CN103938046B

CN103938046B - The corrosion of resistance to aluminium cermet material

Info

Publication number: CN103938046B
Application number: CN201310019101.9A
Authority: CN
Inventors: 何兆龙
Original assignee: JIANGSU ZHAOLONG ELECTRIC Co Ltd
Current assignee: JIANGSU ZHAOLONG ELECTRIC Co Ltd
Priority date: 2013-01-20
Filing date: 2013-01-20
Publication date: 2016-01-20
Anticipated expiration: 2033-01-20
Also published as: CN103938046A

Abstract

The invention discloses a kind of corrosion of resistance to aluminium cermet material, comprise Ti powder, Ni powder, Al2O3 powder and AlN powder, does is weight percent 1-5%Ti, 10-25%Ni, 40-60%? Al2O3,20-40%AlN, 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.The compactness of this corrosion of resistance to aluminium cermet material is high, corrosion resistance and good, long service life, and the corrosion resistance nature in aluminium liquid has very important engineer applied and is worth.

Description

The corrosion of resistance to aluminium cermet material

Technical field:

The present invention relates to the corrosion of resistance to aluminium Material Field, particularly relate to a kind of cermet material.

Background technology:

Along with the increase of aluminum products demand; cause the container of dress metal aluminium liquid, aluminum alloy melt, liquid aluminium transport pipe and thermometric protective casing etc. to increase by the waste of material, the material obtaining the more excellent corrosion of resistance to aluminium has very important engineer applied and is worth 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 comparatively early, be that the composite ceramic material of matrix has high rigidity, the excellent properties such as high temperature resistant, wear-resistant, corrosion-resistant with aluminum oxide, be 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 researcher studies always.Investigation of materials person is by adding in alumina matrix material by metal, the brittleness problems of alumina substrate is obtained improve significantly, large quantity research report shows, while improving alumina material toughness, often with the raising of its cost, the preparation cost therefore how reducing 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, be toughened and reinforced interpolation phase with Al-Ti-B intermediate alloy, rare metal, prepare by the following method: (1) in common intermediate frequency induction furnace 1000 ~ 1300 DEG C, titanium valve and boron powder are added 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%, titanium 3.0 ~ 7.0%, and aluminium is surplus; (2), using alumina-ceramic as body material, be toughened and reinforced interpolation phase with Al-Ti-B intermediate alloy, rare metal, take raw material according to the mass percent of aluminum oxide 86% ~ 95%, Al-Ti-B intermediate alloy 3% ~ 8%, rare metal 2% ~ 6%; (3) the raw material mixing that will weigh up take ethanol as medium Intensive ball mill after 100 ~ 120 hours, places vacuum drying oven dry and cross 200 mesh sieves, obtained Homogeneous phase mixing powder; (4) adopt hot-pressing sintering technique, using nitrogen as sintering atmosphere, sintering temperature 1480 ~ 1580 DEG C, sintering pressure 28 ~ 35MPa, soaking time 25 ~ 35 minutes, can prepare the alumina ceramic composite material of high tenacity, high strength.

Ceramic-metal composites feature is combined with advantage such as good toughness and the bending strength etc. of metal as high temperature resistant, high strength and oxidation-resistance etc. at the advantage of pottery, obtains a kind of material with good over-all properties; In addition, metallographic phase add the sintering character and 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 DEG C to obtain.Because the densification process of pottery is more difficult, so the material density finally obtained is about 95%, the requirement of stupalith to equipment and process wanting to obtain high-compactness (> 98%) is high.Current B4C pottery ultimate compression strength that can be obtained is 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 the density of pottery, density then with sintering temperature, soaking time and moulding pressure closely related, therefore high performance dense ceramic material to be obtained owing to all requiring very high to molding device and technological 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, therefore, the application of shape of its product is also greatly limited.Require high for ceramic preparation, fragility large and not easily mach shortcoming develop B4C/Al cermet material technology prepared by pressure-free impregnation.Adopt and prepare ceramic skeleton relative to lower sintering temperature (about 2000 DEG C) closely knit sintering, reduce the requirement to equipment, decrease preparation time; And adding of metallic aluminium can improve ceramic toughness.Metallic aluminium is selected to be because the similar density of norbide and aluminium, and the ductility of fine aluminium, more flowability, can in the space at a certain temperature by capillary attraction automatic infiltration infiltration norbide skeleton, without the need to Additional pressurizations again.And adding of aluminium makes the cermet product of final molding have electroconductibility, wire cutting machine can be utilized to be processed into any desired shape.Research at present for B4C/Al obtains the sintering temperature (sintering between 1900 DEG C ~ 2000 DEG C) that larger progress is reduction of pottery, the bending strength of stupalith is brought up between 300GPa ~ 600GPa by adding of aluminium, 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 but reduce its hardness (between HV900 ~ 1050) and ultimate compression strength (1.2GPa ~ 1.5GPa) accordingly, and performance is by comparatively large (the wherein porosity of ceramic skeleton of impact of metal aluminum amount, the fluidity determining of the metallic aluminium number of metal aluminum 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: with doped silicon carbide ceramic powder and boron carbide powder for ceramic material, is that doped silicon carbide ceramic powder and the surplus boron carbide powder of 5 ~ 50% adds three-dimensional planetary mixed powder machine and carry out mixed powder by mass percent, add in ceramic material after mixing mass concentration be 4% binding agent PVA and mixing granulation, the add-on of binding agent PVA is 2 ~ 10% of ceramic material total mass, after granulation, then 24 ~ 60 mesh sieve are adopted to sieve, leave standstill and again institute's granulation is placed in cast iron die extrusion forming after 12 hours, obtain precast billet, molding pressure is 50 ~ 120MPa, pressurize 30 ~ 150s, (2) pressureless sintering: precast billet is placed in vacuum sintering furnace, vacuumize, vacuum is 10-2Pa, 1600 ~ 1900 DEG C of sintering are warming up to 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 ceramic metal, (4) thermal treatment: ceramic metal is placed in heat treatment furnace, and be heated to 650 ~ 900 DEG C of temperature, take out after insulation 8 ~ 24h, and be placed in water and do quench treatment.

The heterogeneous composite material that cermet material is made up of one or more ceramic phases and metal or alloy.Heat resistant type can be divided into, wear-resistant type and corrosion resistant type etc. by character and utilization.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; Be metallurgical binding between described low alloy steel and sintering metal, there is diffusion and dissolve each other district between the Binder Phase metal at bonding interface place and described low alloy steel, diffusion is dissolved each other and be there is the gradient transitional lay of hard particles phase in district; Described Binder Phase metal is nickel-based self-fluxing alloy, and the SHS process that described titanium carbide is caused when casting described low alloy steel by the titanium in SHS process reaction system and carbon reacts and generates; It consists of described SHS process reaction 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 to have the very strong corrosion of resistance to aluminium ability, its fragility is large, and especially very easily ftractureing at the working condition of hot and cold alternation limits its use.Metal and ceramic composite effectively can improve the fragility of single stupalith, and overall strong, toughness are improved, and the material not only having had excellent strength-toughness for preparation but also had the high corrosion of a resistance to aluminium performance improves 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.

The purity > of described Ti powder and Ni powder 97.9%, granularity < 20 micron.

The purity > of described AlN powder and Al2O3 powder 97.9%, granularity < 50 micron.

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:

Invention increases the compactness of ceramic-metal composite, thus improve the corrosion resistance nature of ceramic-metal composite, improve the work-ing life of cermet material, the corrosion resistance nature of this material in aluminium liquid has very important engineer applied and is worth simultaneously.

Accompanying drawing illustrates:

Fig. 1 is the scanning electron microscopy macrograph of cermet material of the present invention.

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 one: see 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: mixing and ball milling of (1) preparing burden: load ball mill after first Ti powder and Ni powder being weighed according to weight percent, the purity of described Ti powder and Ni powder is 99.9%, granularity < 20 microns, material: ball weight is than being 1:2, argon shield is filled with in ball mill, start ball milling, Ball-milling Time is 8 hours, secondly in ball mill, Al2O3 powder and AlN powder is added according to per-cent, the purity of described AlN powder and Al2O3 powder is 99.9%, granularity < 50 microns, and according to compound: ball weight carries out secondary ball milling than 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 mixes, and all particle sizes are more and more tiny, (2) pulverize drying: the Ti powder, Ni powder, Al2O3 powder and the AlN powder that mix after ball milling taken out, and dry at 110 DEG C, grind, (3) press forming: be filled in graphite jig by above-mentioned powder mix, is put in blank baby press being pressed into desired shape, (4) sinter: electric field-activate hot pressing assisted sintering is carried out to above-mentioned blank, the vacuum sintering under argon atmosphere of described sintering, in heating, insulating process, 60MPa pressure is applied to blank, described vacuum tightness 10Pa, sintering temperature is 1150 DEG C, soaking time is 5 ~ 10 minutes, and the rear furnace cooling of sintering is 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, and comparatively other metallic substance such as corrosion resistance nature such as stainless steel, cast iron significantly improves.

The present invention's corrosion of resistance to aluminium cermet material sample drainage test density is 99.5%.The present invention's corrosion of resistance to aluminium cermet material sample scans electron microscopic is organized as shown in Figure 1, and the X ray diffracting spectrum of gained cermet specimens as shown in Figure 2.

Two kinds of differing materials corrode the average corrosion rate after 8 hours in 700 DEG C of aluminium liquid, as shown in Table 1.

The corrosion of the resistance to aluminium Performance comparision 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 two: 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: mixing and ball milling of (1) preparing burden: load ball mill after first Ti powder and Ni powder being weighed according to weight percent, the purity of described Ti powder and Ni powder is 99.9%, granularity < 20 microns, material: ball weight is than being 1:2, argon shield is filled with in ball mill, start ball milling, Ball-milling Time is 8 hours, secondly in ball mill, Al2O3 powder and AlN powder is added according to weight percent, the purity of described AlN powder and Al2O3 powder is 99.9%, granularity < 50 microns, and according to compound: ball weight carries out secondary ball milling than for 1:2, and Ball-milling Time is 12 hours, (2) pulverize drying: the Ti powder, Ni powder, Al2O3 powder and the AlN powder that mix after ball milling taken out, and dry at 120 DEG C, grind, (3) press forming: be filled in graphite jig by above-mentioned powder mix, is put in blank baby press being pressed into desired shape, (4) sinter: electric field-activate hot pressing assisted sintering is carried out to above-mentioned blank, the vacuum sintering under argon atmosphere of described sintering, in heating, insulating process, 60MPa pressure is applied to blank, described vacuum tightness 10Pa, sintering temperature is 1100 DEG C, soaking time is 5 ~ 10 minutes, and the rear furnace cooling less than 100 DEG C of sintering is come out of the stove, the demoulding.

The present invention's corrosion of resistance to aluminium cermet material sample drainage test density is 99.6%.

Two kinds of differing materials corrode the average corrosion rate after 8 hours in 700 DEG C of aluminium liquid, as shown in Table 2.

The corrosion of the resistance to aluminium Performance comparision of table two two kinds of differing materials

	Cermet material of the present invention	Cast iron
			Average corrosion rate (mm/h)	5.2Х10-4	8.5Х10-1

Embodiment three: 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: mixing and ball milling of (1) preparing burden: first Ti powder and Ni powder are loaded ball mill according to after weight percent, the purity of described Ti powder and Ni powder is 99.9%, granularity < 20 microns, material: ball weight is than being 1:2, argon shield is filled with in ball mill, start ball milling, Ball-milling Time is 8 hours, secondly in ball mill, Al2O3 powder and AlN powder is added according to weight percent, the purity of described AlN powder and Al2O3 powder is 99.9%, granularity < 50 microns, and according to compound: ball weight carries out secondary ball milling than for 1:2, and Ball-milling Time is 10 hours, (2) pulverize drying: the Ti powder, Ni powder, Al2O3 powder and the AlN powder that mix after ball milling taken out, and dry at 120 DEG C, grind, (3) press forming: be filled in graphite jig by above-mentioned powder mix, is put in blank baby press being pressed into desired shape, (4) sinter: electric field-activate hot pressing assisted sintering is carried out to above-mentioned blank, the vacuum sintering under argon atmosphere of described sintering, in heating, insulating process, 60MPa pressure is applied to blank, described vacuum tightness 10Pa, sintering temperature is 1100 DEG C, soaking time is 5 ~ 10 minutes, and the rear furnace cooling less than 100 DEG C of sintering is come out of the stove, the demoulding.

The present invention's corrosion of resistance to aluminium cermet material sample drainage test density is 99.7%.

Two kinds of differing materials corrode the average corrosion rate after 8 hours in 700 DEG C of aluminium liquid, as shown in Table 3.

The corrosion of the resistance to aluminium Performance comparision of table three two kinds of differing materials

	Cermet material of the present invention	Cast iron
			Average corrosion rate (mm/h)	6.7Х10 ^-4	8.5Х10 ^-1

There is the raising of larger amplitude more than cast iron by the cermet material corrosion of the resistance to aluminium performance obtained in embodiment one, two, three.In addition, corrosion resisting property corresponding when 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 do not depart from technical solution of the present invention interior perhaps above scheme is done according to technical spirit of the present invention any simple modification, equivalent variations and modification, all still belong within scope.

Claims

1. the corrosion of resistance to aluminium cermet material, is characterized in that: comprise Ti powder, Ni powder, Al ₂o ₃powder and AlN powder, weight percent is 1-5%Ti, 10-25%Ni, 40-60%Al ₂o ₃, 20-40%AlN, the purity > of described Ti powder and Ni powder 97.9%, granularity < 20 micron, described AlN powder and Al ₂o ₃the purity > of powder 97.9%, granularity < 50 micron, described Ti powder, Ni powder, Al ₂o ₃powder 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, Ni powder, Al ₂o ₃the purity > 99.9% of powder and AlN powder.