A kind of Metal Substrate super-hard compound material and preparation method thereofTechnical field
The invention belongs to super-hard compound material field, and in particular to a kind of preparation method of Metal Substrate super-hard compound material.
Background technology
With continuing to develop for China's electronic technology, the requirement for electronic package material is improved constantly, and is used as a new generationThe superhard material powder enhancing metal-base composites thermophysical property excellent due to possessing of electronic package material and goodMechanical performance, it is of great interest.
The application of electronic package material needs to consider two big Essential Performance Requirements, is high thermal conductivity first, realizes heatQuick transmission, it is ensured that chip can under preferable temperature conditionss steady operation；Meanwhile, encapsulating material is needed with controllableThermal coefficient of expansion, so as to keep match with chip and encapsulating material at different levels, the harmful effect of reduction thermal stress.Metal class wrapperMaterial is because good with higher thermal conductivity, relatively low thermal coefficient of expansion and machining property, and by as most widely usedGeneral core material, each period developed in electronic package material all has great importance.But with nanometer techniqueThe extensive use of high thermal conductivity material industrially such as development and diamond, and the development of electronic package material starts by metalMaterial develops to the compound direction of the superhard materials such as metal and diamond.
The fusing point of diamond is 3550 DEG C, and cBN fusing point is 3300 DEG C or so.The graphitization of diamond starts in a vacuumIn 1600 DEG C -1700 DEG C (invalid temperatures), cBN heat endurance is up to 1550-1800 DEG C (invalid temperature).Existing compound skillGenerally using infiltration method, composite diamond prepares metal-base composites in a metal in art, and this method has the following disadvantages：It is firstFirst diamond and metal wetability extreme difference, it is difficult to the composite of densification is directly prepared, while also bringing the stone of diamondImpurity causes the problems such as diamond ruptures at high temperature in inkization and diamond；Secondly, infiltration method is by granular size, infiltrationThe factors such as temperature and time influence, and production process is slow, and equipment is complicated；In addition, also having what is applied using gas pressure infiltrationPressure is smaller, in diamond impurity cause at high temperature diamond rupture so as to hyperpyrexia thermal conductivity decline the problems such as.
Therefore, working out a kind of metal class wrapper material that can be prepared with superior function has huge economic meaningJustice.
The content of the invention
It is an object of the invention to provide a kind of Metal Substrate super-hard compound material, there is provided the Metal Substrate super-hard compound materialPreparation method is then another object of the present invention.
Based on above-mentioned purpose, the present invention uses following technical scheme：A kind of Metal Substrate super-hard compound material, by following weightThe raw material of percentage is prepared from：Nano metal powder 20%-68.8%, superhard material powder 30%-75% and wetting agent 0.2%-5%.
Preferably, the Nano metal powder is mixture more than one or both of Al, Cu or Ag nano-powder, grainSpend for 50 nm -200nm.
Preferably, the granularity of the plating diamond and plating cubic boron nitride is 50nm-300 μm.
Preferably, the coating of the superhard material powder is nickel, copper, titanium or tungsten, and thickness of coating is 50nm-2 μm.
Preferably, the wetting agent is Si, Ti, Mg, Fe, B, Cr, Mo or W one or more kinds of mixtures.
The preparation method of the Metal Substrate super-hard compound material, comprises the following steps：By Nano metal powder, superhard material powderIdiosome is cold-pressed into after body and wetting agent ball milling mixing；Idiosome is placed in vacuum or reducing atmosphere and sintered, sintering temperature, which is higher than, to be receivedFusing point, the invalid temperature less than superhard material powder of rice metal powder.
Further, the Nano metal powder is Al powder, and sintering temperature is 680-950 DEG C, sintering time 1-3h.
Further, the Nano metal powder is Cu powder, and sintering temperature is 1100-1300 DEG C, sintering time 1-3h.
Further, the Nano metal powder is Ag powder, and sintering temperature is 980-1200 DEG C, sintering time 1-3h.
Further, cold pressing step uses two-way compacting, and temperature is 15-35 DEG C, and pressure is 100-500MPa, pressurize 5-30s。
The thermal conductivity of diamond is up to 700-2000W/（m·K）, and thermal coefficient of expansion and density only have 1.0 × 10-6K-1And 3.52g/cm3；cBN（Cubic boron nitride）Thermal conductivity be only second to diamond, up to 1300W/（m·K）, it is Cu and Ag4-5 times, linear expansion coefficient is about 4.7 × 10-6K-1.It is fully able to improve its heat if diamond or cBN are combined with metal dustThe requirement of conductance, low bulk.
Al, Cu and Ag fusing point are respectively 660 DEG C, 1083 DEG C, 962 DEG C, thermal conductivity is respectively 238,109,429W/（m·K）.
Compared with prior art, the present invention has advantages below：
（1）The present invention, can be by this after diamond or cBN surfaces carry out plating using the diamond or cBN of platingLayer metal forms stable enhanced primary treatment with parent metal or wetting agent, improves the wetability of diamond or cBN and metal,So as to improve the interface binding power between superhard material and metal, and then improve the thermal conductivity of material.
（2）Diamond can be reduced in diamond surface progress plating to be oxidized and graphited degree；Enter on cBN surfacesRow plating can reduce oxidation and reversionization under cBN high temperature.
（3）Compared with pressure infiltration method, the composite that the method provided by the present invention is prepared can be controlled accuratelyThe volume proportion of superhard material and metal processed, so as to be accurately controlled the thermal physical characteristic for the Metal Substrate super-hard compound material preparedCan, production process is fast, and equipment is simple, and diamond or cBN rupture rates are reduced using the superhard material of plating.
（4）It with the addition of wetting agent in the present invention, the two-phase of wetting agent and composite forms good chemical bond, so thatImprove the interfacial structure of composite.Can also directly be controlled by regulating and controlling plating parameter simultaneously the thickness of coating, structure andThe parameters such as composition composition, so as to purposefully optimize composite material interface；And thickness of coating exceeds after 2 μm, coating can then be ledThe hydraulic performance decline of superhard material is caused, is unfavorable for improving the thermal conductivity for meeting material.
Embodiment
With reference to embodiment, the present invention is described in detail.
Comparative example 1
A kind of Metal Substrate super-hard compound material, is prepared from by the raw material of following percentage by weight：50% granularity is100nm Cu nano-powders, 49.5% granularity are 50 μm of bortz powders（Without coating）With 0.5% Si powder.
The preparation method of above-mentioned Metal Substrate super-hard compound material, comprises the following steps：（1）By Cu nano-powders, diamondPowder（Without coating）Mixed with Si in ball grinder after 4h, two-way compacting 20s, is made idiosome under the conditions of 15 DEG C, 250Mpa；
（2）It is placed in after idiosome is dried in 1100 DEG C of vacuum or reducing atmosphere and sinters 3h, obtains the compound of Cu base diamondsMaterial.
The thermal conductivity of the composite of Cu base diamonds prepared by comparative example 1 is 425 W/ after testing（m·K）, thermal expansionCoefficient is 6.2 × 10-6K-1。
Embodiment 1
A kind of Metal Substrate super-hard compound material, is prepared from by the raw material of following percentage by weight：50% granularity is100nm Cu nano-powders, 49.5% granularity are 50 μm of plating Cu bortz powders and 0.5% Si powder, and wherein thickness of coating is80nm。
The preparation method of above-mentioned Metal Substrate super-hard compound material, comprises the following steps：（1）By Cu nano-powders, plating Cu goldHard rock and Si are mixed after 4h in ball grinder, and two-way compacting 20s, is made idiosome under the conditions of 15 DEG C, 250Mpa；
（2）It is placed in after idiosome is dried in 1100 DEG C of vacuum or reducing atmosphere and sinters 3h, obtains the compound of Cu base diamondsMaterial.
The thermal conductivity of the composite of Cu base diamonds prepared by embodiment 1 is 535W/ after testing（m·K）, thermal expansion systemNumber is 5.6 × 10-6K-1, compared with adding the diamond particles without coating, the composite prepared by Cu diamonds is plated in additionThermal conductivity improves nearly 110 W/ compared with comparative example 1（m·K）, thermal coefficient of expansion reduces 0.4 × 10-6K-1。
Embodiment 2
A kind of Metal Substrate super-hard compound material, is prepared from by the raw material of volumes below percentage：40% granularity is 80nm'sAl nano-powders, 59% granularity are 150 μm of plating Ti bortz powders and 1% Mg powder, and wherein thickness of coating is 200nm.
The preparation method of above-mentioned Metal Substrate super-hard compound material, comprises the following steps：（1）By Al nano-powders, plating Ti goldEmery and Mg powder are mixed after 3h in ball grinder, at 35 DEG C, and two-way compacting 30s, is made idiosome under the conditions of 100MPa；
（2）It is placed in after idiosome is dried in 680 DEG C of vacuum or reducing atmosphere and sinters 2h, obtains the composite wood of Al base diamondsMaterial.
The heat conductivity that embodiment 2 prepares Al base diamonds after testing is 635W/（m·K）, thermal coefficient of expansion is6.7×10-6K-1.Compared with adding the diamond particles without coating, the heat of the composite prepared by addition plating Ni diamondConductance improves nearly 210 W/ compared with comparative example 1（m·K）.
Embodiment 3
A kind of Metal Substrate super-hard compound material, is prepared from by the raw material of following percentage by weight：50% granularity is 60nmAg nano-powders, 49.8% granularity be that 100nm plates Ni bortz powders and 0.2% Si powder, wherein thickness of coating is 300nm.
The preparation method of above-mentioned Metal Substrate super-hard compound material, comprises the following steps：（1）By Ag nano-powders, plating Ni goldEmery and Si powder are mixed after 3h in ball grinder, at 20 DEG C, and two-way compacting 10s, is made idiosome under the conditions of 500Mpa；
（2）It is placed in after idiosome is dried in 1000 DEG C of vacuum or reducing atmosphere and sinters 3h, obtains the compound of Ag base diamondsMaterial.
The heat conductivity that embodiment 3 prepares Ag base diamonds after testing is 647W/（m·K）, thermal coefficient of expansion is5.6×10-6K-1.Compared with adding the diamond particles without coating, the thermal conductivity of the composite prepared by addition plating Ni diamondsRate increases nearly 220 W/ compared with comparative example 1（m·K）, thermal coefficient of expansion reduces 0.6 × 10-6K-1。
Embodiment 4
A kind of Metal Substrate super-hard compound material, is prepared from by the raw material of following percentage by weight：30% granularity is 50nmCu nano-powders, 69.8% granularity be 100 μm of plating Ti bortz powders and 0.2% Si powder, wherein thickness of coating is 100nm.
The preparation method of above-mentioned Metal Substrate super-hard compound material, comprises the following steps：（1）By Cu nano-powders, plating Ti goldHard rock and Si are mixed after 4h in ball grinder, and two-way compacting 10s, is made idiosome under the conditions of 20 DEG C, 300Mpa；
（2）It is placed in after idiosome is dried in 1300 DEG C of vacuum or reducing atmosphere and sinters 1h, obtains the compound of Cu base diamondsMaterial.
The thermal conductivity of the composite of Cu base diamonds prepared by embodiment 4 is 620W/ after testing（m·K）, thermal expansion systemNumber is 5.1 × 10-6K-1, compared with adding the diamond particles without coating, the composite prepared by Ti diamonds is plated in additionThermal conductivity adds about 200 W/ compared with comparative example 1（m·K）, thermal coefficient of expansion reduction about 1.0 × 10-6K-1。
Embodiment 5
A kind of Metal Substrate super-hard compound material, is prepared from by the raw material of following percentage by weight：20% granularity is 200nmAl nano-powders, 75% granularity be 100nm plating Ni bortz powders and 5% Mg powder, wherein thickness of coating be 50nm.
The preparation method of above-mentioned Metal Substrate super-hard compound material, comprises the following steps：（1）By Al nano-powders, plating Ni goldEmery and Mg powder are mixed after 3h in ball grinder, at 35 DEG C, and two-way compacting 30s, is made idiosome under the conditions of 100MPa；
（2）It is placed in after idiosome is dried in 800 DEG C of vacuum or reducing atmosphere and sinters 2h, obtains the composite wood of Al base diamondsMaterial.
The heat conductivity that embodiment 5 prepares Al base diamonds after testing is 524W/（m·K）, thermal coefficient of expansion is6.5×10-6K-1.Compared with adding the diamond particles without coating, the heat of the composite prepared by addition plating Ni diamondConductance lifts about 100 W/ compared with comparative example 1（m·K）.
Embodiment 6
A kind of Metal Substrate super-hard compound material, is prepared from by the raw material of following percentage by weight：40% granularity is 200nmCu nano-powders, 59.5% granularity be 150 μm of plating Wu cBN powder and 0.5% Fe powder, wherein thickness of coating is100nm。
The preparation method of above-mentioned Metal Substrate super-hard compound material, comprises the following steps：（1）By Cu nano-powders, plating WucBNPowder and Fe powder are mixed after 3h in ball grinder, at 35 DEG C, and two-way compacting 30s, is made idiosome under the conditions of 100MPa；
（2）It is placed in after idiosome is dried in 1300 DEG C of vacuum or reducing atmosphere and sinters 1.5h, obtains Cu bases cBN composite woodMaterial.
Cu bases cBN prepared by embodiment 6 heat conductivity is 496W/ after testing（m·K）, thermal coefficient of expansion is5.9×10-6K-1。
Embodiment 7
A kind of Metal Substrate super-hard compound material, is prepared from by the raw material of following percentage by weight：45% granularity is 100nmAl nano-powders, 54.4% granularity be 50nm plating Ti cBN powder, 0.3% B powder and 0.3% Mo powder, wherein coatingThickness is 500nm.
The preparation method of above-mentioned Metal Substrate super-hard compound material, comprises the following steps：（1）By Al nano-powders, plating TicBNPowder and B+Mo powder are mixed after 3h in ball grinder, at 20 DEG C, and two-way compacting 20s, is made idiosome under the conditions of 300MPa；
（2）It is placed in after idiosome is dried in 950 DEG C of vacuum or reducing atmosphere and sinters 3h, obtains Al bases cBN composite.
The heat conductivity that embodiment 7 prepares Al bases cBN after testing is 615W/（m·K）, thermal coefficient of expansion is 7.0×10-6K-1。
Embodiment 8
A kind of Metal Substrate super-hard compound material, is prepared from by the raw material of following percentage by weight：68.8% granularity is 60nmAg nano-powders, 30% granularity be 300 μm of plating Cu cBN powder and 0.2% Ni powder, wherein thickness of coating is 1.5 μm.
The preparation method of above-mentioned Metal Substrate super-hard compound material, comprises the following steps：（1）By Ag nano-powders, plate Cu'sCBN powder and Ni powder are mixed after 3h in ball grinder, at 35 DEG C, and two-way compacting 30s, is made idiosome under the conditions of 100MPa；
（2）It is placed in after idiosome is dried in 980 DEG C of vacuum or reducing atmosphere and sinters 3h, obtains Ag bases cBN composite.
The heat conductivity that embodiment 8 prepares Ag bases cBN after testing is 465W/（m·K）, thermal coefficient of expansion is 5.4×10-6K-1。
Embodiment 9
A kind of Metal Substrate super-hard compound material, is prepared from by the raw material of following percentage by weight：25% granularity is 80nm'sThe cBN powder and 0.2% for the plating Ni that Ag nano-powders, the Cu nano-powders that 25% granularity is 80nm, 49.5% granularity are 500nmTi+Ni powder, wherein thickness of coating are 500m.
The preparation method of above-mentioned Metal Substrate super-hard compound material, comprises the following steps：（1）By Ag nano-powders, Cu nanometersPowder, plating Ni cBN powder and Ti+Ni powder are mixed after 3h in ball grinder, at 35 DEG C, two-way compacting 30s under the conditions of 100MPa, systemInto idiosome；
（2）It is placed in after idiosome is dried in 650 DEG C of vacuum or reducing atmosphere and sinters 3h, obtains Ag/Cu bases cBN composite woodMaterial.
The heat conductivity that embodiment 9 prepares Ag/Cu bases cBN after testing is 582W/（m·K）, thermal coefficient of expansion is5.2×10-6K-1。
Embodiment 10
A kind of Metal Substrate super-hard compound material, is prepared from by the raw material of following percentage by weight：60% granularity is 150nmAg nano-powders, 39.8% granularity for 800nm plating Ni cBN powder and 0.2% Cr+Wu powder, wherein thickness of coating be 2 μm。
The preparation method of above-mentioned Metal Substrate super-hard compound material, comprises the following steps：（1）By Ag nano-powders, plate Ni'sCBN powder and Cr+Wu powder are mixed after 3h in ball grinder, at 35 DEG C, and two-way compacting 30s, is made idiosome under the conditions of 200MPa；
（2）It is placed in after idiosome is dried in 1200 DEG C of vacuum or reducing atmosphere and sinters 2h, obtains Ag bases cBN composite woodMaterial.
The heat conductivity that embodiment 10 prepares Ag bases cBN after testing is 625W/（m·K）, thermal coefficient of expansion is5.5×10-6K-1。
From embodiment 1-10 result, although cBN thermal conductivity slightly below diamond, cBN heat-resisting quantities andChemical inertness is superior to diamond, therefore when using high-heat-conductive composite material under the hot environment for having contact with ferrous material,The composite that complex preparation is done with cBN can be selected.