Patent Application
20170349497
This application is based upon and claims the benefit of priority from Japanese Patent Application No. 2016-111136 filed on Jun. 2, 2016, the contents of which are incorporated herein by reference.
The present invention relates to a porous ceramic structure, and more particularly relates to a porous ceramic structure suitable for achieving a reduction in thermal conductivity of a component containing the porous ceramic structure, as well as to a method of manufacturing such a porous ceramic structure.
As a filler that is filled in a heat insulating material or a film, compositions and hollow particles and the like have been described in Japanese Laid-Open Patent Publication No. 2010-155946, Japanese Laid-Open Patent Publication No. 2004-010903, and Japanese Laid-Open Patent Publication No. 2010-064945.
Japanese Laid-Open Patent Publication No. 2010-155946 describes a curable organopolysiloxane composition, which is capable of forming a porous organopolysiloxane cured product having low thermal conductivity.
Japanese Laid-Open Patent Publication No. 2004-010903 describes the formation of a film having low thermal conductivity, by using a coating material in which hollow particles with low thermal conductivity are used.
Japanese Laid-Open Patent Publication No. 2010-064945 discloses a method in which additive particles are adsorbed on surfaces of base particles by an electrostatic interaction, thereby producing nanocoated composite particles, and further manufacturing a composite material through an ordinary powder metallurgy process by use of the composite particles.
With the technology described in Japanese Laid-Open Patent Publication No. 2010-155946 and Japanese Laid-Open Patent Publication No. 2004-010903, the reduction in thermal conductivity is insufficient. With the technology described in Japanese Laid-Open Patent Publication No. 2010-064945, since it is intended to manufacture a composite material by powder metallurgy, it is kept in mind that fine particles with a particle diameter on the order of nanometers (nm) are coated on the base particles. Therefore, the distance between the base particles becomes short, and in this case as well, the reduction in thermal conductivity is insufficient.
If the particles added to the adhesive are small, it is difficult to uniformly disperse the particles in the adhesive. Further, since it is necessary to fire an adhesive to which particles have been added in advance to form a bulk body, and thereafter place the adhesive on the object, for example, it becomes difficult to place the adhesive in a partial area of the object, and it is difficult to place the adhesive along a complex shape.
The present invention has been made in consideration of the aforementioned problems, and has the object of providing a porous ceramic structure as well as a method of manufacturing the porous ceramic structure, in which it is possible to achieve low thermal conductivity, together with installing the porous ceramic structure directly on an object using an adhesive or the like, and further, it is possible to facilitate installation of a bulk body.
[1] A porous ceramic structure according to a first present invention includes one sheet, and a porous ceramic aggregate bonded on the sheet, wherein the porous ceramic aggregate includes a plurality of porous ceramic particles.
[2] In the first present invention, the porous ceramic aggregate preferably is a member disposed on an object, and a planar shape of the porous ceramic aggregate as viewed from an upper surface thereof preferably is the same as a planar shape, as viewed from an upper surface thereof, of a region within the object where the porous ceramic aggregate is intended to be placed.
[3] In the first present invention, from among the plurality of porous ceramic particles included within the porous ceramic aggregate, there may exist at least one porous ceramic particle for which a planar shape as viewed from an upper surface thereof is a polygonal shape surrounded by a plurality of straight lines.
[4] In this case, from among the plurality of porous ceramic particles included within the porous ceramic aggregate, preferably a percentage of the porous ceramic particles including a curve in the planar shape as viewed from the upper surface thereof is less than or equal to 50%.
[5] Further, the porous ceramic aggregate may include a portion in which five or more porous ceramic particles are arranged with one apex each facing toward each other.
[6] In the first present invention, a gap between adjacent ones of the porous ceramic particles may be greater than or equal to 0.1 μm and less than or equal to 10 μm.
[7] In the first present invention, side surfaces of adjacent ones of the porous ceramic particles preferably face each other in parallel, and include a portion where an angle of inclination of a side surface of one of the adjacent porous ceramic particles is less than or equal to 45 degrees with respect to a normal line that is normal to the sheet.
[8] In the first present invention, preferably, number densities of the porous ceramic particles within the porous ceramic aggregate are different, and a ratio of a maximum value and a minimum value of the number densities defined by maximum number density/minimum number density is greater than 1.2.
[9] In the first present invention, preferably, sizes of planar shapes of the plurality of porous ceramic particles are different, and a ratio of a maximum value and a minimum value of the sizes of the planar shapes defined by the maximum value/the minimum value is greater than 1.2.
[10] In the first present invention, preferably, a thickness of the plurality of porous ceramic particles included within the porous ceramic aggregate is less than or equal to 1000 μm, and a variation in the thickness is less than or equal to 10%.
[11] In the first present invention, a porosity of the porous ceramic particles preferably is 20%˜99%.
[12] In the first present invention, the porous ceramic particles preferably have an average pore diameter of less than or equal to 500 nm.
[13] In the first present invention, a thermal conductivity of the porous ceramic particles preferably is less than 1.5 W/mK.
[14] In the first present invention, a heat capacity of the porous ceramic particles preferably is less than or equal to 1000 kJ/m3K.
[15] A method of manufacturing a porous ceramic structure according to a second present invention, the porous ceramic structure including one sheet, and a porous ceramic aggregate bonded on the sheet, wherein the porous ceramic aggregate includes a plurality of porous ceramic particles, the method including a green body manufacturing step of manufacturing a green body, a firing step of firing the green body to thereby manufacture a sintered body, a bonding step of bonding the sintered body to the sheet, and a dividing step of dividing the sintered body into a plurality of porous ceramic particles.
[16] In the second present invention, there may further be included a step of forming a plurality of cuts in the green body before firing the green body.
[17] In the second present invention, in the green body manufacturing step, the green body preferably is manufactured by applying a slurry on a film having a mirror surface, and tape-casting the slurry.
Owing to the porous ceramic structure according to the present invention, it is possible to achieve a low thermal conductivity, together with installing the porous ceramic structure directly on an object using an adhesive or the like, and further, it is possible to facilitate installation of a bulk body.
The above and other objects, features, and advantages of the present invention will become more apparent from the following description when taken in conjunction with the accompanying drawings, in which preferred embodiments of the present invention are shown by way of illustrative example.
An Example of a porous ceramic structure according to the present invention will be described below with reference to
As shown in
The term “porous” may refer to a state that is neither dense nor hollow, as well as a state composed of a plurality of pores or grains. Moreover, the term “dense” refers to a state in which a plurality of fine grains are bonded without gaps, having no pores. The term “hollow” refers to a state in which the interior is hollow, and in which an outer shell portion thereof is dense.
The porous ceramic particles 16 preferably have an aspect ratio greater than or equal to 3. More preferably, the aspect ratio is greater than or equal to 5, and even more preferably, is greater than or equal to 7. In this case, the aspect ratio is defined by the maximum length La divided by the minimum length Lb, or La/Lb. In this instance, the maximum length La refers to a maximum length on a widest surface (in this case, a single main surface 16a) from among the plurality of surfaces constituting the porous ceramic particles 16. Assuming that the widest surface is a square, a rectangle, a trapezoid, a parallelogram, or a polygon (pentagon, hexagon, etc.), the maximum length La corresponds to the length of a longest diagonal line, whereas if the widest surface is circular, the maximum length La corresponds to the length of a diameter, and if the widest surface is an ellipse, the maximum length La corresponds to the length of a major axis of the ellipse. On the other hand, as shown in
The minimum length Lb preferably is 50˜500 μm, more preferably, is 55˜400 μm, even more preferably is 60˜300 μm, and particularly preferably, is 70˜200 μm.
Concerning the sheet 12, for example, a resin-made sheet or a film having an adhesive strength can be used, and a sheet or film is preferable that becomes peelable due to temporal change or due to external factors such as heat, electricity, or external forces or the like.
The porous ceramic aggregate 14 is placed as a bulk body 20 on an object 22, by being coated with a resin material 18 (matrix) such as an adhesive, as will be described later (see
In this case, rather than placing individual porous ceramic particles 16 on the object 22, it is easier to collectively transfer a plurality of the porous ceramic particles 16 together onto the object 22, which also makes it easy to control the gaps between the porous ceramic particles 16.
A planar shape of the porous ceramic aggregate 14 as viewed from the upper surface is preferably the same as the planar shape as viewed from the upper surface of a region of the object 22 where the porous ceramic aggregate 14 is intended to be placed (hereinafter referred to as an installation area of the object 22). In this instance, the installation area of the object 22 is a concept that includes a portion of the object 22. The term “same” as used above includes a case of being entirely the same, or a case of being similar to the planar shape of the installation area of the object 22. In this instance, the similar relationship implies a shape obtained by enlarging the planar shape of the installation region of the object 22 by 1.1˜2.0 times, or a shape obtained by reducing such a planar shape by 1.1˜2.0 times. In accordance with this feature, a plurality of porous ceramic particles 16 can be transferred onto objects 22 of various shapes without causing a loss of material (a loss of the porous ceramic particles 16).
Further, among the plurality of porous ceramic particles 16 included within the porous ceramic aggregate 14, there may exist at least one porous ceramic particle 16 for which the planar shape as viewed from the upper surface thereof is a polygonal planar shape surrounded by a plurality of straight lines 24 (see
For example, as shown in
In the example of
Further, as shown in
If the planar shapes are solely linear, the porous ceramic particles 16 tend to be easily shifted upon transferring the plurality of porous ceramic particles 16 onto the object 22. However, as a result of the curves 26 existing partially within the porous ceramic aggregate 14, it is unlikely for such shifting to occur, and it also becomes possible to uniformly transfer the plurality of porous ceramic particles 16 onto the object 22.
In the case of determining the percentage of the porous ceramic particles 16 including a curve 26 in the planar shape thereof as viewed from the upper surface, such a percentage may be determined by counting the total number Nz of porous ceramic particles 16 on the sheet 12, and the total number Nw of porous ceramic particles 16 including a curve 26 in the planar shape thereof, and then performing the calculation (Number Nw/Number Nz)×100 (%).
In
In addition, as shown in
It is preferable for the gap d (see
Furthermore, as shown in
Moreover, the gap formed between adjacent porous ceramic particles 16 is not necessarily a linear gap. For example, as shown in
Further, the number densities of the porous ceramic particles 16 preferably differ by location in the porous ceramic aggregate 14. Further, the sizes of respective planar shapes of the plurality of porous ceramic particles 16 preferably are different.
For example, at a portion where the surface of the object 22 is flat, the number density is small (the size of the porous ceramic particles 16 is large), and at a portion where the surface of the object 22 is a curved surface and within the surrounding vicinity thereof, the number density is large (the size of the porous ceramic particles 16 is small). Hence, when the plurality of porous ceramic particles 16 is transferred onto the object 22, it is possible to arrange the plurality of porous ceramic particles 16 in following relation to the surface of the object 22.
The ratio of the maximum value and the minimum value of the number density (maximum number density/minimum number density) is preferably greater than 1.2.
The number density can be calculated in the following manner. More specifically, in the porous ceramic aggregate 14 that is bonded on the sheet 12, ten arbitrary fields of view are observed with an optical microscope, and the number of porous ceramic particles 16 contained within each field of view is measured. In relation to each of such fields of view, for example, a square region of 3 mm×3 mm can be adopted.
In addition, by dividing the number of the porous ceramic particles 16 included within each measured visual field by the area of the visual field (=9 mm2), the number density per unit area (number/mm2) is calculated. By comparing the number densities corresponding to the ten individual fields of view, the maximum number density and the minimum number density are extracted, and the ratio thereof (maximum number density/minimum number density) is calculated.
Further, the ratio (maximum value/minimum value) of the maximum value and the minimum value of the sizes of the planar shapes of the porous ceramic particles 16 preferably is greater than 1.2.
The sizes of the planar shapes of the porous ceramic particles 16 can be calculated in the following manner. More specifically, in the porous ceramic aggregate 14 that is bonded on the sheet 12, ten arbitrary fields of view are observed respectively with an optical microscope. In addition, for each field of view, five arbitrary straight lines are drawn respectively, and the length of line segments within the porous ceramic particles 16 that cross the straight lines are measured, and an average value thereof is taken to represent the size of the porous ceramic particles 16 within the field of view. The sizes of the porous ceramic particles 16 within the ten fields of view are compared, a maximum value and a minimum value of the sizes of the porous ceramic particles 16 are extracted, and the ratio thereof (maximum value/minimum value) is calculated.
A thickness ta (see
In accordance with this feature, as shown in
The porosity of the porous ceramic particles 16 preferably is 20%˜99%. The pores include at least one of closed pores and open pores, and may include both closed pores and open pores. Further, the shape of the pores, i.e., a surface shape of openings thereof, may be of any shape including a square shape, a quadrilateral shape, a triangular shape, a hexagonal shape, a circular shape, etc., or an irregular shape.
The average pore diameter preferably is less than or equal to 500 nm, and more preferably, is 10˜500 nm. This dimension is effective to inhibit the occurrence of lattice vibrations (phonons), which is a primary cause of thermal conductivity.
The porous ceramic particles 16 have a structure in which fine grains are connected in three dimensions. A grain diameter of the fine grains is preferably 1 nm˜5 μm. More preferably, the grain diameter is 50 nm˜1 μm. The porous ceramic particles 16, which are composed of fine grains having such a grain size range, effectively achieve a low thermal conductivity, since the occurrence of lattice vibrations (phonons), which is a primary cause of heat conduction, is inhibited. The fine grains may be a grain composed of one crystalline grain (a single crystalline grain), or a grain composed of a large number of crystalline grains (a polycrystalline grain). Stated otherwise, the porous ceramic particles 16 preferably are aggregations of fine grains having grain diameters lying within the aforementioned ranges. The grain diameter of the fine grains is determined by measuring, from an image of an electronic microscopic observation, the size (a diameter in the case of spherical grains, or a maximum diameter otherwise) of one grain of the grain groups that make up a framework of the porous ceramic particles 16.
The thermal conductivity of the porous ceramic particles 16 is preferably less than 1.5 W/mK, more preferably, is less than or equal to 0.7 W/mK, even more preferably, is less than or equal to 0.5 W/mK, and particularly preferably, is less than or equal to 0.3 W/mK.
The heat capacity of the porous ceramic particles 16 preferably is less than or equal to 1000 kJ/m3K, more preferably, is less than or equal to 900 kJ/m3K, even more preferably, is less than or equal to 800 kJ/m3K, and particularly preferably, is less than 500 kJ/m3K.
The constituent material of the porous ceramic particles 16 preferably contains a metal oxide, and more preferably, consists only of a metal oxide. This is because, if such a metal oxide is contained therein, the thermal conductivity tends to be lower, due to the fact that the ion binding property between metal and oxygen is stronger compared to the case of a non-oxide (for example, a carbide or nitride) of a metal.
In this case, the metal oxide preferably is an oxide of one element or a composite oxide of two or more elements selected from the group consisting of Zr, Y, Al, Si, Ti, Nb, Sr, La, Hf, Ce, Gd, Sm, Mn, Yb, Er, and Ta. This is because, if the metal oxide is an oxide or a composite oxide of such elements, heat conduction due to lattice vibrations (phonons) is unlikely to occur.
Specific examples of the material include ZrO2—Y2O3 to which Gd2O3, Yb2O3, Er2O3, etc., is added. As further specific examples thereof, there may be cited ZrO2—HfO2—Y2O3, ZrO2—Y2O3—La2O3, ZrO2—HfO2—Y2O3—La2O3, HfO2—Y2O3, CeO2—Y2O3, Gd2Zr2O7, Sm2Zr2O7, LaMnAl11O19, YTa3O9, Y0.7La0.3Ta3O9, Y1.08Ta2.76Zr0.24O9, Y2Ti2O7, LaTa3O9, Yb2Si2O7, Y2Si2O7, Ti3O5, and the like.
Next, with reference to
Initially, the first manufacturing method will be described. First, in step S1 of
Thereafter, in step S2, the casting slurry 36 is subjected to a vacuum defoaming treatment, whereby the viscosity of the slurry is adjusted, followed by carrying out tape casting in order to manufacture a cast body 30 (green sheet, green body) (green body manufacturing step). For example, as shown in
Thereafter, in step S3 of
Thereafter, in step S6, the sintered body 40 is divided into a plurality of porous ceramic particles 16 (dividing step). Consequently, a porous ceramic structure 10 having one sheet 12, and a porous ceramic aggregate 14 bonded to the sheet 12 and made up of a plurality of porous ceramic particles 16 is obtained. A surface modification treatment may be performed on the sintered body 40 after the firing step, or may be performed on the porous ceramic particles 16 after the dividing step. Such a surface modification treatment is a treatment (principally a treatment to make permeation of the resin material unlikely) for controlling the degree of penetration of the resin material 18 (matrix: see
The above-described dividing step in step S6 divides the sintered body 40 into a plurality of small pieces, or stated otherwise, a plurality of porous ceramic particles 16. Of course, in the dividing step, such division can be carried out by various methods. For example, a knife may be pressed against the sintered body 40 in order to cut (divide) the sintered body 40 into a plurality of porous ceramic particles 16, or the sintered body 40 may be cut with a laser into a plurality of the porous ceramic particles 16, or the like. In this case, from the fact that the sintered body 40 is firmly bonded to the sheet 12, when division is performed, peeling of the sintered body 40 and the porous ceramic particles 16 from the sheet 12 is prevented.
Next, the second manufacturing method will be described with reference to
Thereafter, in step S104, by carrying out laser machining or press machining, a plurality of cutting lines (cuts) 42 are formed from the upper surface of the cast body 30.
Thereafter, in steps S105 to S107, in the same manner as in the aforementioned steps S4 to S6, the picked cast body 30 is fired, whereby a sheet-shaped sintered body 40 is obtained. In addition, the sintered body 40 is bonded onto the sheet 12 and divided into a plurality of the porous ceramic particles 16.
Consequently, a porous ceramic structure 10 having one sheet 12, and a porous ceramic aggregate 14 bonded to the sheet 12 and made up of a plurality of porous ceramic particles 16 is obtained. Moreover, in the second manufacturing method as well, a surface modification treatment may be performed on the sintered body 40 after the firing step, or may be performed on the porous ceramic particles 16 after the dividing step.
Next, a method of constructing a single bulk body 20 using the porous ceramic structure 10 will be described with reference to
First, as shown in
Then, as shown in
Thereafter, as shown in
Conventionally, as shown in
In contrast thereto, in the present embodiment, the porous ceramic structure 10, which includes the porous ceramic aggregate 14 composed of the plurality of porous ceramic particles 16 bonded on the sheet 12, is placed on the object 22. Thereafter, the sheet 12 is peeled off, and the porous ceramic aggregate 14 is transferred onto the object 22. Then, the porous ceramic aggregate 14 is coated with the resin material 18 (matrix) such as an adhesive or the like to thereby constitute the bulk body 20.
Therefore, it is possible to uniformly disperse and arrange the plurality of porous ceramic particles 16 in the resin material 18. In addition, since regions composed of only the resin material 18 having a thermal conductivity higher than that of the porous ceramic particles 16 are narrowed, the thermal conductivity of the bulk body 20 can be suppressed and remain low. Moreover, the thermal conductivity can be equalized within the bulk body 20, there is no need to change or modify the bulk body 20 corresponding to the location where the bulk body 20 is installed, the process of arranging the bulk body 20 can be simplified, and the number of steps required therefor can be reduced.
Further, since the sintered body 40 bonded to the sheet 12 is divided into a plurality of porous ceramic particles 16, unlike the case of the conventional technique, a plurality of the porous ceramic particles 16 can be arranged uniformly on the object 22. In addition, even in the case that the surface of the object 22 is of an irregular shape (warped or the like) or a curved surface, the plurality of porous ceramic particles 16 can be easily arranged along a surface shape of the object 22, and the degree of freedom of design can be enhanced. Further, since the porous ceramic structure 10 is composed of the sheet 12 and the porous ceramic aggregate 14 having the plurality of porous ceramic particles 16 that are bonded on the sheet 12, handling of the porous ceramic structure 10 is facilitated, while in addition, the operation of transferring the plurality of porous ceramic particles 16 onto the object 22 is simplified. This is advantageous in terms of simplifying the manufacturing process.
Preferably, the adhesive strength (JIS Z0237) of the sheet 12 is greater than or equal to 1.0 N/10 mm, the tensile elongation (JIS K7127) of the sheet 12 is greater than or equal to 0.5%, and the thickness of the sheet 12 is less than or equal to 5 mm. Consequently, the following effects can be obtained.
(a) The higher the adhesive strength, the more firmly the porous ceramic particles 16 can be fixed.
(b) As the tensile elongation increases, it is possible to follow the curved surface.
(c) As the thickness thereof is thinner, it becomes easier to follow the curved surface.
In greater detail, the adhesive strength of the sheet 12 exhibits the following properties. More specifically, the adhesive strength at the time that the porous ceramic particles 16 are retained is greater than or equal to 1.0 N/10 mm, and the adhesive strength at the time of peeling the porous ceramic particles 16 is less than or equal to 0.1 N/10 mm.
The method of evaluating the adhesive strength of the sheet 12 is the same as the method used for evaluating the adhesive strength of an adhesive tape. In particular, the sheet 12 is attached to a stainless steel plate, and the sheet 12 is pulled at an angle of 180 degrees or 90 degrees, whereupon the force applied when peeling the sheet 12 off from the stainless steel plate is regarded as the adhesive force (adhesive strength).
Further, the sheet 12 is formed by applying an adhesive to a base material (support). In this case, as the type of base material, preferably a material is selected from among the following.
More specifically, when the porous ceramic particles 16 are transferred onto the planar object 22, it is preferable to use a film, metal foil, paper, or the like as the base material. In this case, since the base material of the sheet 12 is stiff, it is possible to dispose the sheet 12 in the form of a film without wrinkles with respect to the planar object 22.
In the case of transferring the porous ceramic particles 16 onto an object 22 having a curved surface (convex surface, concave surface, irregular surface) shape, it is preferable to use a cloth, a rubber sheet, foam or the like as the base material. In this case, since the base material of the sheet 12 is soft and stretchable, it is possible to dispose the sheet 12 in following relation to the curved surface shape of the object 22.
Further, by application of heat, water, a solvent, light (ultraviolet light), or microwaves, the adhesive strength of the sheet 12 can be weakened and the sheet 12 can be easily peeled off. At this time, the adhesive strength of the sheet 12 is preferably weaker than the adhesive strength of the adhesive 44 that is used between the object 22 and the porous ceramic structure 10.
A confirmation was carried out concerning the thermal conductivity, a smallness of loss of material, a smallness of positional shifting of the porous ceramic particles 16, ease of following the curved surface, and the likelihood of cracking or chipping of the porous ceramic particles 16 when transferring them onto the object 22 for each of various bulk bodies 20, for cases in which the bulk bodies 20 were constituted using the porous ceramic structures 10 according to Examples 1 to 8, and porous ceramic structures according to Comparative Examples 1 and 2.
Porous ceramic particles 16 each having a porosity of 60% and a thickness of 60 μm were used as the plurality of porous ceramic particles 16 constituting the porous ceramic structure 10, and a bulk body 20 according to Example 1 was prepared according to the above-described first manufacturing method. More specifically, at first, a porous ceramic structure 10 including a sheet 12 and a plurality of porous ceramic particles 16 bonded to one surface of the sheet 12 was used. Then, after coating an adhesive 44 (thermal conductivity 2 W/mK) onto an object 22, the plurality of porous ceramic particles 16 were transferred onto the adhesive 44 of the object 22 using the sheet 12, and by application of heat thereto, the sheet 12 was peeled off. After coating the transferred particles on the object with a resin material 18 (matrix) from above, the resin material 18 was solidified, and the bulk body 20 was installed on the surface of the object 22.
In Example 1, a porous ceramic structure 10 for use in measuring porosity, and a porous ceramic structure 10 for use as a bulk body were manufactured in the following manner. The porous ceramic structures of the later-described Examples 2 to 8, and Comparative Example 2 were also manufactured in a similar manner.
First, a pore forming agent (latex particles or melamine resin particles), a polyvinyl butyral resin (PVB) as a binder, DOP (dioctyl phthalate) as a plasticizer, and xylene and 1-Butanol as solvents were added to yttria-partially-stabilized zirconia powder, and mixed in a ball mill for 30 hours in order to prepare a casting slurry 36. The casting slurry 36 was subjected to a vacuum defoaming treatment, whereby the viscosity thereof was adjusted to 4000 cps, and thereafter, the cast body 30 (green sheet) was produced by the doctor blade device 32 such that a thickness thereof after firing was 60 μm. Thereafter, the cast body 30 was fired at 1100° C. for 1 hour in order to obtain the sintered body 40. Thereafter, the sintered body 40 was bonded onto the upper surface of the sheet 12. Furthermore, the sintered body 40 was divided into a plurality of the porous ceramic particles 16. More specifically, a porous ceramic structure 10 was manufactured, in which a porous ceramic aggregate 14 made up of a plurality of porous ceramic particles 16 was bonded on the sheet 12.
The planar shape of the porous ceramic aggregate 14 on the sheet 12 is a square shape having a length of 100 mm and a width of 100 mm, and the area of one of the porous ceramic particles 16 is about 0.25 mm2. More specifically, the porous ceramic structure 10 is formed in a state with roughly 40000 of the porous ceramic particles 16 being arrayed on the sheet 12.
In the porous ceramic structure 10 according to Example 1, the planar shape of the porous ceramic aggregate 14 made up from the plurality of porous ceramic particles 16 as viewed from the upper surface is different from the planar shape of a region within the object 22 where the porous ceramic aggregate 14 is intended to be placed, as viewed from the upper surface. In the porous ceramic structure 10, the planar shapes of the plurality of porous ceramic particles 16 that make up the porous ceramic structure 10 were all in the form of polygonal shapes surrounded by straight lines 24. The angles of inclination θ of the side surfaces of the respective porous ceramic particles 16 exceeded 45 degrees, respectively, and was less than or equal to 50 degrees with respect to the normal line 28 that is normal to the sheet 12. Further, the thickness to of the porous ceramic particles 16 was 45-55 μm, and the variation in thickness was 10%. The gap d between the porous ceramic particles 16 was 5˜10 μm, the ratio of the maximum number density to the minimum number density (maximum number density/minimum number density) was 1.15, and the ratio of the maximum value and the minimum value of the sizes of the planar shapes (maximum value/minimum value) was 1.15. Further, there were portions where, at a maximum, four porous ceramic particles 16 were arranged with one apex each facing toward each other.
The bulk body 20 according to Example 2 was manufactured in the same manner as in Example 1, except for the feature that, as the porous ceramic structure 10, a porous ceramic structure 10 was used in which the planar shape of the porous ceramic aggregate 14 made up from the plurality of porous ceramic particles 16 as viewed from the upper surface is the same as the planar shape of a region within the object 22 where the porous ceramic aggregate 14 is intended to be placed as viewed from the upper surface.
The bulk body 20 according to Example 3 was manufactured in the same manner as in Example 1, except for the feature that, as the porous ceramic structure 10, a porous ceramic structure 10 was used in which, from among the plurality of porous ceramic particles 16, the percentage Pa of the porous ceramic particles including a curve 26 in the planar shape thereof as viewed from the upper surface is greater than 0% and less than or equal to 50%.
The bulk body 20 according to Example 4 was manufactured in the same manner as in Example 1, except for the feature that, as the porous ceramic structure 10, a porous ceramic structure 10 was used which includes a portion 27 (see
The bulk body 20 according to Example 5 was manufactured in the same manner as in Example 1, except for the feature that, as the porous ceramic structure 10, a porous ceramic structure 10 was used in which the angle of inclination θ of the side surfaces of the plurality of porous ceramic particles 16 constituting the porous ceramic aggregate 14 is greater than or equal to 0 degrees and less than or equal to 45 degrees with respect to a normal line 28 that is normal to the sheet 12.
The bulk body 20 according to Example 6 was manufactured in the same manner as in Example 1, except for the feature that, as the porous ceramic structure 10, a porous ceramic structure 10 was used in which the ratio of the maximum number density to the minimum number density (maximum number density/minimum number density) of the plurality of porous ceramic particles 16 making up the porous ceramic aggregate 14 is 1.25.
The bulk body 20 according to Example 7 was manufactured in the same manner as in Example 1, except for the feature that, as the porous ceramic structure 10, a porous ceramic structure 10 was used in which the ratio (maximum value/minimum value) of the maximum value and the minimum value of the sizes of the planar shapes of the plurality of porous ceramic particles 16 making up the porous ceramic aggregate 14 is 1.25.
The bulk body 20 according to Example 8 was manufactured in the same manner as in Example 1, except for the feature that, as the porous ceramic structure 10, a porous ceramic structure 10 was used in which the thickness ta of the plurality of porous ceramic particles 16 making up the porous ceramic aggregate 14 is 47.5 to 52.5 μm, and the variation in thickness is 5%.
As shown in
A plurality of porous ceramic particles 16 each having a porosity of 60% and a thickness ta of 47.5˜52.5 μm were bonded directly on the object 22 with an adhesive 44 and without using the sheet 12, and after coating the particles bonded on the object with a resin material 18 (matrix) from above, the resin material 18 was solidified to thereby prepare a bulk body 20 according to Comparative Example 2.
In Table 1 appearing below, there is shown a compositional breakdown of Examples 1 to 8 and Comparative Examples 1 and 2. Note that, in Table 1, the upwardly pointing arrows “↑” indicate that the content thereof is the same as the examples shown above.
With respect to Examples 1 to 8, ten porous ceramic particles 16 were selected at random from among the plurality of porous ceramic particles 16 constituting a porous ceramic structure 10 for use in measuring porosity, and the selected porous ceramic particles 16 were embedded in a resin. The resin was polished until producing an observation site at which the porous ceramic particles 16 could be observed with an electron microscope, to thereby obtain a resin-filled polished surface. Then, an electron microscopic observation (image analysis) was performed on the resin-filled polished surface. From such an image analysis, the respective porosities of the ten porous ceramic particles 16 were calculated, and the average value of the ten porous ceramic particles 16 was taken as the porosity of the porous ceramic particles 16. Concerning Comparative Example 2, ten porous ceramic particles 16 for use in measuring porosity were selected, and the porosity of the porous ceramic particles 16 was determined by the same method as described above.
The average pore diameter of the porous ceramic particles 16 was measured using an automated porosimeter (trade name “Autopore 9200”) manufactured by Shimadzu Corporation.
At first, the density of the bulk body 20 was measured with a mercury porosimeter. Next, the specific heat of the bulk body 20 was measured using a DSC (Differential Scanning calorimeter) method. Next, the thermal diffusivity of the bulk body 20 was measured using a laser flash method. Thereafter, the thermal conductivity of the bulk body 20 was calculated from the following relational expression:
Thermal Diffusivity×Specific Heat×Density=Thermal Conductivity
Then, based on the following evaluation criteria, the thermal conductivities of Examples 1 to 8 and Comparative Examples 1 and 2 were evaluated.
A: Less than or equal to 0.9 W/mK
B: Greater than or equal to 1.0 W/mK and less than or equal to 1.4 W/mK
C: Greater than or equal to 1.5 W/mK and less than or equal to 1.9 W/mK
D: Greater than or equal to 2.0 W/mK
The gaps d between the plurality of porous ceramic particles 16 that make up the porous ceramic aggregate 14 were measured respectively with an optical microscope.
The thicknesses ta of the plurality of porous ceramic particles 16 that make up the porous ceramic aggregate 14 were measured respectively with an optical microscope.
The angles of inclination θ of the plurality of porous ceramic particles 16 that make up the porous ceramic aggregate 14 were measured respectively with an optical microscope.
A total number of the plurality of porous ceramic particles 16 constituting the porous ceramic aggregate 14, and the number of the porous ceramic particles 16 including a curve 26 in the planar shape thereof were determined, and the value (number/total number)×100 (%) was calculated.
In the porous ceramic aggregate 14 that is bonded on the sheet 12, ten arbitrary fields of view were observed with an optical microscope, and the number of porous ceramic particles 16 contained within each field of view was measured. In relation to each of such fields of view, for example, a square region of 3 mm×3 mm was adopted. In addition, by dividing the number of the porous ceramic particles 16 included within each measured visual field by the area of the visual field (=9 mm2), the number density per unit area (number/mm2) was calculated. By comparing the number densities corresponding to the ten individual fields of view, the maximum number density and the minimum number density were extracted, and the ratio thereof (maximum number density/minimum number density) was calculated.
In the porous ceramic aggregate 14 that is bonded on the sheet 12, ten arbitrary fields of view were observed with an optical microscope. In addition, for each field of view, five arbitrary straight lines were drawn respectively, the length of line segments within the porous ceramic particles 16 that cross the straight lines were measured, and an average value thereof was taken to represent the size of the porous ceramic particles 16 within the field of view. The sizes of the porous ceramic particles 16 within the ten fields of view were compared, a maximum value and a minimum value of the sizes of the porous ceramic particles 16 were extracted, and the ratio thereof (maximum value/minimum value) was calculated.
The number Na of porous ceramic particles 16 existing on the object 22 was confirmed using an optical microscope, and the percentage of the number Na with respect to the total number Nz of porous ceramic particles 16 on the sheet 12, or more specifically, the value (Number Na/Total Number Nz)×100 (%), was determined. In addition, Examples 1 to 8 and Comparative Examples 1 and 2 were evaluated on the basis of the following Evaluation Standards.
A: Greater than or equal to 95%
B: Greater than or equal to 85% and less than 95%
C: Less than 85%
Among the porous ceramic particles 16 present on the object 22, the porous ceramic particles 16 having a largest amount of positional shifting were confirmed with an optical microscope, and the amount of positional shifting was measured. In addition, Examples 1 to 8 and Comparative Examples 1 and 2 were evaluated on the basis of the following Evaluation Standards.
A: Amount of shifting less than 0.5 mm
B: Amount of shifting greater than or equal to 0.5 mm
The number Nb of the porous ceramic particles 16 whose peripheral portion remains floating from among the porous ceramic particles 16 existing on the object 22 was confirmed with an optical microscope, and the percentage of the number Nb with respect to the total number Nz of porous ceramic particles 16 on the sheet 12, or more specifically, the value (Number Nb/Total Number Nz)×100 (%), was determined. In addition, Examples 1 to 8 and Comparative Examples 1 and 2 were evaluated on the basis of the following Evaluation Standards.
A: Less than 5%
B: Greater than or equal to 5%
[Evaluation of Likelihood of Cracking or Chipping of Porous Ceramic Particles 16 at a Time of Transfer Thereof onto the Object 22]
The number Nc of porous ceramic particles 16 lacking peripheral portions from among the porous ceramic particles 16 existing on the object 22 was confirmed using an optical microscope, and the percentage of the number Nc with respect to the total number Nz of porous ceramic particles 16 on the sheet 12, or more specifically, the value (Number Nc/Total Number Nz)×100 (%), was determined. In addition, Examples 1 to 8 and Comparative Examples 1 and 2 were evaluated on the basis of the following Evaluation Standards.
A: Less than 5%
B: Greater than or equal to 5%
Evaluation results of Examples 1 to 8 and Comparative Examples 1 and 2 are shown below in Table 2.
As can be understood from Table 2, in Comparative Example 1, the thermal conductivity was greater than or equal to 2.0 W/mK. In the bulk body 54 according to Comparative Example 1, it is considered that the reason the thermal conductivity was increased is because there were many regions 58 in which only the adhesive 56 was present. In Comparative Example 2 as well, the thermal conductivity was greater than or equal to 1.5 W/mK. In the bulk body 54 according to Comparative Example 2, this is considered to be due to the fact that, since the porous ceramic particles 16 were bonded individually to the object 22, wide gaps occurred between the porous ceramic particles 16, and many regions existed in which only the resin material 18 was present.
In contrast thereto, in any of Examples 1 to 8, the thermal conductivity was low at less than or equal to 1.4 W/mK, and in particular, in Examples 5 and 8, the thermal conductivity was extremely low at 0.9 W/mK. This is considered to be due to the fact that, since the plurality of porous ceramic particles 16 were uniformly dispersed in the resin material 18, and regions composed of only the resin material 18 having a high thermal conductivity were narrowed, the thermal conductivity of the bulk body 20 can be suppressed to remain at a low value.
Among Examples 1 to 8, concerning the smallness of the loss of the material, the loss of material was lowest in Example 2. Concerning the smallness of positional shifting, the amount of shifting was smallest in Example 3. Concerning the ease of following the curved surface of the object 22, a high evaluation therefor was indicated in Examples 4, 6 and 7. Concerning the likelihood of cracking or chipping, cracking or chipping was most unlikely to occur in Example 5.
The porous ceramic structure and the method of manufacturing the same, according to the present invention, are not limited to the above-described embodiments, and it is a matter of course that various configurations can be adopted therein without departing from the scope of the present invention.
In the above examples, the porous ceramic aggregate 14 is coated with the resin material 18 when the bulk body 20 is manufactured. However, alternatively, a portion of the porous ceramic aggregate 14 may be coated with the resin material 18 to thereby form the bulk body 20, or the bulk body 20 may be formed merely by installing the porous ceramic aggregate 14 on the object 22 without using the resin material 18.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2016-111136 | Jun 2016 | JP | national |
