CN108754206A - A method of manufacture ceramics and metallic composite - Google Patents

Abstract

The invention discloses a kind of method of manufacture ceramics and metallic composite, the composite material of this kind of low-gravity high-compactness can be used for manufacturing light armoring and other engineer applications for having the performance and weight of material rigors.Method includes：Material powder that a kind of or plural kind can form carbide is uniformly mixed with the carbide ceramic powder of a kind of or plural kind of infusibility and the substance of carbon or a kind of or multiple several carbonaceous, mixture is molded at ambient temperature, obtained periporate base is in single carbonaceous gas or the atmosphere being made of the mixing of a variety of carbonaceous gas, it is heat-treated at 600-1200 DEG C, the carbon for making carbonaceous gas decompose and generating, is deposited on inside and outside porous powder base；Powder base containing enough equivalent carbon is heat-treated at 1100-2000 DEG C, powder base is made to form a continuous carbide ceramics skeleton.So that molten metal or alloy is penetrated into ceramic skeleton finally by infiltrating method, obtains fine and close composite material.

Description

A method of manufacture ceramics and metallic composite

Technical field

The invention and manufacture low-gravity, fine and close ceramics and metal, ceramics are related with ceramic composite and its technique.More Precisely, with manufacture low-gravity, the method for the light metals composite material such as carbide and aluminium, magnesium of high-compactness and thus just Method and the product that manufactures is related.The composite material of the carbide and light metal of this kind of low-gravity high-compactness, can be used for Manufacture light armoring and other engineer applications for there are rigors to the performance and weight of material.

Background technology

It is a kind of general to manufacture carbide structure material using the substance and carbon chemically reactive that can form carbide Logical PM technique.United States Patent (USP) 3725105 proposes following methods：(1) carbide powder is molded；It (2) will be carbon containing Penetration carbide green body；(3) heating makes carbonaceous material be transformed into free carbon；(4) metallic silicon or silicon alloy are penetrated into In carbide green body containing free carbon；(5) heat-agglomerating, to obtain the compound of carbide and silicon carbide and a small amount of metallic silicon Material.

United States Patent (USP) 4097275 and 4326922 is proposed powder base and hydrocarbon containing carbide-formers matter Atmosphere is reacted, and carbide material is prepared.

United States Patent (USP) 3977896,4080927 and 3944686 proposes respectively to be cracked using hydrocarbon, in powder Grain, body surface and porous internal deposition carbon method.

Russian Patent 2078748, which proposes, cracks hydrocarbon in Carbon deposition to the powder base of crome metal, then high temperature Processing is allowed to reaction and generates porous chromium carbide green body.Then the metals such as copper, silver or gold are penetrated into chromium carbide porous body, from And obtain the composite material of fine and close chromium carbide and metal.European patent PCT/EP97/01566 then improves this, by carbon The range of compound formation element is expanded to titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten, and by the range of metal for infiltration It is expanded to the alloy of silver, gold, copper, gallium, titanium, nickel, iron, cobalt or these metals.European patent PCT/EP00/11025 is in this base It is improved again on plinth, i.e.,：Green body is done by carbide former was used alone in the past, is changed to using at least one carbide shape Green body is done at the mixture of element and at least one carbide.Purpose is the time shortened needed for deposition carbon technique, and makes to sink Long-pending carbon is distributed more uniformly inside and outside powder base.

The above invention has shortcomings：Green body is done using carbide former and carbonaceous material mixture, when heat treatment, Due to the carbide volume change of generation, blank deformation, peeling and cracking are easily caused.Base is made using carbide former Body, in conjunction with cracking Carbon deposition technique, although the problems such as deformation of workpiece can preferably be solved, but carbon is easier to be deposited on The surface layer of workpiece, on powder base different depth, the degree of Carbon deposition is different, to influence the quality and performance of material；And Cracking Carbon deposition technique needs the very long time.Although European patent PCT/EP00/11025 replaces a part of carbon using carbide Compound formation element, to reduce requirement of the carburizing reagent to equivalent carbon, so as to shorten the time needed for cracking carbon technique, but still It so needs strictly to control technological parameter, needs the processing time up to more than ten a hours.

It is to provide a kind of technological means to the mesh of the present invention, to avoid the various disadvantages in the above patented method.It is not only big The big time shortened needed for cracking Carbon deposition technique, and keep distribution of the carbon in powder base more uniform.Simultaneously as powder base The reinforcing of deposition carbon is obtained, reduces the workpiece caused by chemical reaction and deforms, peeling and cracking.Greatly improve production effect Rate improves product quality and performances.

Invention content

Using the chemical reaction of carbide former and carbon come to obtain carbide be a common engineering method.In the past Each addition manner in relation to the be a difference in that carbon of patented method is had nothing in common with each other.It is disposably incorporated enough in batch mixing It carbon or is cracked by hydrocarbon, makes the upper enough carbon of deposition in workpiece.One of core of the invention be in batch mixing, Most of carbon or carbonaceous material is added, remaining small part carbon is then obtained by decomposing carbonaceous gas.It the advantage is that：(1) it splits Carbon deposition is solved in powder base, the bond strength between powder particle in powder base can be reinforced, to make powder base intensity greatly improve. Powder base by reinforcing, in pyroreaction, it is not easy to strain cracking.(2) carbon being added when batch mixing can shorten cracking carbon work Time needed for sequence, and the carbon for making cracking generate faster, is more uniformly deposited in entire workpiece.(3) most of carbon is mixed It is added when material, the carbon of deposition is only used as the adjusting of last total carbon.The difficulty of technology controlling and process can be reduced.

According to the present invention, this process includes the following steps：

1 by can be formed containing a kind of or plural kind carbide material powder and a kind of or plural kind of carbide powder with And carbonaceous material uniformly mixes, the group of mixture becomes：Carbide-formers matter content is 7-89wt%, and the carbide of infusibility is made pottery Porcelain content of powder is 7-89wt%, carbon content 1-30wt%.

The substance that carbide can be formed includes：The all elements and boron of IVB in the periodic table of elements, VB and group vib and Silicon；It can individually a kind of addition or a variety of carbide-formers matter be added together, content 7-89%wt；

The carbide ceramic powder of infusibility can be added in singular form, or together with the carbide ceramic powder of a variety of infusibilities It is added, content 7-89wt%；

Carbonaceous material refers to the organic substance containing carbon, content 1-30wt%；

2 use unidirectional, two-way, isostatic pressed or the methods of slurry cast, gel-cast, extruding, environment temperature will be with Upper mixture molding, makes the relative density of powder base reach 25-75%.

If 3 using carbonaceous material as forming agent, need powder base in single carbonaceous gas or by a variety of carbon containing gas 600 DEG C are heated in the atmosphere of body mixing composition, so that organic forming agent is transformed into carbon, is then heated to 650-1000 DEG C, i.e., The decomposition temperature of carbonaceous gas makes decomposition Carbon deposition inside and outside powder base, until the weightening of powder base reaches 1-20%, obtains containing enough Stoichiometric carbon and the powder base by reinforcing；

Here, carbon equivalent enough refers to that carbide-formers matter be added to be made fully to react, it is above-mentioned each to obtain Kind carbide：Boron carbide (B4C), silicon carbide (SiC) and titanium (TiC), zirconium (ZrC), hafnium (HaC), vanadium (VC), niobium (NbC), Tantalum (TaC), chromium (Cr3C2), molybdenum (MoC), the required carbon molal quantity of tungsten (WC)；

Carbonaceous gas includes：At 650-1000 DEG C, it can be cleaved the gas for generating carbon, such as：Carbon monoxide or methane, second The hydrocarbons such as alkane, propane, butane, pentane, hexane and benzene.

4 by the powder base Jing Guo (3) step in vacuum or inert atmosphere, be heated to 1100-2000 DEG C heat treatment；Make carbon Compound forming material is fully reacted with carbon, to form a continuous carbon together with the refractory carbides ceramics being added when batch mixing Compound ceramic skeleton.

5 in vacuum, inert atmosphere or reducing atmosphere, and a kind of metal or alloy is heated to the temperature of its fusing point or more Degree, makes the metal or alloy melt and penetrates into the porous carbide ceramics skeleton obtained through step (4), obtains densification Composite material.

Here, the metal of infiltration is that aluminium, magnesium, silicon is one such or the alloy of these metals.

Specific implementation mode

The implementation of the present invention, will include the following steps：

1, using the conventional batch mixer such as v-shaped, roll-type or ball milling, will contain at least one substance that can form carbide Powder and at least one carbide powder and carbon black or carbon containing organic matter, such as industrial paraffin, phenolic resin mixing are equal It is even.The ratio of mixture is：Carbide-formers matter powder accounts for 7-89% (weight percent)；The carbide powder of infusibility accounts for 7- 89%；Remaining carbon amounts is based on the chemical equivalent of used carbide-formers matter after carbon black or carbon containing organic matter decompose It calculates：

For chemically reacting xM+yC → MxCy, then the carbon weight Mc being added is needed to be in total：Mc=m0 γ Acy/ (A·x)

Wherein：M0 is the initial mass of powder base；

γ is the mass percent of the carbide-formers matter in mixture；

Ac and A is respectively the molal weight of carbon and carbide-formers matter；

X and y is respectively the atomicity in carbide molecular formula；

Therefore Mc=λ+Δ m, i.e. λ are the weight for the carbon being incorporated in batch mixing, and Δ m is to be obtained during organic cracking The weight of the carbon obtained.

So-called " substance that can form carbide " includes VIB in the periodic table of elements, VB, all elements of VIB isofamily, with And the elements such as boron in IIIA and VIA isofamily and silicon.Used carbide includes at least one of carbide of these elements.

2 use unidirectional, two-way, isostatic pressed or the methods of slurry cast, gel-cast, extruding, by the above mixture at Type.The porosity and pore size of powder base, should be depending on the tenor that final composite material needs.Best powder base is opposite Density is 25-75%, and best average pore size is 0.1-100 microns.

Molding periporate base is heated to 650-1000 degrees Celsius, the i.e. decomposition of carbon-containing atmosphere by 3 in carbon containing atmosphere Temperature makes the Carbon deposition of decomposition inside and outside powder base, until the weightening of powder base reaches the Δ m of requirement, generally in 1-20%.In this way, powder The intensity of base is improved, while being obtained containing carbon stoichiometric enough.

Carbon-containing atmosphere refers to the hydrocarbons such as carbon monoxide or methane, ethane, propane, butane, pentane, hexane and benzene and works as In one or more kinds of mixed gas.

If doing forming agent using carbon containing organic matter, needs powder base in carbon-containing atmosphere, it is Celsius to be slowly heated to 600 Degree, makes organic forming agent be transformed into carbon.

4 by the powder base Jing Guo (3) step in vacuum or inert atmosphere, be heated to 1100-2000 DEG C heat treatment, make powder Carbide-formers matter in base is fully reacted with carbon, obtains strong porous carbide green body.

5 in inert atmosphere (including vacuum) or reducing atmosphere, by a kind of metal or alloy be heated to its fusing point with On temperature, so that the metal or alloy is melted and be impregnated into the porous carbide green body obtained through step (4), caused Close composite material.

The metal of infiltration is that aluminium, magnesium, silicon etc. is one such or alloys of these metals.

Application example：

1 presses the proportioning of 23wt%, 72wt% and 5wt%, the boron carbide powder and amorphous boron that mistake -140+270 mesh is sieved Powder and polyethylene hexylene glycol uniformly mix.With the unidirectional method suppressed and limit, it is 10 millis that a diameter of 100 mm of thickness, which is made, The powder base of rice.The porosity of powder base is about 38%.Powder is placed in methane atmosphere and is heated slowly to 600 degree Celsius, removal is big Part polyethylene hexylene glycol.800 degree Celsius are then heated to, and is stopped about 3 hours, until sample obtains 20wt% weightenings.

Powder base containing enough equivalent carbon is placed in graphite resistor furnace, 1700 degrees Celsius of guarantors are heated in 1mbar vacuum Temperature 30 minutes, makes powder base grow into strong carbide skeleton.

Aluminium alloy containing 5% magnesium is heated to 950-1000 degrees Celsius in argon gas, is then dipped into carbide skeleton molten In the alloy liquid of change.After infiltration, fine and close boron carbide-Al alloy composite is obtained.Wherein boron carbide > 69%, aluminium alloy > 30% (percentage by volume), porosity < 1%.

The proportion of the composite material is 2.55 grams/cc, elasticity modulus=360GPa, hardness HV=34GPa, bending resistance Intensity=422MPa, fracture toughness (KIC)=5MPam1/2.

2 by boron carbide skeleton made from example above in 900-1000 degree argon gas atmosphere Celsius, immerse 10wt% containing aluminium Magnesium alloy melt in.Fine and close boron carbide-the composite material of magnesium alloy being had the following performance：

Wherein boron carbide > 69% (percentage by volume), magnesium alloy > 30%, pore volume < 1%.Proportion be 2.25 grams/ Cubic centimetre, elasticity modulus=337GPa, hardness HV=32GPa, bending strength=405MPa, fracture toughness (KIC)= 6.5MPam1/2。

3 by the silicon carbide (d50=50 microns) that weight percent is respectively 56%, 38wt%, 1% and 5%, silica flour (d50=5 microns), carbon black and polyethylene hexylene glycol uniformly mix.With the unidirectional method suppressed and limit, it is made a diameter of The powder base that 100 mm of thickness are 10 millimeters.The porosity of powder base is about 46%.Powder is placed in methane atmosphere and is heated slowly to 600 degree Celsius, remove most of polyethylene hexylene glycol.800 degree Celsius are then heated to, and is stopped about 4.5 hours, until sample Product obtain 15.8wt% weightenings.

Powder base containing enough equivalent carbon is placed in graphite resistor furnace, 1450 degrees Celsius of guarantors are heated in 1mbar vacuum Temperature 30 minutes, makes powder base grow into strong carbide skeleton.

The aluminium alloy of the 5wt% containing magnesium is heated to 950-1000 degrees Celsius in argon gas, is then dipped into carbide skeleton In the alloy liquid of fusing.After infiltration, fine and close silicon carbide-aluminium alloy composite materials are obtained.The wherein body of silicon carbide, aluminium alloy Product percentage is respectively greater than 54% and 44%, and porosity is less than < 2%.

The proportion of the composite material is 2.91 grams/cc, elasticity modulus=200GPa, hardness HV=23GPa, bending resistance Intensity=360MPa, fracture toughness (KIC)=7.1MPam1/2.

4 by silicon carbide skeleton made from example above in 900-1000 degree Celsius, argon gas atmosphere, immerse 10wt% containing aluminium Magnesium alloy melt.Fine and close silicon carbide-the composite material of magnesium alloy being had the following performance：

Wherein silicon carbide > 54%, magnesium alloy > 44% (percent by volume), pore volume < 2%.The composite material Proportion is 2.37 grams/cc, elasticity modulus=212GPa, hardness HV=20GPa, bending strength=342MPa, and fracture is tough Property (KIC)=7MPam1/2.

Claims (2)

1. a kind of method of manufacture ceramics and metallic composite, it is characterised in that：Carbide can be formed by least one Material powder is uniformly mixed with the carbide ceramic powder of at least one infusibility and at least one carbonaceous material, and mixture is existed Compacting or slurry moulding by casting, obtained periporate base are mixed in single carbonaceous gas or by a variety of carbonaceous gas under environment temperature It in the atmosphere being combined into, is heat-treated at 650-1000 DEG C, makes the carbon of carbonaceous gas decomposition and generation, be deposited in porous powder base So that powder base is increased weight to 1-20% outside, powder base is heat-treated in 1100-2000 DEG C of vacuum or inert atmosphere then, is made in powder base The substance and carbon that carbide can be formed chemically react, to form one together with the refractory carbides ceramics being added when batch mixing A continuous carbide ceramics skeleton；Make fusing in vacuum, inert atmosphere or reducing atmosphere finally by infiltrating method Metal or alloy infiltrate through in ceramic skeleton, obtain fine and close ceramic-metal composite material；

Here, can form the substance of carbide is：IV B in the periodic table of elements, V B and VI B race's all elements and boron and Silicon；It is added together with individually a kind of addition or a variety of carbide-formers matter, content 7-89wt%；

Here, the carbide ceramic powder of infusibility includes IV B in the periodic table of elements, V B and VI B races all elements, boron and silicon Carbide；It is added together with individually a kind of addition or a variety of carbide-formers matter, content 7-89wt%；

Here, carbonaceous gas refers to：One or both of carbon monoxide methane, ethane, propane, butane, pentane, hexane and benzene with On mixed gas；

Here, carbonaceous material refers to carbon containing organic substance, content 1-3wt%；

Here, the metal of infiltration is that aluminium, magnesium, silicon is one such or the alloy of these metals.

2. the method for a kind of manufacture ceramics and metallic composite according to claim 1, which is characterized in that if used Carbonaceous material as forming agent, need one kind in carbon monoxide, methane, ethane, propane, butane, pentane, hexane and benzene or In the atmosphere of two or more mixed gas, powder base is heated to 600 DEG C, so that organic forming agent is become carbon, is then again heated to 650-1000℃。