CN104209498B - Preparing method of interface modification layer of ceramic particle enhanced metal base composite material - Google Patents
Preparing method of interface modification layer of ceramic particle enhanced metal base composite material Download PDFInfo
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- CN104209498B CN104209498B CN201410352403.2A CN201410352403A CN104209498B CN 104209498 B CN104209498 B CN 104209498B CN 201410352403 A CN201410352403 A CN 201410352403A CN 104209498 B CN104209498 B CN 104209498B
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Abstract
The invention discloses a preparing method of an interface modification layer of a ceramic particle enhanced metal base composite material, and belongs to the technical field of a metal base composite material. The method comprises the following steps that ceramic particles and modification element particles are uniformly mixed according to a certain proportion, are pressed into a prefabricated body and are sintered, then, the sintered prefabricated body is placed into a casting die cavity, a metal substrate with the melting point lower than the melting point of the modification elements is cast on the sintered prefabricated body, next, the metal base composite material is prepared by adopting a pressure casting method, the melting point of the modification elements is a little higher than the melting point of molten liquid, so the modification elements are in a molten state when the molten liquid is cast into the die cavity, then, the modification elements move together with the molten liquid under the pressure effect, when meeting the blocking effect of the ceramic particles, the modification elements and the molten metal can go around the surface of the ceramic particles for forming a micrometer level interface modification layer on the surfaces of the ceramic particles, and the bonding intensity of the ceramic particles and the metal interfaces can be improved. When the method provided by the invention is adopted, great significance can be realized on the preparation of high-performance and low-cost metal base composite material.
Description
Technical field
The present invention relates to a kind of preparation method of ceramic particle reinforced metal base composites interface modification layer, belong to metal
Based composites technical field.
Background technology
Due to the excellent wear resistence of metal-base composites, high-temperature behavior, relatively low cost etc., gradually in thermal structure material
The fields such as material, high-abrasive material, tool die material obtain application.But ceramic particle is with metallic matrix interface bond strength often relatively
Difference, leads to composite macro-mechanical property undesirable.At present, improve in composite and strengthen the side mutually combining with basal body interface
Method has three classes substantially：1. strengthening phase surface coating.2. adding in parent metal can be with the alloying element strengthening phase reaction.③
Reaction in-situ self-generating strengthens phase.In order to solve the problems, such as Metal Matrix Composite Interface poor bonding strength：
Chinese invention patent CN103302268A proposes to prepare the ceramic preform with hole with ceramic powders first；Lead to again
Cross mode nickel plating on ceramic preform of chemical nickel plating, the thickness of nickel coating is 10 μm -200 μm；Will be pre- for the pottery after nickel plating
Product is fixed in casting mold, and negative pressure casting matrix molten metal obtains metal ceramic composite wear-resistant material.Comparison letter of the present invention
Single, it is particularly suitable for the production of big part plate part.The combination of high yield rate, stable performance, matrix and precast body can form good
Metallurgical binding.But the method is by way of chemical nickel plating, relatively costly, higher to equipment requirement.
Chinese invention patent CN101899631A discloses a kind of metal-based composite material reinforcement surface high wettability and applies
Layer method of modifying, comprises the steps：1. it is less than magnesium using conventional coating production in reinforcement surface coating
Coating of metal oxides；2. the reinforcement of coated metal oxide coating and pure magnesium are put in vacuum drying oven, pure magnesium is placed in furnace bottom,
Reinforcement is placed in above pure magnesium, vacuumizes, and keeps vacuum to be less than 10Pa, is warming up to 600-700 DEG C, is incubated 5-60 minute, makes
There is oxidation-reduction reaction with increasing body surface face coating of metal oxides in magnesium vapor, generate the internal layer being made up of compound and quilt
The composite bed that the outer layer of reducing metal composition is constituted.But the method needs to complete in vacuum environment, and operates ratio
More complicated, relatively low for industrial possibility.
Chinese invention patent CN103193507A is related to a kind of raising method to SiC ceramic wetability for the metal.The present invention
By injecting the metal ion of doses in SiC ceramic surface, reduce the contact angle to SiC ceramic surface for the metal, improve gold
Belong to the interface cohesion with pottery, the heat of raising SiC ceramic and metal contact interface, electrical property.Although the method can improve gold
Belong to ceramic wetability, but be confined to SiC, range of application is not very wide.
The method that these improve the bond strength between metal-base composites ceramic particle and metallic matrix at present, or many
Or few all can there is relatively costly, complex operation, DeGrain, inapplicable industrial production, the problems such as range of application is wide.
Content of the invention
In order to solve metallic matrix and ceramic particle poor bonding strength, composite in metal-base composites preparation process
The critical problem of poor-performing, it is an object of the invention to provide a kind of ceramic particle reinforced metal base composites interface changes
The preparation method of property layer, specifically includes following steps：
（1）Batch mixing：Ceramic particle, modifying element powder, bonding agent are mixed and obtain mixture, makes pottery in the mixture
The mass percent of porcelain particle is 75% ~ 95%, and the mass percent of modifying element is 5% ~ 25%, and bonding agent mass percent is 3%
~5%；
（2）The preparation of precast body：Take out ceramic particle, be pressed into the precast body of required form under 5 ~ 40MPa pressure；
（3）Casting：By precast body in 100 DEG C ~ 1200 DEG C roasting 30min ~ 120min, after coming out of the stove, it is quickly placed into casting mold die cavity
In, casting metals liquid-based body, using compression casting so that molten metal is infiltrated up in the gap between ceramic particle, obtain compound
Material interface modified layer.
Step of the present invention（1）Described in batch mixing can be mixed in ball mill, incorporation time be 30min ~ 120min,
Rotating speed is 50 ~ 300r/min.
Ceramic particle of the present invention is A12O3、ZrO2、SiO2、SiC、B4C、TiC、TiN、TiB2One or more of,
Its granularity is 10-300 mesh.
Modifying element of the present invention is one of Ni, Ti, Cr, Cu, Si, B, Co, Al element, and its granularity is 100-
500 mesh.
Molten metal basic material of the present invention is cast steel, cast iron, Al alloy, Cu alloy, Zn alloy, Mg alloy, Ti close
One of gold, Ni alloy.
In step A of the present invention, bonding agent is water glass solution, Ludox, aluminium metaphosphate solution, poly-vinyl alcohol solution
One or more.
The fusing point of modifying element of the present invention is higher than the fusing point of metallic matrix 100-400 DEG C, because modifying element is molten
Select the fusing point of slightly above molten metal, be cast in die cavity in molten metal, modifying element is in molten condition, then the work in pressure
Moved together with lower and then molten metal, when running into the inhibition of ceramic particle, can be around ceramic grain surface, on its surface
Form the bond strength that one layer of micron-sized interface modification layer can improve ceramic particle and metal interface.
The principle of the present invention：After ceramic particle and modifying element particle are mixed according to a certain percentage, compacting
Become precast body and sinter, be then placed in mould cavity, fusing point of casting above is slightly below the metal of modifying element fusing point, then leads to
The method of excess pressure casting prepares the metal-base composites of interface modification；Fusing point due to modifying element is slightly above molten metal
Fusing point, be cast in die cavity in molten metal, modifying element is in molten condition, more under the effect of the pressure follow molten metal
Move together, when running into the inhibition of ceramic particle, one layer of micron order can be formed around ceramic grain surface on its surface
Interface modification layer because the wetability of ceramic particle and metallic matrix is generally poor, at this layer of micron-sized interface modification layer
In the interface of ceramic particle and metallic matrix, the angle of wetting between ceramic particle and metallic matrix can be reduced, such that it is able to change
Kind ceramic particle and the bond strength of metal interface.
The invention has the beneficial effects as follows：
（1）The metal-base composites prepared by the method, its ceramic grain surface has the modified layer of layer cladding, permissible
Increase bond strength between ceramic particle and metallic matrix, improve the combination property of composite；Hardness is to weigh Metal Substrate again
One important indicator of condensation material interface bond strength, hardness is higher, and interface bond strength is better, Al2O3- 40Cr as cast condition grand
Seeing hardness is 28.7, and after adding Si powder, hardness reaches 39.4, illustrates that interface bond strength improves significantly；
（2）Selectivity between modifying element and matrix is wider, and preparation method is simple, easily operates, and low cost
Honest and clean, suitable industrialized production；
（3）Ensure that the reliability using under top load wear working condition by metal-base composites prepared by the method
Property；Compared to Castingother method, using pressure casting processes, ceramic particle reinforced metal base composites once infiltrate and become
Shape, products obtained therefrom interface cohesion is tightr, does not have microdefect, good in conjunction with uniformity, and intensity and toughness are all improved.
Brief description
Fig. 1. it is the precast body schematic diagram of present invention preparation；
Fig. 2 is the preparation method schematic diagram of the Metal Matrix Composite Interface modified layer of the present invention；
Fig. 3 is the schematic illustration of tissue of the Metal Matrix Composite Interface modified layer of the present invention；
Fig. 4 is 5%Ti-Al2O3- 45 structure of steel schematic diagrames；
Fig. 5 is 5%Ti-Al2O3- 45 steel and Al2O3Wear extent contrast under -45 steel different rotating speeds；
In figure：1- ceramic particle, 2- modifying element particle, 3- precast body, 4- metallic matrix, 5- interface modification layer.
Specific embodiment
Below in conjunction with the accompanying drawings and specific embodiment is described in further detail to the present invention, but protection scope of the present invention is simultaneously
It is not limited to described content.
Embodiment 1
The present embodiment methods described is used for preparing Al2O3Particle reinforced iron matrix composites, specifically include following steps：
（1）Weigh the Al that granularity is 10 ~ 50 mesh2O3Particle 375g, granularity are 500 purposes pure Ni powder 125g, and with 3%
Na2SiO3And 2%H2The bonding agent 25g mixing that O prepares, is sufficiently mixed 30min in ball mill；
（2）Take out step（1）The particle mixing, is pressed into the circular precast body of a diameter of 90mm under 20MPa pressure
（As Fig. 1）；
（3）By precast body in 800 DEG C of roastings 2 hours, it is quickly placed into after coming out of the stove in mold cavity, pour liquid cast-iron, cast temperature
Spend for 1380 ~ 1430 DEG C, cast so that iron liquid is infiltrated up to Al in 70MPa pressure2O3In gap between particle（As figure
2）, obtain densified composite interface modification layer（As Fig. 3）.
The Al of Ni is wrapped on surface2O3Wetability between pottery and molten steel is improved, and bond strength is from Al2O3Between/Fe
0.7 MPa bring up to nickel coat Al2O34.05 MPa of/Fe, and interface has more preferable non-oxidizability.There is Ni and be not added with Ni
Al2O3The wearability of particle reinforced steel-base composite material is 2. 5 times and 1. 6 times of homogeneity base steel respectively.
Embodiment 2
The present embodiment methods described is used for preparing Al2O3Particle strengthens 45 base steel composite materials, specifically includes following steps：
（1）Weigh the Al that granularity is 80 ~ 120 mesh2O3Particle 425g, granularity are the Ti powder 75g of 100 mesh, and with 4%
Na2SiO3And 2%H2The bonding agent 30g mixing that O prepares, is sufficiently mixed 1 hour in ball mill；
（2）Take out step（1）The particle mixing, is pressed into the circular precast body of a diameter of 90mm under 10MPa pressure；
（3）By precast body in 1000 DEG C of roastings 2 hours, it is quickly placed into after coming out of the stove in mold cavity, 45 molten steel of casting, cast
Temperature is 1500 ~ 1550 DEG C, is cast so that molten steel is infiltrated up to Al in 40MPa pressure2O3In gap between particle, obtain
Densified composite interface modification layer.
The 5%Ti-Al that the present embodiment prepares2O3- 45 structure of steel schematic diagrames are as shown in figure 4, by metallographic structure schematic diagram
It can be seen that Al2O3Particle and 45 steel matrix interface cohesion closely, do not have microdefect, good in conjunction with uniformity, have cladding at interface
One layer of Ti and its titaniferous compound, can increase Al2O3Bond strength between ceramic particle and 45 steel matrix, improves the resistance to of composite
Mill performance.5%Ti-Al2O3- 45 steel and Al2O3Under -45 steel different rotating speeds wear extent contrast schematic diagram as shown in Figure 5 it can be deduced that
There is the composite-material abrasive of interface modification layer preferable.
Embodiment 3
The present embodiment methods described is used for preparing SiC particulate reinforced aluminum matrix composites, specifically includes following steps：
（1）Weighing granularity for the SiC particulate 450g of 150 ~ 180 mesh, granularity is 500 purposes pure Cu powder 50g, molten with 5% silicon
Glue and 3%H2The bonding agent 40g mixing that O prepares, is sufficiently mixed 1.5 hours in ball mill；
（2）Take out step（1）The particle mixing, is pressed into the circular precast body of a diameter of 90mm under 20MPa pressure；
（3）By precast body in 500 DEG C of roastings 2 hours, it is quickly placed into after coming out of the stove in mold cavity, pour aluminium liquid, pouring temperature
For 660 ~ 680 DEG C, cast so that in the gap that is infiltrated up between SiC particulate of aluminium liquid, obtaining fine and close multiple in 40MPa pressure
Condensation material interface modification layer.
Embodiment 4
The present embodiment methods described is used for preparing Al2O3Granule reinforced copper base composite material, specifically includes following steps：
（1）Weigh the Al that granularity is 80 ~ 150 mesh2O3Particle 400g, granularity are 500 purposes pure Cr powder 100g, and with 5% inclined
Aluminum phosphate solution bonding agent 25g mixes, and is sufficiently mixed 1.5 hours in ball mill；
（2）Take out step（1）The particle mixing, is pressed into the circular precast body of a diameter of 90mm under 30MPa pressure；
（3）By precast body in 600 DEG C of roastings 2 hours, it is quickly placed into after coming out of the stove in mold cavity, pour copper liquid, pouring temperature
For 950 ~ 1000 DEG C, cast so that copper immersion is seeped into Al in 60MPa pressure2O3In gap between particle, obtain fine and close
Composite material interface modified layer.
Embodiment 5
The present embodiment methods described is used for preparing TiN granule reinforced copper base composite material, specifically includes following steps：
（1）Weigh granularity be the TiN particle 475g of 250 ~ 300 mesh, granularity be 500 purposes pure Ti powder 25g, and with 2%
Na2SiO3The bonding agent 25g mixing of solution and the preparation of 3% Ludox, is sufficiently mixed 2 hours in ball mill；
（2）Take out step（1）The particle mixing, is pressed into the circular precast body of a diameter of 90mm under 40MPa pressure；
（3）By precast body in 800 DEG C of roastings 2 hours, it is quickly placed into after coming out of the stove in mold cavity, pour titanium liquid, pouring temperature
For 950 ~ 1000 DEG C, cast in 70MPa pressure so that copper immersion is seeped in the gap between TiN particle, obtained fine and close multiple
Condensation material interface modification layer.
Embodiment 6
The present embodiment methods described is used for preparing WC particle enhancing iron base composite material, specifically includes following steps：
（1）Weigh granularity be the WC particle 450g of 80 ~ 150 mesh, granularity be 500 purposes pure Co powder 50g, and use 5% Ludox
Bonding agent 25g mixes, and is sufficiently mixed 2 hours in ball mill；
（2）Take out step（1）The particle mixing, is pressed into the circular precast body of a diameter of 90mm under 20MPa pressure；
（3）By precast body in 1000 DEG C of roastings 2 hours, it is quickly placed into after coming out of the stove in mold cavity, pour rich chromium cast iron metal
Liquid, pouring temperature is 1500 ~ 1550 DEG C, is cast so that iron liquid is infiltrated up to the gap between WC particle in 50MPa pressure
In, obtain densified composite interface modification layer.
Embodiment 7
The present embodiment methods described is used for preparing TiC particle reinforced steel-base composite material, specifically includes following steps：
（1）Weigh granularity be the TiC particle 425g of 80 ~ 120 mesh, granularity be 300 purposes pure Si powder 75g, and with 5% poly- second
Enol bonding agent 25g mixes, and is sufficiently mixed 1 hour in ball mill；
（2）Take out step（1）The particle mixing, is pressed into the circular precast body of a diameter of 90mm under 10MPa pressure；
（3）By precast body in 600 DEG C of roastings 2 hours, it is quickly placed into after coming out of the stove in mold cavity, 40Cr steel metal of casting
Liquid, pouring temperature is 1450 ~ 1550 DEG C, is cast so that molten steel is infiltrated up to the gap between TiC particle in 60MPa pressure
In, obtain densified composite interface modification layer.
Claims (6)
1. a kind of preparation method of ceramic particle reinforced metal base composites interface modification layer is it is characterised in that specifically include
Following steps：
（1）Batch mixing：Ceramic particle, modifying element, bonding agent mixed and obtain mixture, in the mixture ceramic particle
Mass percent is 75% ~ 95%, and the mass percent of modifying element is 5% ~ 25%, and bonding agent mass percent is 3% ~ 5%；
（2）The preparation of precast body：Take out ceramic particle, be pressed into the precast body of required form under 5 ~ 40MPa pressure；
（3）Casting：By precast body in 100 DEG C ~ 1200 DEG C roasting 30min ~ 120min, it is quickly placed into after coming out of the stove in casting mold die cavity,
Casting metals liquid-based body, using compression casting so that molten metal is infiltrated up in the gap between ceramic particle, obtains composite
Interface modification layer；
Described modifying element is one of Ni, Ti, Cr, Cu, Si, B, Co, Al element, and its granularity is 100-500 mesh.
2. the preparation method of ceramic particle reinforced metal base composites interface modification layer according to claim 1, it is special
Levy and be：Step（1）Described in batch mixing be in ball mill mixing 30min ~ 120min, rotating speed be 50 ~ 300r/min.
3. the preparation method of ceramic particle reinforced metal base composites interface modification layer according to claim 1, it is special
Levy and be：Described ceramic particle is A12O3、ZrO2、SiO2、SiC、B4C、TiC、TiN、TiB2One or more of, its particle
Spend for 10-300 mesh.
4. the preparation method of ceramic particle reinforced metal base composites interface modification layer according to claim 1, it is special
Levy and be：Described molten metal basic material is cast steel, cast iron, Al alloy, Cu alloy, Zn alloy, Mg alloy, Ti alloy, Ni close
One of gold.
5. the preparation method of ceramic particle reinforced metal base composites interface modification layer according to claim 1, it is special
Levy and be：Described bonding agent be water glass solution, Ludox, aluminium metaphosphate solution, poly-vinyl alcohol solution one or more.
6. the preparation method of ceramic particle reinforced metal base composites interface modification layer according to claim 1, it is special
Levy and be：The fusing point of modifying element is higher than the fusing point of molten metal matrix 100-400 DEG C.
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