CN115286411B - Titanium dioxide whisker reinforced magnesium oxide ceramic substrate material and preparation method thereof - Google Patents
Titanium dioxide whisker reinforced magnesium oxide ceramic substrate material and preparation method thereof Download PDFInfo
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 239000000395 magnesium oxide Substances 0.000 title claims abstract description 82
- 239000000919 ceramic Substances 0.000 title claims abstract description 53
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 title claims abstract description 38
- 239000000758 substrate Substances 0.000 title claims abstract description 34
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 17
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000005452 bending Methods 0.000 claims abstract description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 15
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 239000010431 corundum Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 239000004570 mortar (masonry) Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- 238000007873 sieving Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 231100000956 nontoxicity Toxicity 0.000 abstract description 3
- 238000000748 compression moulding Methods 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000011449 brick Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001144 powder X-ray diffraction data Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/03—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
- C04B35/04—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on magnesium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5276—Whiskers, spindles, needles or pins
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Abstract
The invention relates to the technical field of electronic ceramics, in particular to a titanium dioxide whisker reinforced magnesia ceramic substrate material and a preparation method thereof, which are characterized in that the material is a mixture composed of inorganic components and organic components, wherein the inorganic components are magnesium oxide micropowder and TiO 2 Whisker is mixed, and the organic component is polyvinyl alcohol Ding Quanzhi (PVB). The preparation method comprises the steps of 1) presintering, 2) ball milling, 3) drying and grinding, 4) mixing, 5) compression molding and 6) sintering. Compared with the prior art, the invention has the advantages that: 1) The bending strength is up to 165-221 MPa, the Vickers hardness is 585-1048 Hv, the dielectric constant is 10.6-11.9 (300 kHz), and the dielectric loss is less than 2.44 multiplied by 10 ‑4 . 2) The invention has the advantages of easily obtained raw materials, simple production process, no toxicity or pollution of all components, meeting the requirements of microminiature integrated substrate materials and being suitable for mass production.
Description
Technical Field
The invention relates to the technical field of electronic ceramics, in particular to a titanium dioxide whisker reinforced magnesia ceramic substrate material and a preparation method thereof.
Background
Magnesium oxide is an ionic compound, mgO in chemical formula, belongs to a cubic system, and has the advantages of face-centered cubic structure, compact and ordered internal ion accumulation, and high ionic bond strength, so that the dielectric loss of the magnesium oxide is reduced with the increase of frequency, and the magnesium oxide is macroscopically white, and is a typical alkaline earth metal oxide, the melting point of the magnesium oxide is 2800+/-13 ℃, the boiling point of the magnesium oxide is 3600 ℃, and the density of the magnesium oxide is 3.58g/cm 3 The high-temperature-resistant metal crucible is a good insulator, has the resistivity of about 2.4X108 ohm cm at room temperature, and has the resistivity which is sharply reduced along with the temperature rise, and has good high-temperature resistance, and can be used as a crucible for smelting metal; is also suitable for smelting in the atomic energy industryUranium and thorium of high purity; can also be used as a thermocouple protective sleeve; by utilizing the property of the ceramic material that electromagnetic waves can pass through, the ceramic material is used as a radar cover, an infrared radiation transmission window material and the like, however, the sintering of pure magnesia ceramic is not easy to compact, and the bending strength and the hardness are relatively poor.
Along with the development of technology, electronic devices are developed, and accordingly, the material requirements for packaging chips are also increased. The traditional substrate material can not meet the requirements, and the novel heat dissipation packaging material with high heat conduction, low dielectric constant, low dielectric loss and good mechanical property is invented. Although the magnesium oxide ceramic has excellent dielectric property, so that the magnesium oxide ceramic can meet the requirement of a high-frequency dielectric material, the mechanical property of the magnesium oxide ceramic is relatively poor, and under the requirement of microminiature integration, the magnesium oxide ceramic does not meet the requirement, and how to improve the mechanical property of the magnesium oxide ceramic has very important significance.
For example, patent application CN105439544A0 discloses a magnesia ceramic and a preparation method thereof, the components of which include: 960-1000 parts of magnesium oxide micropowder, 20-40 parts of magnesium oxide nanopowder, 8-16 parts of water reducer, 25-35 parts of dextrin, 90-130 parts of maltose, 20-45 parts of mineral oil, 30-60 parts of carboxymethyl cellulose, 2-4 parts of glycerol and 15-25 parts of hydroxypropyl cellulose. And extrusion molding and three-section sintering processes are utilized, so that the sintering rejection rate is reduced, and the sintering strength and density are improved. Patent application CN201010281144.0 discloses a preparation method of high-density magnesia ceramic, which comprises calcining nanoscale high-purity basic magnesium carbonate to obtain nano magnesia powder, and sintering at 1300deg.C for 180min at a temperature rise rate of 10deg.C/min under 800MPa pressure molding to obtain magnesia ceramic with a relative density of 98.2%. The production process is too complex; although the two methods can prepare relatively dense magnesia ceramics, the two methods have the defects of various raw materials, severe raw material requirements, complex operation process and adverse industrial production. Both methods are to show the mechanical properties of the magnesia ceramics, and the compact magnesia ceramics have lower bending strength and lower hardness.
The main stream substrate in the market at present is still an alumina ceramic substrate, and magnesia ceramic has higher heat conductivity coefficient compared with the alumina ceramic substrate, which is very beneficial to the substrate, and under the condition of not affecting the dielectric property and the heat conductivity of magnesia ceramic, the mechanical property of magnesia ceramic is improved so as to meet the practical requirement of the field, and no related report exists at present.
Disclosure of Invention
The invention aims to provide a titanium dioxide whisker reinforced magnesia ceramic substrate material and a preparation method thereof, which overcome the defects of the prior art and utilize TiO 2 (w) improving mechanical properties of MgO ceramics, tiO 2 The whisker and MgO crystal grain are chemically reacted to generate new phase which is uniformly distributed at MgO crystal boundary, the MgO ceramic composite material is best sintered, and all mechanical properties are maximum. The invention has the advantages of available raw materials, simple production process, no toxicity or pollution of the used medicines, meeting the requirements of industrial production and microminiature integrated substrate materials, and being suitable for mass production.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
one of the technical proposal is as follows: the titanium dioxide whisker reinforced magnesia ceramic substrate material is characterized in that the material is a mixture of inorganic components and organic components in a weight ratio of 9:1, wherein the inorganic components comprise 82-97wt% of magnesia micro powder and 3-18wt% of TiO 2 Whisker is mixed, and the organic component is polyvinyl alcohol Ding Quanzhi (PVB).
Further, the granularity of the magnesium oxide micro powder is 0.5-1.0 mu m, the magnesium oxide content is more than or equal to 98.5%, and the water content is less than or equal to 1.0%.
Further, the TiO 2 The whisker has length of 15-30 μm, diameter of 1-3 μm, length-diameter ratio of more than 10, and TiO 2 The content is more than or equal to 99.9 percent, and the water content is less than or equal to 1.0 percent.
Further, the polyvinyl butyral Ding Quanzhi is prepared from polyvinyl butyral and absolute ethyl alcohol according to the weight ratio of 1:9, at room temperature, oscillating by an ultrasonic oscillator and stirring for 10-20 minutes by a glass rod, so that the polyvinyl butyral is completely dissolved in the absolute ethyl alcohol.
Further, the inorganic component comprises magnesium oxide micropowder and TiO 2 The weight percentage of the whisker is any one of 94:6, 91:9, 88:12 and 85:15.
Further, the bending strength of the substrate material is 165-221 MPa, vickers hardness is 585-1048 Hv, dielectric constant is 10.6-11.9 (300 kHz), and dielectric loss is less than 2.44×10 -4 。
The second technical scheme is as follows: the preparation method of the titanium dioxide whisker reinforced magnesia ceramic substrate material is characterized by comprising the following preparation steps:
1) Presintering, namely presintering raw material magnesium oxide micro powder for 2-4 hours at 900-960 ℃ to decompose magnesium hydroxide into magnesium oxide;
2) Ball milling, weighing MgO: tiO (titanium dioxide) 2 The formula amount of (w) is that an ethanol grinding medium is put into a ball milling tank, the materials are mixed with ethanol according to the mass volume ratio of 1g to 3.5ml, ball milling is carried out for 6 hours, the rotating speed of the ball mill is 450-550 r/min, and the granularity after ball milling is 200 meshes;
3) Drying and grinding, namely drying and grinding the materials which are ball-milled in the step 2), wherein the drying adopts drying oven equipment, the water content after drying is less than or equal to 0.1%, the grinding adopts a corundum mortar, and the granularity of the mixture after grinding is more than 300 meshes;
4) Mixing, namely adding the mixture obtained in the step 3) into PVB with the formula amount for continuous uniform mixing;
5) Press molding, namely press molding the mixture in the step 4) in a die, putting the green body into a cold isostatic press, maintaining the pressure at 200MPa for at least 30 seconds, and demoulding to obtain the green body;
6) Sintering, namely performing glue discharging sintering on the green body in the step 5) under the air atmosphere, preserving heat for 1-3 hours at 600-650 ℃, and then raising the temperature to 1450-1550 ℃ and preserving heat for 3-6 hours;
further, the drying temperature in the step 2) is 100 ℃, and the drying time is 60 minutes.
The working principle of the invention is to use TiO 2 (w) improving mechanical properties of MgO ceramics, tiO 2 The whisker and MgO crystal grain are chemically reacted to generate new phase which is uniformly distributed at MgO crystal boundary, and the new phase is compared with the traditional TiO 2 The micro powder is different from MgO in that the new phase generated by the reaction is not multiple crystalsGrain boundaries are uniformly distributed at the grain boundaries of any two adjacent grains. The structure is just like a 'building piled by bricks', and the cement is used for bonding any two adjacent bricks together, so that the mechanical property of the MgO ceramic with the structure is greatly improved, and the structure has the advantages of simple process and low raw material price, and is very suitable for industrial production.
Compared with the prior art, the invention has the beneficial effects that:
1) TiO of the invention 2 The bending strength of (w) -MgO composite ceramic substrate material reaches 165-221 MPa, the Vickers hardness is 585-1048 Hv, the dielectric constant is 10.6-11.9 (300 kHz), and the dielectric loss is less than 2.44 multiplied by 10 -4 When TiO 2 When the whisker addition amount is 12wt%, the MgO ceramic composite material is best sintered, and all mechanical properties reach the maximum.
2) The invention has the advantages of easily obtained raw materials, simple production process, no toxicity or pollution of the raw material components, meeting the requirements of industrial scale production and microminiature integrated substrate materials, and having popularization value.
Drawings
FIG. 1 shows the addition of 12wt% TiO in example 4 of the present invention 2 Ceramic powder XRD pattern of whiskers;
FIG. 2 shows the addition of 12wt% TiO in example 4 of the present invention 2 SEM image of ceramic surface of whisker;
FIG. 3 shows the addition of 12wt% TiO in example 4 of the present invention 2 SEM images of ceramic fracture of whiskers;
FIG. 4 shows MgO grains and Mg in example 4 of the present invention 2 TiO 4 Schematic diagram of grain boundary.
Detailed description of the preferred embodiments
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. 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.
The following description of the embodiments of the present invention will be made apparent and fully in view of the accompanying drawings, in which some, but not all embodiments of the invention are shown.
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other embodiments may be obtained according to the description without the need of inventive effort for a person skilled in the art. Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention.
Example 1
The embodiment provides a titanium dioxide whisker reinforced magnesia ceramic substrate material, which comprises the following raw materials in percentage by weight: 90wt% (97% MgO, 3% TiO) 2 Whisker), PVB:10wt%.
The preparation steps of the embodiment are as follows: firstly, presintering magnesium oxide micro powder for 2 hours at 900 ℃; weighing the raw materials, putting the raw materials into a ball mill, mixing the raw materials with ethanol in a ratio of 1g to 3.5ml, and ball milling for 6 hours, wherein the rotating speed of the ball mill is 450r/min; placing the ball-milled materials into a drying box, preserving heat for 1 hour at 100 ℃, drying, and adding PVB and uniformly mixing; pressing the mixed materials under the axial pressure of 5MPa, removing the film to obtain a green body, and carrying out cold isostatic pressing on the green body for 200MPa; and (3) performing glue discharging sintering on the prepared green body in an air atmosphere, heating to 600 ℃ at a heating rate of 5 ℃/min, preserving heat for 1 hour, heating to 1100 ℃ at a heating rate of 4 ℃/min, heating to 1450 ℃ at a heating rate of 3 ℃/min, preserving heat for 3 hours, and cooling along with the furnace temperature to obtain a ceramic sample, wherein each property of the ceramic sample is shown in table 1.
Example 2
The embodiment provides a titanium dioxide whisker reinforced magnesia ceramic substrate material, which comprises the following components: raw materials: 90wt% (94% MgO, 6% TiO) 2 Whisker), PVB:10wt%.
The procedure for the preparation of this example was the same as in example 1.
Example 3
The embodiment provides a titanium dioxide whisker reinforced magnesia ceramic substrate material, which comprises the following components: raw materials: 90wt% (91% MgO, 9% TiO) 2 Whisker), PVB:10wt%.
The procedure for the preparation of this example was the same as in example 1.
Example 4
The embodiment provides a titanium dioxide whisker reinforced magnesia ceramic substrate material, which comprises the following components: raw materials: 90wt% (88% MgO, 12% TiO) 2 Whisker), PVB:10wt%.
The procedure for the preparation of this example was the same as in example 1.
Example 5
The embodiment provides a titanium dioxide whisker reinforced magnesia ceramic substrate material, which comprises the following components: raw materials: 90wt% (85% MgO, 15% TiO) 2 Whisker), PVB:10wt%.
The procedure for the preparation of this example was the same as in example 1.
Example 6
The embodiment provides a titanium dioxide whisker reinforced magnesia ceramic substrate material, which comprises the following components: raw materials: 90wt% (82% MgO, 18% TiO) 2 Whisker), PVB:10wt%.
The procedure for the preparation of this example was the same as in example 1.
The comparison of the properties of the ceramic samples of examples 1-6 of the present invention is shown in Table 1.
TABLE 1
See FIGS. 1-4 for preferred embodiments of the inventionThe associated drawing of example 4. Wherein FIG. 1 is the addition of 12wt% TiO 2 Ceramic powder XRD patterns of whiskers, which demonstrate TiO 2 The whisker does react with MgO to generate new phase Mg 2 TiO 4 The method comprises the steps of carrying out a first treatment on the surface of the FIG. 2 is a graph of the addition of 12wt% TiO 2 SEM image of the ceramic surface of whisker, can be seen from the image, the "pile up" structure that the invention belongs to; FIG. 3 is a graph of the addition of 12wt% TiO 2 SEM image of ceramic fracture of whisker. FIG. 4 shows MgO grains and Mg 2 TiO 4 The grain boundary diagram shows that the new phase generated by the reaction is not at the boundary of a plurality of crystal grains, but is uniformly distributed at the grain boundary of any two adjacent crystal grains. The structure is just like a 'building piled by bricks', and the cement is used for bonding any two adjacent bricks together, so that the mechanical property of the substrate material is greatly improved. The dielectric constant of the normal alumina ceramic substrate is 9.7, the dielectric loss is 4 multiplied by 10 < -4 >, the heat conductivity of the magnesia is higher than that of magnesia, and the lower the dielectric loss is, the higher the heat conductivity is, the better the substrate performance is.
The foregoing is only a limited example of the substrate material and the preparation method of the titanium dioxide whisker reinforced magnesia ceramic of the present invention, but not limited to any limitation on the technical scope of the present invention, and any modification or equivalent change of the above examples according to the technical substance of the present invention falls within the scope of the technical proposal of the present invention.
Claims (6)
1. The titanium dioxide whisker reinforced magnesia ceramic substrate material is characterized by being a mixture of an inorganic component and an organic component in a weight ratio of 9:1, wherein the inorganic component comprises 82-97wt% of MgO and 3-18wt% of TiO 2 Whisker is mixed, and the organic component is polyvinyl alcohol Ding Quanzhi;
the granularity of MgO is 0.5-1.0 mu m, the content of magnesia is more than or equal to 98.5 percent, and the water content is less than or equal to 1.0 percent;
the TiO 2 The whisker has length of 15-30 μm, diameter of 1-3 μm, length-diameter ratio of more than 10, and TiO 2 The content is more than or equal to 99.9 percent, and the water content is less than or equal to 1.0 percent.
2. The titanium dioxide whisker reinforced magnesia ceramic substrate material according to claim 1, wherein the polyvinyl butyral Ding Quanzhi comprises the following components in parts by weight: 9, at room temperature, oscillating by an ultrasonic oscillator and stirring for 10-20 minutes by a glass rod, so that the polyvinyl butyral is completely dissolved in the absolute ethyl alcohol.
3. The titanium dioxide whisker reinforced magnesia ceramic substrate material of claim 1, wherein MgO and TiO in the inorganic component 2 The weight percentage of the whisker is any one of 94:6, 91:9, 88:12 and 85:15.
4. The titanium dioxide whisker reinforced magnesia ceramic substrate material according to claim 1, wherein the substrate material has a flexural strength of 165-221 mpa, a vickers hardness of 585-1048 hv, a dielectric constant of 10.6-11.9 at 300kHz, and a dielectric loss of < 2.44×10 -4 。
5. The method for preparing the titanium dioxide whisker reinforced magnesia ceramic substrate material according to claim 1, which is characterized by comprising the following preparation steps:
1) Presintering, namely presintering raw material MgO for 2-4 hours at 900-960 ℃ to decompose magnesium hydroxide into magnesium oxide;
2) Ball milling, weighing magnesium oxide and TiO according to the formula amount 2 Placing the whiskers and ethanol into a ball milling tank together, mixing the raw materials and the ethanol according to the mass-volume ratio of 1g to 3.5ml, ball milling for 6 hours, rotating the ball milling machine at the speed of 450-550 r/min, and sieving the ball milled materials with a 200-mesh sieve;
3) Drying and grinding, namely drying and grinding the materials which are ball-milled in the step 2), wherein the drying adopts drying oven equipment, the water content after drying is less than or equal to 0.1%, the grinding adopts a corundum mortar, and the granularity of the mixture after grinding is more than 300 meshes;
4) Mixing, namely adding the mixture obtained in the step 3) into the polyvinyl butyral ester with the formula amount, and continuously and uniformly mixing;
5) Press molding, namely press molding the mixture in the step 4) in a die, putting the green body into a cold isostatic press, maintaining the pressure at 200MPa for at least 30 seconds, and demoulding to obtain the green body;
6) Sintering, namely performing glue discharging sintering on the green body in the step 5) in an air atmosphere, preserving heat for 1-3 hours at 600-650 ℃, and then raising the temperature to 1450-1550 ℃ and preserving heat for 3-6 hours;
7) The prepared ceramic sample is tested by a universal tester, a Vickers hardness tester and a precise LCR tester at 300kHz, the bending strength, the Vickers hardness and the dielectric constant are 165-221 MPa, 585-1048 Hv and 10.6-11.9, and the dielectric loss is less than 2.44 multiplied by 10 -4 。
6. The method for preparing a titanium dioxide whisker reinforced magnesia ceramic substrate material according to claim 5, wherein the drying temperature in step 3) is 100 ℃ and the drying time is 60 minutes.
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| CA2152298A1 (en) * | 1994-06-22 | 1995-12-23 | Etsuji Kimura | Magnesia-titania refractory and method for manufacturing the same |
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| CN112624755A (en) * | 2020-12-02 | 2021-04-09 | 无锡市高宇晟新材料科技有限公司 | Microwave dielectric ceramic material and preparation method thereof |
| CN112876270A (en) * | 2021-01-26 | 2021-06-01 | 山东丁鼎科技发展有限公司 | Microwave dielectric ceramic injection feed, microwave dielectric ceramic and preparation method thereof |
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| CA2152298A1 (en) * | 1994-06-22 | 1995-12-23 | Etsuji Kimura | Magnesia-titania refractory and method for manufacturing the same |
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