention's corrosion of resistance to aluminium high desnity metal ceramic material density is high, the corrosion of resistance to aluminium performance is good. The present invention's corrosion of resistance to aluminium high desnity metal ceramic material carries out corrosion test in the aluminium liquid of melting, compared with other metal materials, as the decay resistance such as stainless steel, cast iron obviously improves. The present invention's corrosion of resistance to aluminium high desnity metal ceramic material sample is 99.6% by drainage test density, the present invention's corrosion of resistance to aluminium high desnity metal ceramic material sample scanning electron microscopy is organized as shown in Figure 1, and the XRD diffracting spectrum of the present invention's corrosion of resistance to aluminium high desnity metal ceramic material sample as shown in Figure 2.
Two kinds of different materials are the average corrosion rate after 8 hours at 700 DEG C of aluminium corrosions, as shown in Table 1.
The corrosion of the resistance to aluminium Performance Ratio of table one or two kind of different materials
| The present invention | Cast iron | |
| Average corrosion rate (mm/h) | 6.3Х10-5 | 8.5Х10-1 |
Embodiment bis-: a kind of corrosion of resistance to aluminium high desnity metal ceramic material, comprise Ti powder, Ni powder, AlN powder, TiN powder, Y2O3 powder and Al2O3 powder, percentage by weight is 12 ﹪ Ti powder, 3 ﹪ Ni powder, 13 ﹪ AlN powder, 7 ﹪ TiN powder, 5 ﹪ Y2O3 powder and 60 ﹪ Al2O3 powder, described Ti powder, Ni powder, AlN, TiN, the purity > 99.8% of Y2O3 powder and Al2O3 powder, described AlN, TiN, the granularity of Y2O3 and Al2O3 powder is 5 microns, described Ti powder and the granularity of Ni powder are 2 microns, described Ti powder, Ni powder, AlN powder, TiN powder, Y2O3 powder and Al2O3 powder are through mixing and ball milling, compacting, electric field-activate hot pressing auxiliary combustion stove sintering forms, its preparation method is with embodiment mono-.
The present invention's corrosion of resistance to aluminium high desnity metal ceramic material sample is 99.7% by drainage test density.
Two kinds of different materials are the average corrosion rate after 8 hours at 700 DEG C of aluminium corrosions, as shown in Table 2.
The corrosion of the resistance to aluminium Performance Ratio of two kinds of different materials of table two
| The present invention | Cast iron | |
| Average corrosion rate (mm/h) | 5.4Х10-5 | 8.5Х10-1 |
Embodiment tri-: a kind of corrosion of resistance to aluminium high desnity metal ceramic material, comprise Ti powder, Ni powder, AlN powder, TiN powder and Al2O3 powder, percentage by weight is 16 ﹪ Ti powder, 4 ﹪ Ni powder, 20 ﹪ AlN powder, 10 ﹪ TiN powder and 50 ﹪ Al2O3 powder, described Ti powder, Ni powder, AlN, the purity > 99.8% of TiN and Al2O3 powder, described AlN, the granularity of TiN and Al2O3 powder is 5 microns, described Ti powder and the granularity of Ni powder are 2 microns, described Ti powder, Ni powder, AlN powder, TiN powder and Al2O3 powder are through mixing and ball milling, compacting, electric field-activate hot pressing auxiliary combustion stove sintering forms, its preparation method is with embodiment mono-.
The present invention's corrosion of resistance to aluminium high desnity metal ceramic material sample is 99.5% by drainage test density.
Two kinds of different materials are the average corrosion rate after 8 hours at 700 DEG C of aluminium corrosions, as shown in Table 3.
The corrosion of the resistance to aluminium Performance Ratio of two kinds of different materials of table three
| The present invention | Cast iron | |
| Average corrosion rate (mm/h) | 4.3Х10-5 | 8.5Х10-1 |
There is raising by a relatively large margin by obtaining the ceramic-metal composite corrosion of the resistance to aluminium performance that density is very high in embodiment mono-, two, three more than cast iron. In addition, corrosion resisting property corresponding it can also be seen that cermet density is higher from three tables time is higher, and the present invention can prepare the cermet material with heterogeneity proportioning, and the higher corrosion of resistance to aluminium of density is higher.
Embodiment tetra-: a kind of corrosion of resistance to aluminium high desnity metal ceramic material, comprise Ti powder, Ni powder, AlN powder, TiN powder, Y2O3 powder and Al2O3 powder, percentage by weight is 20 ﹪ Ti powder, 5 ﹪ Ni powder, 33 ﹪ AlN powder, 5 ﹪ TiN powder, 2 ﹪ Y2O3 powder and 35 ﹪ Al2O3 powder, described Ti powder, Ni powder, AlN, TiN, the purity > 99.8% of Y2O3 powder and Al2O3 powder, described AlN, TiN, the granularity of Y2O3 and Al2O3 powder is 1 micron, described Ti powder and the granularity of Ni powder are 0.5 micron, described Ti powder, Ni powder, AlN powder, TiN powder, Y2O3 powder and Al2O3 powder are through mixing and ball milling, compacting, electric field-activate hot pressing auxiliary combustion stove sintering forms, its preparation method is with embodiment mono-.
Embodiment five: a kind of corrosion of resistance to aluminium high desnity metal ceramic material, comprise Ti powder, Ni powder, AlN powder and Al2O3 powder, percentage by weight is 28 ﹪ Ti powder, 7 ﹪ Ni powder, 35 ﹪ AlN powder and 30 ﹪ Al2O3 powder, the purity > 99.8% of described Ti powder, Ni powder, AlN powder and Al2O3 powder, the granularity of described AlN and Al2O3 powder is 1 micron, described Ti powder and the granularity of Ni powder are 0.5 micron, and described Ti powder, Ni powder, AlN powder and Al2O3 powder form through mixing and ball milling, compacting, electric field-activate hot pressing auxiliary combustion stove sintering; Its preparation method is with embodiment mono-.
Embodiment is just for the ease of understanding technical scheme of the present invention; do not form limiting the scope of the invention; every interior any simple modification, equivalent variations and modification of perhaps according to technical spirit of the present invention, above scheme being done that does not depart from technical solution of the present invention, within all still belonging to protection domain of the present invention.
Claims (7)
1. the preparation method of the corrosion of resistance to aluminium high desnity metal ceramic material, the corrosion of resistance to aluminium high desnity metal ceramic material, comprises Ti powder, Ni powder, AlN and Al2O3Powder, percentage by weight is 12-28 ﹪ Ti powder, 3-7 ﹪ Ni powder, 13-35 ﹪ AlN powder and 30-60 ﹪ Al2O3Powder, the weight ratio=4:1 of Ti powder and Ni powder; Described Ti powder and the purity > 97.8% of Ni powder, 20 microns of granularity <; Described AlN and Al2O3The purity > 97.8% of powder, 50 microns of granularity <; Described Ti powder, Ni powder, AlN powder and Al2O3Powder forms through mixing and ball milling, compacting, electric field-activate hot pressing auxiliary combustion stove sintering, and its preparation method comprises the following steps:
(1) the mixing and ball milling of preparing burden: according to percentage by weight batching mixing and ball milling, ball-milling medium is ethanol, and Ball-milling Time is 10-16 hour;
(2) pulverize dry: the powder mixing after ball milling is pulverized, is dried;
(3) compressing: the blank that above-mentioned mixed-powder is packed into mould and is pressed into required form;
(4) sintering: above-mentioned blank is carried out to electric field-activate hot pressing assisted sintering; the vacuum-sintering under argon shield atmosphere of described sintering; described vacuum < 10Pa; sintering temperature is 1150 DEG C-1250 DEG C; temperature retention time is 5～10 minutes, after sintering with stove coolingly come out of the stove, the demoulding.
2. the preparation method of the corrosion of resistance to aluminium high desnity metal ceramic material according to claim 1, is characterized in that: described step (4) in heating, be 55-65MPa to the auxiliary pressure applying of blank electric field-activate hot pressing in insulating process.
3. the preparation method of the corrosion of resistance to aluminium high desnity metal ceramic material according to claim 2, it is characterized in that: the described corrosion of resistance to aluminium high desnity metal ceramic material also comprises TiN, its percentage by weight is 5-10 ﹪, the purity > 97.8% of TiN powder, 50 microns of granularity <.
4. the preparation method of the corrosion of resistance to aluminium high desnity metal ceramic material according to claim 3, is characterized in that: the described corrosion of resistance to aluminium high desnity metal ceramic material also comprises Y2O3, its percentage by weight is 2-10 ﹪, Y2O3The purity > 97.8% of powder, 50 microns of granularity <.
5. according to the preparation method of the corrosion of the resistance to aluminium high desnity metal ceramic material described in claim 1,2,3 or 4, it is characterized in that: described step (1) in mixing and ball milling according to powder mixture: ball: the mode that the weight ratio of ethanol is 1:2:1 is carried out.
6. according to the preparation method of the corrosion of the resistance to aluminium high desnity metal ceramic material described in claim 1,2,3 or 4, it is characterized in that: the mould of described step in is (3) graphite jig.
7. the preparation method of the corrosion of resistance to aluminium high desnity metal ceramic material according to claim 5, is characterized in that: the mould of described step in is (3) graphite jig.
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| CN1037323A (en) * | 1988-01-13 | 1989-11-22 | 唐化学原料公司 | The densification of ceramic-metal composites |
| CN101037731A (en) * | 2007-04-26 | 2007-09-19 | 武汉理工大学 | Stainless steel-TiC nano composite powder and preparation method |
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| CN101037731A (en) * | 2007-04-26 | 2007-09-19 | 武汉理工大学 | Stainless steel-TiC nano composite powder and preparation method |
| CN102731071A (en) * | 2011-04-06 | 2012-10-17 | 鲁东大学 | Preparation method of Al-Ti-B and rare metal synergistically-toughened alumina |
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