CN103938046A - Cermet material resistant to molten aluminum corrosion - Google Patents
Cermet material resistant to molten aluminum corrosion Download PDFInfo
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- CN103938046A CN103938046A CN201310019101.9A CN201310019101A CN103938046A CN 103938046 A CN103938046 A CN 103938046A CN 201310019101 A CN201310019101 A CN 201310019101A CN 103938046 A CN103938046 A CN 103938046A
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Abstract
The invention discloses a cermet material resistant to molten aluminum corrosion. The cermet material comprises, by weight, 1-5% of Ti powder, 10-25% of Ni powder, 40-60% of Al2O3 powder and 20-40% of AlN powder, the material is made of the Ti powder, the Ni powder, the Al2O3 powder and the AlN powder through mixing ball milling, pressing, activating through an electric field, auxiliary hot-pressing and sintering through a combustion furnace. The cermet material resistant to molten aluminum corrosion is high in compactness, good in corrosion resistance and long in service life and has important engineering application value due to the corrosion resistance in molten aluminum.
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.
Background technology:
Increase along with aluminum products demand; cause the waste of the use materials such as container, liquid aluminium transport pipe 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 corrodibility, are had higher requirement to the solidity to corrosion of the materials such as dress aluminum alloy melt, aluminum alloy melt transport pipe and survey aluminium liquid thermocouple protective casing.
Aluminum oxide is a kind of research stupalith early, the composite ceramic material that the aluminum oxide of take is 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 aerospace; 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, when 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, take Al-Ti-B intermediate alloy, rare metal is toughened and reinforced interpolation phase, preparation by the following method: (1) in common medium-frequency induction furnace 1000～1300 ℃, 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 alumina-ceramic as body material, take Al-Ti-B intermediate alloy, rare metal is toughened and reinforced interpolation phase, according to the mass percent of aluminum oxide 86%～95%, Al-Ti-B intermediate alloy 3%～8%, rare metal 2%～6%, takes raw material; (3) the raw material weighing up is mixed, take ethanol as medium Intensive ball mill is after 100～120 hours, place vacuum drying oven 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 ℃ of sintering temperatures, sintering pressure 28～35MPa, soaking 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 oxidation-resistance etc. with the advantage of metal as good toughness and bending strength etc. combine, obtain a kind of material with good over-all properties; In addition, metallographic phase adds 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 compound, silicide, boride, carbide and nitride etc.; Wherein, norbide, because having excellent over-all properties, is more and more subject to the extensive concern of Chinese scholars.Norbide has ultrahigh hardness, low-density characteristic.Mostly the pure B4C ceramic plate of current closely knit sintering is to adopt the mode of high-temperature pressurizing sintering at 2300 ℃ to obtain.Because ceramic densification process is more difficult, thus the stupalith 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 ultimate 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 norbide is relevant to ceramic density, density with sintering temperature, soaking time and moulding pressure are closely related, therefore to obtain high performance dense ceramic material owing to all requiring very high to molding device and technological process, caused 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 shape of its product is also greatly limited.For pottery preparation, require highly, fragility is large and be difficult for mach shortcoming and developed B4C/Al cermet material technology prepared by pressure-free impregnation.Employing lower sintering temperature (2000 ℃ of left and right) with respect to closely knit sintering is prepared ceramic skeleton, has reduced the requirement to equipment, has reduced preparation time; And adding of metallic aluminium can improve ceramic toughness.Select metallic aluminium to be because the density of norbide and aluminium is close, and the ductility of fine aluminium, more flowability, can infiltrate in the space of norbide skeleton by capillary attraction automatic infiltration at a certain temperature, without additionally pressurization again.And adding of aluminium makes the sintering metal product of final molding have electroconductibility, can utilize wire cutting machine to be processed into any desired shape.It is to have reduced ceramic sintering temperature (sintering between 1900 ℃～2000 ℃) that the current research for B4C/Al obtains larger progress, adding of aluminium brought up to the bending strength of stupalith between 300GPa～600GPa, fracture toughness property also improves, the bending strength of B4C/Al matrix material prepared by the people such as domestic Li Qing reaches 601MPa, fracture toughness property is 9.2MPam1/2, but its hardness (between HV900～1050) and ultimate compression strength (1.2GPa～1.5GPa) have but been reduced accordingly, and the large (porosity of ceramic skeleton wherein of the impact that performance is subject to 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: take doped silicon carbide ceramic powder and boron carbide powder as ceramic material, the doped silicon carbide ceramic powder 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 add-on of binding agent PVA is 2～10% of ceramic material total mass, after granulation, then adopt 24～60 order sieve, after standing 12 hours, again institute's granulation is placed in to cast iron die extrusion forming, obtain precast billet, molding pressure is 50～120MPa, pressurize 30～150s, (2) pressureless sintering: precast billet is placed in to vacuum sintering furnace, vacuumize, vacuum is 10-2Pa, with 5～10 ℃/min speed, be warming up to 1600～1900 ℃ of sintering, 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 ℃, insulation 0.5～2h, obtain ceramic metal, (4) thermal treatment: ceramic metal is placed in heat treatment furnace, and be heated to 650～900 ℃ of temperature, after insulation 8～24h, take out, and be placed in water and do quench treatment.
The heterogeneous composite material that cermet material is comprised of one or more ceramic phases and metal or alloy.By performance and purposes, can be divided into heat resistant type, wear-resistant type and corrosion resistant type etc.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 sintering metal is metal matrix 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 sintering metal, be metallurgical binding, between the Binder Phase metal at bonding 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 building-up reactions that the titanium of described titanium carbide in self propagating high temperature building-up reactions system and carbon cause when the described low alloy steel of casting generates; It consists of described self propagating high temperature building-up reactions system by percentage to the quality: nickel-based self-fluxing alloy 35～45%, titanium Ti44～52%, carbon C11～13%.
Although match the grand stupalith that waits, have the very strong corrosion of resistance to aluminium ability, its fragility is large, especially at the working condition of hot and cold alternation, very easily ftractures and has limited its use.Metal and ceramic composite can effectively improve the fragility of single stupalith, and whole strong, toughness 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 is fine and close, has the corrosion of the resistance to aluminium cermet material of the corrosion of resistance to aluminium performance.
The present invention is achieved by the following technical solution:
The corrosion of resistance to aluminium cermet material, comprise Ti powder, Ni powder, Al2O3 powder and AlN powder, weight percent is 1-5%Ti, 10-25%Ni, 40-60% Al2O3,20-40%AlN, and described Ti powder, Ni powder, Al2O3 powder and AlN powder form through mixing and ball milling, compacting, electric field-activate hot pressing aid burning stove sintering.
Described Ti powder and the purity > 97.9% of Ni powder, 20 microns of granularity <.
Described AlN powder and the purity > 97.9% of Al2O3 powder, 50 microns of granularity <.
The purity > 99.9% of described Ti powder, Ni powder, Al2O3 powder and AlN powder.
The present invention compared with prior art has following row beneficial effect:
The present invention has improved the compactness of ceramic-metal composite, thereby improved the corrosion resistance nature of ceramic-metal composite, improved the work-ing life of cermet material, the corrosion resistance nature of this material in aluminium liquid has very important engineering using value simultaneously.
Accompanying drawing explanation:
Fig. 1 is that the scanning electron microscopy of cermet material of the present invention is organized photo.
Fig. 2 is the X-ray diffraction analysis collection of illustrative plates of cermet material of the present invention.
Embodiment:
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 cermet material, comprise Ti powder, Ni powder, Al2O3 powder and AlN powder, described weight percent is 4%Ti, 17%Ni, 55% Al2O3, 24%AlN, described Ti powder, Ni powder, Al2O3 powder and AlN powder are through mixing and ball milling, compacting, electric field-activate hot pressing aid burning stove sintering forms, its preparation method comprises the following steps: the mixing and ball milling of (1) preparing burden: after first Ti powder and Ni powder being weighed according to weight percent, pack ball mill into, the purity of described Ti powder and Ni powder is 99.9%, 20 microns of granularity <, material: ball weight is than being 1:2, in ball mill, be filled with argon shield, start ball milling, Ball-milling Time is 8 hours, secondly according to per-cent, in ball mill, add Al2O3 powder and AlN powder, the purity of described AlN powder and Al2O3 powder is 99.9%, 50 microns of granularity <, and according to compound: ball weight is than carrying out secondary ball milling for 1:2, and Ball-milling Time is 14 hours, the mechanical milling process Main Function of Ti powder, Ni powder is the granularity of refinement bonded metal Ti powder, Ni powder, and two kinds of metal-powders are fully mixed, and the Main Function of Al2O3 powder, AlN sphere of powder mill is to mix, and all particle sizes are more and more tiny, (2) pulverize dry: the Ti powder mixing after ball milling, Ni powder, Al2O3 powder and AlN powder are taken out, and at 110 ℃, dry, grind, (3) press forming: above-mentioned powder mix is filled in graphite jig, is put in the blank that is pressed into desired shape on baby press, (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, in heating, insulating process, blank is applied to 60MPa pressure, described vacuum tightness 10Pa, sintering temperature is 1150 ℃, soaking time is 5～10 minutes, after sintering furnace cooling come out of the stove, the demoulding.
The present invention's corrosion of resistance to aluminium cermet material density is high, the corrosion of resistance to aluminium performance is good.The present invention's corrosion of resistance to aluminium cermet material carries out corrosion test in the aluminium liquid of melting, compared with other metallic substance, obviously improves as corrosion resistance natures such as stainless steel, cast irons.
The present invention's corrosion of resistance to aluminium cermet material sample is 99.5% by drainage test density.The present invention's corrosion of resistance to aluminium cermet material sample scanning electron microscopy is organized as shown in Figure 1, and the X ray diffracting spectrum of gained sintering metal sample as shown in Figure 2.
Two kinds of differing materials corrode the average corrosion rate after 8 hours in 700 ℃ of aluminium liquid, as shown in Table 1.
The corrosion of the resistance to aluminium Performance Ratio of table one or two kind of differing materials
| ? | Cermet material of the present invention | Cast iron |
| Average corrosion rate (mm/h) | 6.3Х10-4 | 8.5Х10-1 |
Embodiment bis-: a kind of corrosion of resistance to aluminium cermet material, comprise Ti powder, Ni powder, Al2O3 powder and AlN powder, described weight percent is 4%Ti, 15%Ni, 50% Al2O3, 31%AlN, described Ti powder, Ni powder, Al2O3 powder and AlN powder are through mixing and ball milling, compacting, electric field-activate hot pressing aid burning stove sintering forms, its preparation method comprises the following steps: the mixing and ball milling of (1) preparing burden: after first Ti powder and Ni powder being weighed according to weight percent, pack ball mill into, the purity of described Ti powder and Ni powder is 99.9%, 20 microns of granularity <, material: ball weight is than being 1:2, in ball mill, be filled with argon shield, start ball milling, Ball-milling Time is 8 hours, secondly according to weight percent, in ball mill, add Al2O3 powder and AlN powder, the purity of described AlN powder and Al2O3 powder is 99.9%, 50 microns of granularity <, and according to compound: ball weight is than carrying out secondary ball milling for 1:2, and Ball-milling Time is 12 hours, (2) pulverize dry: the Ti powder mixing after ball milling, Ni powder, Al2O3 powder and AlN powder are taken out, and at 120 ℃, dry, grind, (3) press forming: above-mentioned powder mix is filled in graphite jig, is put in the blank that is pressed into desired shape on baby press, (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, in heating, insulating process, blank is applied to 60MPa pressure, described vacuum tightness 10Pa, sintering temperature is 1100 ℃, soaking time is 5～10 minutes, after sintering 100 ℃ of furnace cooling come out of the stove below, the demoulding.
The present invention's corrosion of resistance to aluminium cermet material sample is 99.6% by drainage test density.
Two kinds of differing materials corrode the average corrosion rate after 8 hours in 700 ℃ of aluminium liquid, as shown in Table 2.
The corrosion of the resistance to aluminium Performance Ratio of two kinds of differing materials of table two
| ? | Cermet material of the present invention | Cast iron |
| Average corrosion rate (mm/h) | 5.2Х10-4 | 8.5Х10-1 |
Embodiment tri-: a kind of corrosion of resistance to aluminium cermet material, comprise Ti powder, Ni powder, Al2O3 powder and AlN powder, described weight percent is 3%Ti, 13%Ni, 50% Al2O3, 34%AlN, described Ti powder, Ni powder, Al2O3 powder and AlN powder are through mixing and ball milling, compacting, electric field-activate hot pressing aid burning stove sintering forms, its preparation method comprises the following steps: the mixing and ball milling of (1) preparing burden: first pack Ti powder and Ni powder into ball mill after according to weight percent, the purity of described Ti powder and Ni powder is 99.9%, 20 microns of granularity <, material: ball weight is than being 1:2, in ball mill, be filled with argon shield, start ball milling, Ball-milling Time is 8 hours, secondly according to weight percent, in ball mill, add Al2O3 powder and AlN powder, the purity of described AlN powder and Al2O3 powder is 99.9%, 50 microns of granularity <, and according to compound: ball weight is than carrying out secondary ball milling for 1:2, and Ball-milling Time is 10 hours, (2) pulverize dry: the Ti powder mixing after ball milling, Ni powder, Al2O3 powder and AlN powder are taken out, and at 120 ℃, dry, grind, (3) press forming: above-mentioned powder mix is filled in graphite jig, is put in the blank that is pressed into desired shape on baby press, (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, in heating, insulating process, blank is applied to 60MPa pressure, described vacuum tightness 10Pa, sintering temperature is 1100 ℃, soaking time is 5～10 minutes, after sintering 100 ℃ of furnace cooling come out of the stove below, the demoulding.
The present invention's corrosion of resistance to aluminium cermet material sample is 99.7% by drainage test density.
Two kinds of differing materials corrode the average corrosion rate after 8 hours in 700 ℃ of aluminium liquid, as shown in Table 3.
The corrosion of the resistance to aluminium Performance Ratio of two kinds of differing materials of table three
| ? | Cermet material of the present invention | Cast iron |
| Average corrosion rate (mm/h) | 6.7Х10 -4 | 8.5Х10 -1 |
The cermet material corrosion of the resistance to aluminium performance obtaining in embodiment mono-, two, three has the raising of larger amplitude more than cast iron.Corrosion resisting property corresponding while in addition, it can also be seen that sintering metal density is higher from three tables is higher.The present invention can prepare the cermet material with heterogeneity proportioning, and the higher corrosion of resistance to aluminium of density is higher.
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 (5)
1. the corrosion of resistance to aluminium cermet material, it is characterized in that: comprise Ti powder, Ni powder, Al2O3 powder and AlN powder, weight percent is 1-5%Ti, 10-25%Ni, 40-60% Al2O3,20-40%AlN, and described Ti powder, Ni powder, Al2O3 powder and AlN powder form through mixing and ball milling, compacting, electric field-activate hot pressing aid burning stove sintering.
2. the corrosion of resistance to aluminium cermet material according to claim 1, is characterized in that: described Ti powder and the purity > 97.9% of Ni powder, 20 microns of granularity <.
3. the corrosion of resistance to aluminium cermet material according to claim 1 and 2, is characterized in that: described AlN powder and the purity > 97.9% of Al2O3 powder, 50 microns of granularity <.
4. the corrosion of resistance to aluminium cermet material according to claim 1 and 2, is characterized in that: the purity > 99.9% of described Ti powder, Ni powder, Al2O3 powder and AlN powder.
5. the corrosion of resistance to aluminium cermet material according to claim 3, is characterized in that: the purity > 99.9% of described Ti powder, Ni powder, Al2O3 powder and AlN powder.
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Cited By (2)
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| CN104959103A (en) * | 2015-07-03 | 2015-10-07 | 苏州市科迪石化工程有限公司 | Corrosion-resistant filler and processing method for same |
| CN114058919A (en) * | 2021-11-15 | 2022-02-18 | 郑州大学 | Metal ceramic die material for sintering diamond saw blade and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104959103A (en) * | 2015-07-03 | 2015-10-07 | 苏州市科迪石化工程有限公司 | Corrosion-resistant filler and processing method for same |
| CN114058919A (en) * | 2021-11-15 | 2022-02-18 | 郑州大学 | Metal ceramic die material for sintering diamond saw blade and preparation method thereof |
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