CN1060531C

CN1060531C - Method for preparation of composite ceramic-Ni-Al intermetallic material

Info

Publication number: CN1060531C
Application number: CN98101296A
Authority: CN
Inventors: 韩光炜; 冯涤; 殷明
Original assignee: Central Iron and Steel Research Institute
Current assignee: Central Iron and Steel Research Institute
Priority date: 1998-04-21
Filing date: 1998-04-21
Publication date: 2001-01-10
Anticipated expiration: 2018-04-21
Also published as: CN1199102A

Abstract

The present invention belongs to the field of manufacturing a metal ceramic composite material, particularly to a preparation method suitable for an in-situ near termination ceramic/Ni3Al composite material. In the method of the present invention, ceramic powder and nickel alloy powder with a certain granularity are mixed with an adhesive for casting and molding; after the adhesive is removed, the powder is sintered in a vacuum furnace, and carries out calorizing reaction in liquid aluminium; finally, a ceramic/Ni3Al composite material with good toughness and high intensity is obtained by high-temperature homogenization processing. Compared with the prior art, the preparation method has the advantages of simple fabrication process and convenient operation. Particularly, the preparation method has an obviously superior effect on near termination molding of a component with a large size and a complicated shape.

Description

The preparation method of pottery-intermetallic Ni-Al compound matrix material

The invention belongs to the manufacturing field of ceramic-metal composite.Be specially adapted to the nearly end form pottery/Ni of original position ₃The preparation method of Al matrix material.

Has in the high-temperature material of development prospect intermetallic compound Ni in the prior art ₃Al possesses unusual yield strength-temperature effective, and very high wear-resistant and corrosion resistance nature.If adopt the Ni of boracic malleableize ₃Al alloy network is as the toughness phase in the pottery, the pottery/Ni that develops like this ₃The Al matrix material will have more wide application prospect in the high-temperature structural material field.At present both at home and abroad to adopting Ni ₃Al also reports to some extent as the production method that tough cohesive prepares ceramic composite mutually.For example a kind of method is to adopt powder metallurgical technique (Materials Science and EngineeringA209 (1996) 243), and this preparation technology is with a certain amount of Ni ₃Al powdered alloy and ceramic powder (Al ₂O ₃, WC, TiC etc.) behind the uniform mixing, hot compacting under 1300 ℃ of-1500 ℃ of high temperature, and form pottery/Ni ₃Al matrix material, the shortcoming of this method are the technological operation complexity, and large size and complex-shaped member just are difficult to realize that having is exactly the pottery/Ni that adopts this method preparation again ₃Ni in the Al matrix material ₃Al toughness is easy to form the arc island mutually, and its performance is obviously reduced.This explained hereafter cost is higher in addition.Another prepares pottery/Ni ₃The production method of Al matrix material is to adopt (to be higher than Ni under the pyroprocessing condition ₃1390 ℃ of the fusing points of Al) make liquid Ni ₃Al infiltrates pottery to be strengthened in the batch mixing of body.(Adv．Iudus，Mater，Prog．Ann．Prog，Rep，ORNL，TM2763，(1994)252)。The shortcoming of this method is because liquid Ni ₃Al infiltration temperature is too high, and operation is difficult to support and holds.In addition, ceramic phase is not linked to be network, makes composite material rigidity low.

The objective of the invention is to propose a kind ofly have operating procedure simply, economically and reasonably, and be not subjected to the nearly end form pottery/Ni of original position of product size, shape restriction ₃The preparation method of Al matrix material.

The inventive method is to adopt at ceramic size or in ceramic powder to stir behind a certain amount of nickel powder of adding, adopt traditional ceramics forming technology (slurry casting or cold-press moulding) to prepare the ceramics preparative blank again, again this prefabricated component is obtained having the ceramics preparative spare of three-dimensional communication hole behind the sintering in High Temperature Furnaces Heating Apparatus, and then this ceramics preparative spare is immersed in the crucible of liquid aluminium, generate the Ni of intermetallic compound by nickel in the ceramics preparative spare and aluminium generation thermopositive reaction ₃Al (volumetric shrinkage) makes liquid aluminium constantly penetrate into connected holes in the ceramics preparative spare under the reaction pressure effect, and continues reaction and form the Ni that is communicated with nickel in the ceramics preparative spare ₃The Al network.Then product is taken out to be cooled to and carry out a homogenizing after the room temperature again and handle and just obtain even pottery/Ni ₃The Al matrix material.According to purpose of the present invention, pottery/Ni that we proposed ₃The preparation method of Al intermetallic compound composite material prepares the sintering processes of carrying out different systems after powder and binding agent uniform mixing, the moulding again by planner's composition requirement, it is characterized in that batching, be mixed and moulding with organic binder bond after should getting the nickelalloy powder uniform mixing of ceramic powder that granularity is 0.2-60 μ m and granularity 5-40 μ m, available slurry casting method is made ceramics preparative green bodies when powder is made slurry in emulsion hydrosol after again.Also can with the powder that is mixed and paraffin wax or resin aqueous solution be cold-pressed into prefabricated blank after being mixed.Then prefabricated blank being put into 200 ℃-400 ℃ anti-oxidation gas heating stove is incubated 1-2 hours and sloughs binding agent.The prefabricated component that to slough binding agent again puts into that vacuum tightness is not less than the 2.7Pa vacuum oven or an oxygen-proof property institute part stove carries out high temperature sintering, sintering temperature is that the aluminum melt that the prefabricated component behind 1150 ℃-1350 ℃, sintering should be put into oxygen-proof property gas again carries out the aluminising reaction, the temperature of aluminising reaction is 850 ℃-1000 ℃, soaking time is 0.5-10 hours, aluminising finishes back taking-up prefabricated component and is cooled to room temperature, and then with prefabricated component in 1100 ℃-1250 ℃, be incubated 5-10 hours and carry out the homogenizing processing, just can obtain pottery/Ni ₃The matrix material of Al.At pottery/Ni of the present invention ₃In the Al composite material and preparation method thereof, it is 0.5-30 μ m that other feature also includes the better size range of ceramic powder.The better size range of nickelalloy powder is 10-20 μ m.The optimum treatment temperature that removes tackiness agent is 200 ℃-300 ℃, is incubated 2 hours.The high temperature sintering optimum treatmenting temperature of prefabricated component is 1250 ℃-1350 ℃, is incubated 2 hours.The aluminising optimum temps is 850 ℃-950 ℃, is incubated 2-4 hours.Remove the protection of binding agent and aluminising processing optimal gas and should adopt rare gas element.1200 ℃-1250 ℃ of the optimum tempss that homogenizing is handled are incubated 5-10 hours.The ceramic powder that is proposed is meant SiC, Al in the method for the invention ₂O ₃, ceramics powder such as WC.The nickelalloy powder that is proposed in the methods of the invention is meant nickel content in the nickel alloy powder more than 95%, can also include boron or other element below 0.2% in nickel alloy powder.In the method for the invention, as the proportion of ceramic enhancement phase and volume fraction and toughness Ni mutually ₃After the weight % content of nickel alloy powder was determined in the Al alloy, it importantly adopted this method can make the nickel alloy powder in the ceramics preparative spare want to generate Ni with the liquid aluminium generation thermopositive reaction of being infiltrated fully ₃Al, and make the Ni that is generated ₃All be full of the volume that original nickel alloy powder is occupied in connected holes in the prefabricated component and the prefabricated component after Al solidifies, reach the good pottery/Ni of strength high toughness ₃The Al intermetallic compound composite material.

Adopt the inventive method compared with prior art, it is simpler than powder metallurgy process technology to have a prepared matrix material of this method.Economical and easy to operate, especially more obvious superior to large size and complex-shaped member near-net forming.Adopt this method to prepare matrix material, Ni in addition ₃The Al malleableize can not form the arc island mutually, but is the contiguous network shape.

Embodiment

According to pottery/Ni of the present invention ₃The preparation method of Al intermetallic compound composite material, we have done following 6 groups of tests altogether and have compared, and the technical parameter of its test and performance are listed in respectively in the following table, and wherein table 1 is the preparation technology parameter contrast table of nickel-containing alloys powder ceramics preparative spare.Table 2 is pottery/Ni ₃The preparation technology of Al intermetallic compound composite material and performance comparison table.

Table 1 contains the preparation technology parameter contrast table of Ni alloy powder ceramics preparative

Sequence number	Raw material	Granularity (μ m)	Ceramics powder/Ni powder weight ratio	Binding agent	Forming method	Forming pressure (Mpa)	Preform sizes (mm)	Remove the technology of binding agent			Sintering condition
								Remove the technology of binding agent			Sintering condition			Temperature (℃)	Time (h)	Gas part	Temperature (℃)	Time (h)	Environment
								1	WC／Ni	20／10	12．9	The 4vol% emulsion hydrosol	Cold pressing	Temperature (℃)	Time (h)	Gas part	Temperature (℃)	Time (h)	Environment	35	8×10×50	200	2．0	H ₂	1350	2	Vacuum
2	SiC／Ni	50／20	1．85	Paraffin wax	Cold pressing	50	8×10×50	1	WC／Ni	20／10	12．9	The 4vol% emulsion hydrosol	Cold pressing	250	1．5	Ar	1250	2	Ar	35	8×10×50	200	2．0	H ₂	1350	2	Vacuum
2	SiC／Ni	50／20	1．85	Paraffin wax	Cold pressing	50	8×10×50	3	SiC／Ni	25／35	3．3	The 3.0vol% resin	Cast	250	1．5	Ar	1250	2	Ar	／	φ1．5×50	350	1．5	H ₂	1250	3．5	Vacuum
4	Al ₂O ₃／Ni	0．5／10	3．0	Paraffin wax	Cold pressing	50	8×10×50	3	SiC／Ni	25／35	3．3	The 3.0vol% resin	Cast	250	2．0	Ar	1300	2	Vacuum	／	φ1．5×50	350	1．5	H ₂	1250	3．5	Vacuum
4	Al ₂O ₃／Ni	0．5／10	3．0	Paraffin wax	Cold pressing	50	8×10×50	5	Al ₂O ₃／Ni	2．0／5	11．5	Paraffin wax	Cold pressing	250	2．0	Ar	1300	2	Vacuum	40	8×10×50	250	2．5	H ₂	1350	2	Vacuum
6	WC／Ni	10／10	1．6	The 8vol% emulsion hydrosol	Cast	／	10×10×55	5	Al ₂O ₃／Ni	2．0／5	11．5	Paraffin wax	Cold pressing	250	2	H ₂	1200	3	Ar	40	8×10×50	250	2．5	H ₂	1350	2	Vacuum

Table 2 pottery/Ni ₃The preparation technology of Al intermetallic compound composite material and performance comparison table

Sequence number	Temperature in the prefabricated component immersion aluminium liquid (℃)	Shielding gas	The aluminising reaction process		Be chilled to	Homogenization process		The finished product tissue	End properties
		Shielding gas	The aluminising reaction process			Homogenization process			End properties		Gas	Temperature ℃	Time h	Temperature ℃	Time h	Fracture toughness property Mpa m ^1／2	Hardness GPa
		1	750	Ar		900	2．5		Room temperature	1250	Gas	Temperature ℃	Time h	Temperature ℃	Time h	Fracture toughness property Mpa m ^1／2	Hardness GPa	5	Evenly	15	14
2	800	1	750	Ar	N ₂	900	2．5	950	Room temperature	1250	2．0	Room temperature	1200	8	Evenly	10．8	10．3	5	Evenly	15	14
2	800	3	750	N ₂	N ₂	900	3．0	950	Room temperature	1250	2．0	Room temperature	1200	8	Evenly	10．8	10．3	4	Evenly	8．5	12．6
4	800	3	750	N ₂	Ar	900	3．0	950	Room temperature	1250	2．5	Room temperature	1200	9	Evenly	10．2	10．5	4	Evenly	8．5	12．6
4	800	5	780	N ₂	Ar	1000	2．0	950	Room temperature	1250	2．5	Room temperature	1200	9	Evenly	10．2	10．5	6	Evenly	16．7	12．9
6	800	5	780	N ₂	N ₂	1000	2．0	850	Room temperature	1250	4．5	Room temperature	1150	12	Evenly	12．6	9．6	6	Evenly	16．7	12．9

Claims

1, a kind of pottery/Ni ₃The preparation method of Al intermetallic compound composite material, this method are that powder and the binding agent through preparation mixes, carry out the sintering processes of different systems after the moulding again, it is characterized in that preparing burden and get the SiC that granularity is 0.2-60 μ m, Al ₂O ₃Among the WC any one ceramic powder and granularity be 5-40 μ m content less than 1%B and greater than behind the nickelalloy powder uniform mixing of 99%Ni again with emulsion hydrosol, paraffin wax, in the resin glue any one is mixed and moulding, then, the prefabricated component base being put into anti-oxidation gas part process furnace of 200 ℃-400 ℃ is incubated 1-2 hours and removes above-mentioned binding agent again, the prefabricated component that will remove binding agent is again put into the vacuum oven that vacuum tightness is not less than 2.7Pa and is carried out high temperature sintering, its sintering temperature is 1150 ℃-1350 ℃, be incubated 2-4 hours, the aluminum melt that prefabricated component after vacuum high-temperature sintering is handled should be put into oxygen-proof property gas again carries out the aluminising reaction, the aluminising temperature of reaction is 850 ℃-1000 ℃, be incubated 0.5-10 hours, aluminising finishes back taking-up prefabricated component and is cooled to room temperature, carrying out homogenizing at last handles, the homogenizing treatment temp is 1100 ℃-1250 ℃, and soaking time is 5-10 hours.

2, according to the described method of claim 1, it is characterized in that high temperature sintering is handled also can carry out in oxygen-proof property gas part stove.

3, according to the described method of claim 1, the size range that it is characterized in that ceramic powder is 0.5-30 μ m.

4, according to the described method of claim 1, the size range that it is characterized in that the nickelalloy powder is 10-20 μ m.

5, according to the described method of claim 1, the thermal treatment temp that it is characterized in that removing tackiness agent is 200 ℃-300 ℃, is incubated 2 hours.

6, according to the described method of claim 1, the high temperature sintering treatment temp that it is characterized in that prefabricated component is 1250 ℃-1350 ℃, is incubated 2 hours.

7,, it is characterized in that the aluminising temperature is 850 ℃-950 ℃, is incubated 2-4 hours according to the described method of claim 1.

8, according to the described method of claim 1, it is characterized in that the temperature that homogenizing is handled is 1200 ℃-1250 ℃, be incubated 5-10 hours.

9,, it is characterized in that removing the gas shield that binding agent and aluminising handle and to adopt protection of inert gas according to claim 1,5,7 described methods.