A kind of ceramic-metal composite and preparation method thereof
Technical field
The present invention relates to ceramic-metal composite, ceramic-metal composite of particularly a kind of high rigidity, high-wearing feature and preparation method thereof.
Background technology
Ceramic-metal composite is classified according to the difference of ceramic phase.Be divided into oxide compound-metal composite, carbide-metal composite, nitride-metal composite, boride-metal composite, boron carbide-metal composite material and silicide-metal composite.It is numerous in variety, and structure is different, all with its different intensity, hardness, wear-resisting and antioxidant property, has a wide range of applications at aspects such as electron device, metallurgy, chemical industry, aerospace.
Ti (C, N)/Al
2O
3Sintering metal not only have higher hardness, wear resistance, red hardness, excellent chemical stability, with the low frictional coefficient of metal compole, and also have certain toughness and intensity.Compare with common Wimet, it has remarkable advantages in the following aspects: higher cutting speed is arranged; Workpiece to be machined has surface property preferably; Wear resisting property is higher.But (C, N) powder very expensive (700,000 yuan/ton) hinders its widespread use to commercially produce one of the raw material Ti of this type of material at present.
And the ilmenite resource reserve is big, and it is wide, almost all over the world to distribute.According to U.S. Department of Mines " mineral products summary " statistical information of nineteen ninety-five, the existing explored ilmenite resource reserve in the world is 20,700,000,000 tons, mainly is distributed in Canada, Norway, South Africa, Australia, the U.S., India, the former Soviet Union, Sri Lanka, Brazil, states such as Finland, wherein, the reserves maximum in South Africa accounts for 23.4% of world's total reserves.The ilmenite resource of China is very abundant, spreads all over 20 provinces and regions, and also there is placer in existing rock ore deposit, and wherein, the rock ore deposit accounts for major part.The total reserves of China's titanium iron ore is about 3,000 ten thousand tons, and at present, the aggregated capacity of China's titanium iron ore is 300,000 tons/year, and by this calculating, ilmenite also can be exploited 100 years.At present, the main approach that utilizes of ilmenite has the following aspects: (1) produces the solubility in acid titanium slag with concentrated ilmenite with electric furnace smelting process, is used for sulfate process titanium dioxide production then; (2) concentrated ilmenite becomes titanium slag (TiO through the enrichment processing
2More than 90%) or artificial rutile (TiO
2More than 96%) afterwards, adopt fluidizing chlorination or fused salt chlorimation legal system to get TiCl
4(3) be used for the production of titanium sponge.The method of comprehensive utilization of above-mentioned ilmenite exist otherwise energy consumption too high, or the comprehensive utilization degree of iron is low, or problem such as the spent acid mother liquor is difficult, has influenced the efficient that ilmenite utilizes and the industrialization process of ilmenite.For this reason, the approach that utilizes of the new ilmenite of development is very urgent and necessary thing.
Summary of the invention
Given this, the purpose of this invention is to provide low, the applied range of a kind of cost; And improve the alumina ceramic composite material of ilmenite utilising efficiency.
Another object of the present invention provides a kind of simple, easy handling of technological process that is suitable for industrial application, is fit to the alumina ceramic composite material preparation method that the different shape the part with complicated structure is produced.
The object of the present invention is achieved like this: a kind of alumina ceramic composite material is characterized in that, with Al
2O
3Pottery is a matrix, and Ti (C, N) ceramic hard particle and Fe metal are as the ceramic-metal composite of disperse phase; Wherein, body of material composition quality degree is: Al
2O
3: 50~70%; Ti (C, N): 20~30%; Fe: 5~20%; Impurity surpluses such as inevitable Mn, Si, Ca.
Further, its body material is ilmenite powder, aluminium powder and Graphite Powder 99, and proportioning satisfies following formula:
FeTiO
3+ xAl+ (4-3x/2) C+yFe+ (x/2) N
2→ Ti (C, N)+(x/2) Al
2O
3+ (y+1) Fe+CO, wherein, (0<x<2.7,0≤y≤2);
The preparation method of alumina ceramic composite material of the present invention is characterized in that, comprises the steps:
The first step is even, dry with raw material ilmenite powder, aluminium powder and Graphite Powder 99 and ball-milling medium, tensio-active agent (binding agent) mixing and ball milling;
In second step, the mixed powder after the first step handled adds in the hot pressing furnace, under nitrogen atmosphere according to the mold shape hot compacting.
The significant parameter of described ball milling is: ratio of grinding media to material 24: 1~12: 1; Ball milling time 4~10h; Rotating speed 300~500r/min;
Hot pressing parameters: 1200~1500 ℃ of sintering temperatures; Sintering time: 15min~2h; Pressure: 10~50MPa.
Compared to existing technology, the present invention has following advantage:
1. main raw material adopts China to be rich in resource and with low cost, and energy is the main body composition of efficent use of resources fully, and has opened up new way for China is rich in fully effective utilization of resource.
2. original position is synthetic, interface bond strength height, excellent property.Matrix material of the present invention is compared similar ceramic-metal composite and is had suitable good comprehensive mechanical properties and good performances such as wear-resistant, corrosion-resistant, anti-oxidant and anti-thermal shock.Ceramic-metal composite vickers hardness number of the present invention reaches 17~19GPa, and bending strength reaches 320~370MPa.
3. technology is simple.The present invention utilizes traditional hot-pressing sintering technique, selects the abundant Flos Bombacis Malabarici ilmenite (FeTiO of China's reserves
3) as raw material, adding aluminium powder and Graphite Powder 99, hot pressed sintering can directly be prepared the Al of excellent property behind the ball mill mixing
2O
3/ Ti (C, N)/the Fe ceramic-metal composite.Used preparation method's equipment is conventional general-purpose equipment, and technological process is simple, easy handling.
Description of drawings
Fig. 1 is that the typical gold of embodiments of the invention 1 ceramic-metal composite is as microstructure picture;
Fig. 2 is the typical scan backscattered electron microphotograph of ceramic-metal composite of the present invention.
Embodiment
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1:
A kind of preparation technology of ceramic-metal composite, its concrete steps are as follows:
(1) molar ratio by FeTiO3+2Al+C+0Fe takes by weighing ilmenite powder 49.91 grams, aluminium powder 17.72 grams, graphite 3.94 grams on electronic balance.
(2) powder mix is poured in the ball grinder into ratio of grinding media to material 12: 1, ball milling 4 hours; Then, the powder behind the ball milling is put into the moisture eliminator drying.
(3) the compound hot pressing graphite jig of packing into, put into hot pressing furnace, vacuumize the logical nitrogen protection in back.
(4) first precompressed powder once waits pressurization 21Mpa when arriving 1400 ℃ then in the process that heats up.
(5) be incubated 30min under 1400 ℃ of pressurization 21MPa, cooling at last obtains ceramic-metal composite A.
The mechanical property of the composite A that (6) obtains is as shown in table 1, and chemical composition analysis is as shown in table 2, and the typical gold of its ceramic-metal composite as microstructure as shown in Figure 1 and Figure 2.
Embodiment 2
A kind of preparation method of ceramic-metal composite utilizes the preparation of ball grinding technique and hot-pressing technique, and its step is as follows:
(1) starting material are ilmenite powder, aluminium powder, graphite and iron powder.Molar ratio by FeTiO3+2Al+C+1Fe on electronic balance takes by weighing ilmenite powder 39.71 grams, aluminium powder 14.11 grams, graphite 3.13 grams, iron powder 14.63 grams.
(2) powder mix is poured in the ball grinder, ratio of grinding media to material 12: 1, ball milling 4 hours is put into the moisture eliminator drying with the powder behind the ball milling then.
(3) the compound hot pressing graphite jig of packing into, put into hot pressing furnace, vacuumize the logical nitrogen protection in back;
(4) first precompressed powder once waits pressurization 21MPa when arriving 1200 ℃ then in the process that heats up;
(5) be incubated 30min under 1200 ℃ of pressurization 21MPa, cooling at last obtains ceramic-metal composite B.
(6) mechanical property of the matrix material B that obtains is as shown in table 1, and chemical composition analysis is as shown in table 2.
The mechanical property of table 1 ceramic-metal composite
(vickers hardness number Hv20, bending strength σ av, fracture toughness property Kic)
Material |
??Hv20 |
??σav(Mpa) |
??Kic(Mpa*M(1/2)) |
??A |
??1779 |
??339 |
??5.32 |
??B |
??1826 |
??260 |
??5.57 |
The composition of table 2 ceramic-metal composite
Material |
??Al
2O
3 |
??Ti(C,N) |
??Fe |
??A |
??60.05 |
??28.59 |
??10.80 |
??B |
??62.35 |
??25.77 |
??11.17 |
Ceramic-metal composite of the present invention, belonging to Ti (C, N) is a kind of continuous solid solution Ti (C that TiC and TiN form
1-x, N
x).Ti (C
1-x, N
x) performance change to some extent with the change of x.TiC hardness is higher, and TiN toughness is better, in general, reduces with the hardness of the increase material of x value, and toughness improves.Ti (C, N) sintering metal not only have higher hardness, wear resistance, red hardness, excellent chemical stability, with the low frictional coefficient of metal compole, and also have certain toughness and intensity.Compare with common Wimet, it has remarkable advantages in the following aspects: higher cutting speed is arranged; Workpiece to be machined has surface property preferably; Wear resisting property is higher.Ti (C, N) sintering metal has good use properties, compare with the WC base cemented carbide, demonstrate higher red hardness, close intensity, lower corrodibility, thermal conductivity and frictional coefficient in the processing, have the higher life-span or can adopt higher cutting speed under identical situation of life-span, work piece has surface smoothness preferably.Therefore, (C, N) sintering metal can successfully replace the WC base cemented carbide to Ti under many processing occasions, has filled up WC base hard Ti (C, N) blank between alloy and the pottery.
Titanium carbonitride is a kind of excellent property, and broad-spectrum non-oxide ceramic material has the advantage of TiC and TiN concurrently, has high-melting-point, high rigidity, wear-resisting, resistance to oxidation, characteristic such as corrosion-resistant, and having good thermal conductivity, electroconductibility and chemical stability are at machinery, chemical industry, many fields such as automobile making and aerospace are widely used.
The present invention is in conjunction with the china natural resources characteristics, select China's reserves abundant, the Flos Bombacis Malabarici that includes Fe and two kinds of main elements of Ti produces ilmenite (FeTiO3) as raw material (~1000 yuan/ton), by heat pressing process prepare a kind of novel Al203/Ti (C, N)/the Fe sintering metal.This matrix material made full use of two kinds of main elements in the ilmenite, and technological process is simple because raw materials cost is cheap, and excellent property has great application value and vast market prospect.Therefore, the present invention is for the effective utilization that promotes the China's titanium iron ore deposit, and the development of quickening China's sintering metal and metal-base composites has very important significance.