Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a heat conductive composite material, a preparation method and application thereof; the heat conducting composite material has high heat conductivity, and reduces the difference between the heat conductivity between the surfaces and the heat conductivity between the surfaces.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a heat conductive composite material, comprising the steps of:
providing a composite body comprising an aluminum material and a graphite layer provided on a surface of the aluminum material;
applying a second pressure to the surface of the graphite layer, wherein the included angle between the direction of the second pressure and the surface of the graphite layer is beta, and beta is more than or equal to 60 degrees;
and under the conditions of vacuum and heating, applying a first pressure on the side wall of the composite body to enable the graphite layer to form a plurality of graphite aggregates distributed in different directions, and simultaneously, melting and mixing the aluminum material with the graphite aggregates to obtain the heat-conducting composite material, wherein an included angle between the direction of the first pressure and the surface of the aluminum material is alpha, and alpha is more than or equal to 0 degree and less than or equal to 60 degrees.
In one embodiment, the step of applying the second pressure is by rolling.
In one embodiment, in the step of applying a first pressure, the first pressure is applied to the composite at two opposing sidewalls of the composite.
In one embodiment, 0.ltoreq.α.ltoreq.30 °.
In one embodiment, the graphite layer has a thickness of 20 μm to 50 μm;
and/or the thickness of the aluminum material is 10-100 mu m;
and/or the mass ratio of the graphite layer to the aluminum material is 40:60-70:30.
In one embodiment, the heating temperature is 500 ℃ to 1000 ℃;
and/or the first pressure is 10 MPa-100 MPa, and the dwell time of the first pressure is 10 min-300 min;
and/or the second pressure is 0.1-10 MPa, and the pressing time of the second pressure is 1-10 min.
In one embodiment, the composite further comprises a bonding layer disposed between the aluminum material and the graphite layer, the graphite layer being adhered to the aluminum material by the bonding layer.
In one embodiment, the number of the composite bodies is set to be plural, and the plural composite bodies are arranged in a stacked manner in a direction perpendicular to the surface of the aluminum material.
According to another aspect of the present invention, there is provided a thermally conductive composite material comprising an aluminum skeleton and a plurality of graphite aggregates filled in the aluminum skeleton, a plurality of the graphite aggregates being arranged in an anisotropic manner, the thermally conductive composite material having an in-plane thermal conductivity of 300W/m-K to 500W/m-K, and an in-plane thermal conductivity of 20% or more of the in-plane thermal conductivity.
According to still another aspect of the present invention, there is provided a thermally conductive article comprising the thermally conductive composite material described above; or,
the heat-conducting product is made of the heat-conducting composite material.
In the preparation method, firstly, under the second pressure, graphite materials in the graphite layer are directionally arranged, so that the graphite layer is better attached to the surface of the aluminum material, and the porosity of the composite body in the vacuum hot-pressing treatment process can be reduced; and secondly, under the first pressure, the graphite material which is arranged in an oriented way can enable the graphite layer to bend and deform more uniformly towards the direction vertical to the surface of the aluminum material, so that a plurality of graphite aggregates which are arranged at any angle of 0-90 degrees with the surface direction of the aluminum material are formed, and meanwhile, the aluminum material can be melted, flowed and filled between the graphite aggregates to form an aluminum framework, so that the graphite and aluminum composite heat-conducting composite material is obtained.
In this way, the first, can make the in-plane high thermal conductivity of the original graphite layer turn into the high thermal conductivity of the surface to the surface at least partially, in order to overcome the problem of the heat conduction anisotropism of the graphite material; secondly, aluminum is used as a good heat conductor, and the skeleton of the heat-conducting composite material can obviously improve the heat conductivity of the heat-conducting composite material in the direction between the surfaces, so that the heat-conducting composite material has good heat conductivity in all directions; thirdly, aluminum has good mechanical properties, and as a skeleton of the heat-conducting composite material, the problem of brittleness of the graphite material can be solved, and the strength and other properties of the heat-conducting composite material are improved; fourth, when the aluminum material flows and fills between the graphite aggregates, bad heat conductor air between the graphite aggregates can be removed, the porosity of the heat conducting composite material is reduced, and the density of the heat conducting composite material is improved.
Therefore, the in-plane thermal conductivity of the heat conducting composite material obtained by the invention is 300W/m.K-500W/m.K, and the in-plane thermal conductivity reaches more than 20% of the in-plane thermal conductivity, so that the in-plane thermal conductivity of the heat conducting composite material is greatly improved, and the difference between the in-plane thermal conductivity and the in-plane thermal conductivity is reduced. Therefore, the heat-conducting composite material can meet the requirement of electronic devices on heat conduction performance, and has wide application prospects in the fields with high requirements on heat conduction, such as microelectronic equipment thermal management materials with high power density and high heat flux density.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
As used herein, the term "direction of the surface of the aluminum material" or "transverse direction" refers to the direction along the surface of the aluminum material, i.e., the direction of the surface of the graphite layer, and the in-plane direction refers to the direction of the length and width of the thermally conductive composite material, corresponding to the direction of the XY plane in the three-dimensional coordinate system; as used herein, the term "direction perpendicular to the surface of the aluminum material" or "longitudinal direction" refers to a direction perpendicular to the surface of the aluminum material, and the in-plane direction indicates the thickness direction of the thermal composite material, corresponding to the Z direction in the three-dimensional coordinate system.
Referring to fig. 1 to 3, the preparation method of the heat conductive composite material includes the following steps:
s1: providing a composite body 100, wherein the composite body 100 comprises an aluminum material 10 and a graphite layer 20 arranged on the surface of the aluminum material 10;
s2: applying a second pressure to the surface of the graphite layer, wherein the included angle between the direction of the second pressure and the surface of the graphite layer is beta, and beta is more than or equal to 60 degrees;
s3: and under the conditions of vacuum and heating, applying a first pressure F1 to the side wall of the composite body 100 to enable the graphite layer 20 to form a plurality of graphite aggregates 202 which are distributed in an opposite direction, and simultaneously, melting and mixing the aluminum material 10 with the graphite aggregates 202 to obtain the heat-conducting composite material, wherein an included angle between the direction of the first pressure F1 and the direction of the surface of the aluminum material 10 is alpha, and the included angle is more than or equal to 0 degree and less than or equal to 60 degrees.
In step S1, the material of the graphite layer 20 includes at least one of flake graphite, spheroidal graphite, and graphite fibers.
The thickness of the aluminum material 10 is 10-100 mu m, the thickness of the graphite layer 20 is 20-50 mu m, and the mass ratio of the graphite layer 20 to the aluminum material 10 is 40:60-70:30. The graphite layer 20 is less likely to undergo bending deformation by the first pressure F1, whereas if the graphite layer 20 is relatively high in mass, it will be difficult to be press-formed due to the brittle nature of graphite. Therefore, proper mass ratio between the graphite layer 20 and the aluminum material 10 is very important for the heat conduction performance and final morphology of the prepared heat conduction composite material.
Further, the composite body 100 may further include a bonding layer disposed between the aluminum material 10 and the graphite layer 20, and the graphite layer 20 is adhered to the aluminum material 10 through the bonding layer, so as to avoid uneven distribution of the graphite layer 20 on the aluminum material 10. Meanwhile, the bonding layer can make the graphite layer 20 more tightly bonded on the surface of the aluminum material 10, thereby facilitating the preparation of the composite body 100.
Further, the adhesive layer may be formed on the surface of the aluminum material 10 by spraying, coating, spin coating, or the like.
In step S2, the adhesive layer is thermally decomposed.
Further, after the graphite material is covered on the surface of the bonding layer to form the graphite layer 20, a blower or the like is used to remove the excessive graphite material, so that the graphite layer 20 is covered on the surface of the bonding layer more uniformly.
Preferably, the material of the bonding layer comprises at least one of atomized glue, glue and solidified glue.
In one embodiment, the mass ratio of the graphite layer 20, the aluminum material 10 and the adhesive layer is (40-70): (29-59.9): (0.1-1).
Of course, besides using the adhesive layer, the graphite layer 20 may be better laid on the surface of the aluminum material 10 by electrostatic adsorption, providing a rough structure on the surface of the aluminum material 10, or mechanical engagement.
Further, the number of the composite bodies 100 may be set to be plural, and the plural composite bodies 100 may be arranged in a stacked manner in a direction perpendicular to the surface of the aluminum material 10.
Preferably, the number of the composite bodies 100 is set to 50 to 500, and more preferably 100 to 300, to prepare a thermally conductive composite material having a desired thickness and capable of maintaining interfacial thermal conductivity.
Specifically, in the production process, a plurality of composite bodies 100 are produced, respectively, and the plurality of composite bodies 100 are stacked on each other. In the case of lamination, the aluminum material 10 of one composite 100 is preferably bonded to the graphite layer 20 of the other composite 100.
Before the first pressure F1 is applied to the composite body 100, a step S2 may be further performed, in which a second pressure F2 is applied to the graphite layer 20 on the surface of the graphite layer 20, where an angle between the direction of the second pressure F2 and the surface of the graphite layer 20 is β, and β is greater than or equal to 60 °.
Preferably, the graphite material in the graphite layer 20 is oriented by rolling the surface of the graphite layer 20. Thus, the graphite layer 20 can be better attached to the surface of the aluminum material 10, the porosity of the composite body 100 in the vacuum hot-pressing treatment process can be reduced, the density of the heat-conducting composite material is increased, and the heat conductivity of the heat-conducting composite material is improved.
In addition, after the graphite materials in the graphite layer 20 are aligned, the graphite layer 20 can be bent more uniformly towards the direction perpendicular to the surface of the aluminum material 10, so that the interfacial thermal conductivity of the heat conducting composite material is more uniform.
It will be appreciated that in other embodiments, graphite layer 20 may be acted upon by other compressive means, as the invention is not limited in this regard.
Preferably, the second pressure F2 is 0.1MPa to 10MPa, and the pressing time of the second pressure F2 is 1min to 10min.
In step S3, when the first pressure F1 is applied to the composite 100 by the side wall of the composite 100, the graphite layer 20 is bent and deformed in a direction perpendicular to the surface of the aluminum material 10 to form a plurality of graphite aggregates 202 arranged at any angle of 0 ° to 90 ° with respect to the direction of the surface of the aluminum material 10, so that the in-plane high thermal conductivity of the raw graphite layer 20 is at least partially converted into the in-plane high thermal conductivity, thereby overcoming the problem of the thermal conductivity anisotropy of the graphite material.
Meanwhile, the aluminum material 10 can be melted, flowed and filled between the graphite aggregates 202 to form an aluminum skeleton 201 under vacuum and a preset temperature. The heat conductivity of the heat-conducting composite material in the direction between the surfaces can be remarkably improved, so that the heat-conducting composite material has good heat conductivity in all directions, the brittleness problem of the graphite material can be overcome, and the strength and other performances of the heat-conducting composite material are improved.
Meanwhile, when aluminum flows and fills between the graphite aggregates 202, bad heat conductor air between the graphite aggregates 202 and gas generated by decomposition of the bonding layer can be removed, the porosity of the heat-conducting composite material is reduced, and the density of the heat-conducting composite material is improved.
Preferably, α is less than or equal to 30 °; more preferably, α is less than or equal to 5; further preferably, α=0°.
α=0°, that is, the direction in which the first pressure F1 is applied to the composite body 100 on the side wall of the composite body 100 is parallel to the surface of the aluminum material 10.
Preferably, after the composite body 100 is prepared, the composite body 100 is placed in a hot press mold, and the hot press mold is vertically placed so that the lateral direction of the composite body 100 is converted into the longitudinal direction. Then, the composite body 100 is subjected to a vacuum hot press treatment, and a first pressure F1 is applied to the composite body 100 at a side wall of the composite body 100.
Preferably, the first pressure F1 is 10MPa to 100MPa, more preferably 30MPa to 600MPa, and the graphite layer 20 can be more uniformly deformed by bending.
Preferably, the dwell time at the first pressure is from 10 minutes to 300 minutes, more preferably from 10 minutes to 30 minutes, to facilitate the final shaping of the thermally conductive composite material.
Further, there are a plurality of first pressures F1 applied to the composite body 100 at the side walls of the composite body 100, and it is preferable that the first pressures F1 are applied to the composite body 100 at two opposite side walls of the composite body 100, and the magnitudes and angles α of the first pressures F1 may be the same or different.
Further, the preset temperature is preferably 500 ℃ to 1000 ℃, and more preferably 600 ℃ to 650 ℃. At this preset temperature, the aluminum material 10 will be in a semi-molten state or a molten state, and will flow under the first pressure F1, filling between the graphite aggregates 202, to form an aluminum skeleton 201.
According to another aspect of the present invention, there is also provided a thermally conductive composite material including an aluminum skeleton 201 and a plurality of graphite aggregates 202 filled in the aluminum skeleton 201, the plurality of graphite aggregates 202 being arranged in an opposite direction, the thermally conductive composite material having an in-plane thermal conductivity of 300W/m-K to 500W/m-K, and the thermally conductive composite material having an in-plane thermal conductivity of 20% or more of the in-plane thermal conductivity. Therefore, the invention greatly improves the interfacial thermal conductivity of the heat conducting composite material and reduces the gap between the interfacial thermal conductivity and the in-plane thermal conductivity.
Preferably, the thermally conductive composite material has an in-plane thermal conductivity of greater than 24% of the in-plane thermal conductivity.
According to still another aspect of the present invention, there is also provided a thermally conductive article comprising the thermally conductive composite material described above; alternatively, the thermally conductive article is made of the thermally conductive composite material described above.
Specifically, the heat-conducting composite material can be directly used as a heat sink component to be attached to a substrate of a heat dissipation source. Of course, the thermally conductive composite material may also be further processed into a grid-like material for use as a heat sink.
Therefore, the heat-conducting composite material has the characteristics of high heat conductivity and small difference between in-plane heat conductivity and in-plane heat conductivity, and can be used as a heat sink material for heat dissipation elements with high requirements on heat dissipation capacity, such as computer heat dissipation modules, metal bushings, rotary sealing rings for medium load and medium speed application, thrust washers and the like, so that the stable operation of the device is ensured.
It should be noted that the application of the present invention to the above heat conductive composite material is merely illustrative, and not restrictive.
Hereinafter, preferred examples and comparative examples are listed for better understanding of the present invention. However, the following examples are only for illustrating the present invention, and are not limited thereto or thereby.
Example 1:
an aluminum foil of 60 μm thickness was taken and atomized glue was sprayed on the surface of the aluminum foil. And then pouring spherical graphite powder into the atomized glue layer, and blowing off excessive graphite powder by using a blower to form a graphite layer with the thickness of 40 mu m, wherein the mass ratio of the graphite layer to the aluminum foil is 50:50, so as to obtain the graphite-aluminum composite. The graphite-aluminum composite body is vertically placed into a hot pressing die and sintered in a vacuum unidirectional hot pressing sintering furnace, the temperature in the sintering furnace is heated to 650 ℃ at a heating rate of 10 ℃/min for sintering, the heat preservation time is 60min, the first pressure is 40MPa, the included angle alpha between the direction of the first pressure and the direction of the surface of the aluminum material is 0 DEG, and then the heat conduction composite material is prepared by cooling the heat conduction composite material to room temperature along with the furnace.
Example 2:
an aluminum foil of 80 μm thickness was taken and atomized glue was sprayed on the surface of the aluminum foil. And then pouring the graphite fiber powder onto the atomized glue layer, and blowing away the excessive graphite powder by using a blower to form a graphite layer with the thickness of 20 mu m, wherein the mass ratio of the graphite fiber powder to the aluminum foil is 55:45. And then carrying out rolling treatment on the graphite fiber powder, wherein the rolling pressure is 0.1MPa, and the rolling time is 10 minutes, so as to form the graphite-aluminum composite.
The graphite-aluminum composite body is vertically placed into a hot pressing die and sintered in a vacuum unidirectional hot pressing sintering furnace, the temperature in the sintering furnace is heated to 500 ℃ at a heating rate of 5 ℃/min for sintering, the heat preservation time is 300min, the first pressure is 100MPa, the included angle alpha between the direction of the first pressure and the direction of the surface of the aluminum material is 60 degrees, and then the heat conduction composite material is prepared by cooling the heat conduction composite material to room temperature along with the furnace.
Example 3:
an aluminum foil of 60 μm thickness was taken and atomized glue was sprayed on the surface of the aluminum foil. And then pouring the spherical graphite powder onto the atomized glue layer, and blowing away the excessive graphite powder by using a blower to form a graphite layer with the thickness of 40 mu m, wherein the mass ratio of the spherical graphite powder to the aluminum foil is 50:50. And then carrying out rolling treatment on the graphite powder, wherein the rolling pressure is 5MPa, and the rolling time is 5 minutes, so as to form the graphite-aluminum composite.
The graphite-aluminum composite body is vertically placed into a hot pressing die and sintered in a vacuum unidirectional hot pressing sintering furnace, the temperature in the sintering furnace is heated to 650 ℃ at a heating rate of 10 ℃/min for sintering, the heat preservation time is 60min, the first pressure is 40MPa, the included angle alpha between the direction of the first pressure and the direction of the surface of the aluminum material is 0 DEG, and then the heat conduction composite material is prepared by cooling the heat conduction composite material to room temperature along with the furnace.
Example 4:
this embodiment is substantially the same as embodiment 3, except that: the number of the composite bodies is set to 50, and the 50 composite bodies are arranged in a stacking manner along the longitudinal direction of the composite bodies.
Example 5:
this embodiment is substantially the same as embodiment 3, except that: the number of the composite bodies is set to 100, and the 100 composite bodies are arranged in a stacking manner along the longitudinal direction of the composite bodies.
Example 6:
this embodiment is substantially the same as embodiment 3, except that: the number of the composite bodies is set to 300, and 300 composite bodies are arranged in a stacked manner along the longitudinal direction of the composite bodies.
Example 7:
this embodiment is substantially the same as embodiment 3, except that: the number of the composite bodies is 500, and the 500 composite bodies are arranged in a stacking manner along the longitudinal direction of the composite bodies.
Comparative example 1:
an aluminum foil of 60 μm thickness was taken and atomized glue was sprayed on the surface of the aluminum foil. Then, spherical graphite powder having a particle diameter of 500 μm and a thickness of 40 μm was poured onto the atomized gel layer, and the excess graphite powder was blown off with a blower. The mass ratio of the spherical graphite powder to the aluminum foil is 50:50. And then carrying out rolling treatment on the graphite powder, wherein the rolling pressure is 5MPa, and the rolling time is 5 minutes, so as to form the graphite-aluminum composite.
The graphite-aluminum composite is horizontally placed into a hot pressing die and sintered in a vacuum unidirectional hot pressing sintering furnace, the temperature in the sintering furnace is heated to 650 ℃ at a heating rate of 10 ℃/min for sintering, the heat preservation time is 60min, the first pressure is 40MPa, the included angle alpha between the direction of the first pressure and the direction of the surface of the aluminum material is 90 degrees, and then the heat conduction composite is prepared by cooling the heat conduction composite to room temperature along with the furnace.
Comparative example 2:
an aluminum foil with a thickness of 2 μm was taken and atomized glue was sprayed on the surface of the aluminum foil. Then, spherical graphite powder having a particle diameter of 500 μm and a thickness of 40 μm was poured onto the atomized gel layer, and the excess graphite powder was blown off with a blower. The mass ratio of the spherical graphite powder to the aluminum foil is 95:5. And then carrying out rolling treatment on the graphite powder, wherein the rolling pressure is 5MPa, and the rolling time is 5 minutes, so as to form the graphite-aluminum composite.
And vertically placing the graphite-aluminum composite body into a hot pressing die, sintering in a vacuum unidirectional hot pressing sintering furnace, heating the temperature in the sintering furnace to 650 ℃ at a heating rate of 10 ℃/min, sintering for 60min, wherein the first pressure is 40MPa, the included angle alpha between the direction of the first pressure and the direction of the surface of the aluminum material is 0 ℃, and then cooling to room temperature along with the furnace to obtain the heat-conducting composite material.
The thermal conductive composites prepared in examples 1 to 7 and comparative examples 1 to 2 were subjected to in-plane and out-of-plane thermal conductivity measurement and in-plane and out-of-plane thermal expansion coefficient measurement, and the measurement results are shown in table 1.
TABLE 1
As can be seen from table 1, the heat conductive composite materials prepared in examples 1 to 7 have higher in-plane thermal conductivity, which reaches more than 20% of in-plane thermal conductivity, so that the difference between the in-plane thermal conductivity and the in-plane thermal conductivity of the heat conductive composite material is greatly reduced, the heat conductive composite material can conduct heat in all directions, and the requirement of an electronic device on heat conductivity is met. In addition, the heat-conducting composite materials prepared in examples 1 to 7 all have good thermal expansion performance.
The heat conduction composite material prepared in comparative example 1 has high in-plane thermal conductivity, but the in-plane thermal conductivity is too small, is only 1.6% of the in-plane thermal conductivity, is heat conduction anisotropic, and is difficult to conduct heat outwards at a heating end in practical application due to the low in-plane thermal conductivity, so that the heat conduction requirement cannot be met.
In comparative example 2, the aluminum skeleton cannot be formed in the hot pressing process due to the low aluminum foil content, and the graphite material is brittle and the heat conductive composite material cannot be molded in the vacuum hot pressing process.
Further, the heat-conducting composite material obtained in example 3 was subjected to SEM scanning in cross section, and as shown in fig. 3, graphite aggregates 202 in the heat-conducting composite material were arranged in opposite directions, and metal aluminum was filled between adjacent graphite aggregates 202 and connected to each other to form an aluminum skeleton 201, which was stable in structure. As shown in fig. 4, the interface between the aluminum skeleton 201 and the graphite aggregate 202 is clear, almost has no pores, and has high compactness, and the vacuum hot pressing treatment basically eliminates the gas in the heat-conducting composite material.
As a result of SEM scanning of the cross section of the heat conductive composite material prepared in comparative example 1, as shown in fig. 5, graphite aggregates 202 in the heat conductive composite material were almost all arranged in the lateral direction, metal aluminum was filled between adjacent graphite aggregates 202 and partially connected, and the connection strength of aluminum skeleton 201 was weaker than that of example 3.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.