CN115286411A - 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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- CN115286411A CN115286411A CN202210967841.4A CN202210967841A CN115286411A CN 115286411 A CN115286411 A CN 115286411A CN 202210967841 A CN202210967841 A CN 202210967841A CN 115286411 A CN115286411 A CN 115286411A
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 title claims abstract description 147
- 239000000395 magnesium oxide Substances 0.000 title claims abstract description 82
- 239000000919 ceramic Substances 0.000 title claims abstract description 58
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims abstract description 39
- 239000000758 substrate Substances 0.000 title claims abstract description 38
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 title claims abstract 16
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 239000013078 crystal Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 238000005452 bending Methods 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000002245 particle 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
- 150000002148 esters Chemical class 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
- 238000007873 sieving Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 238000000748 compression moulding Methods 0.000 abstract 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 11
- 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
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 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
- 239000004568 cement Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001144 powder X-ray diffraction data Methods 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
- 229910052770 Uranium Inorganic materials 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
- 238000005056 compaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 238000010586 diagram Methods 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
- 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
- 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
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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
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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
- 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
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- Chemical & Material Sciences (AREA)
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- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention relates to the technical field of electronic ceramics, in particular to a titanium dioxide whisker reinforced magnesium oxide ceramic substrate material and a preparation method thereof 2 The crystal whisker is mixed, and the organic component is polyvinyl butyral (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 as high as 165 to 221MPa, the Vickers hardness is 585 to 1048Hv, the dielectric constant is 10.6 to 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, non-toxic and pollution-free components, and capability of meeting the requirements of microminiature integrationThe substrate material is required and is 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 magnesium oxide ceramic substrate material and a preparation method thereof.
Background
The magnesium oxide is an ionic compound, has a chemical formula of MgO, belongs to a cubic crystal system, has a crystal in a face-centered cubic structure, has the characteristics of compact ion packing in the crystal, ordered arrangement and high ionic bond strength, reduces dielectric loss along with the increase of frequency, is white macroscopically, is a typical alkaline earth metal oxide, has a melting point of 2800 +/-13 ℃, a boiling point of 3600 ℃ and a density of 3.58g/cm 3 The high-temperature-resistant silicon carbide is a good insulator, has the resistivity of about 2.4 multiplied by 108 omega cm at room temperature, is sharply reduced along with the temperature rise, has better high temperature resistance, and can be used as a crucible for smelting metal; is also suitable for smelting high-purity uranium and thorium in the atomic energy industry; can also be used as a thermocouple protective sleeve; the material can be used as radar cover and infrared radiation transmission window material, etc. by using the property of enabling electromagnetic waves to pass through, however, the sintering of pure magnesia ceramic is not easy to be compact, and the bending strength and hardness are relatively poor.
With the continuous development of science and technology, electronic equipment develops along with the development of the science and technology, and the requirements on materials for packaging chips of the electronic equipment are correspondingly increased. The conventional substrate material can not meet the requirements, and the requirements of inventing a novel heat dissipation packaging material with high heat conductivity, low dielectric constant, low dielectric loss and good mechanical property are urgent. Although the magnesia ceramic has excellent dielectric property, the magnesia ceramic can meet the requirement of high-frequency dielectric materials, but the mechanical property of the magnesia ceramic is relatively poor, and the magnesia ceramic does not meet the requirement under the requirement of microminiature integration, so that the magnesia ceramic has very important significance on how to improve the mechanical property of the magnesia ceramic.
For example, patent application CN105439544A0 discloses a magnesia ceramic and a process for its preparation, the composition of which comprises: 960-1000 parts of magnesium oxide micro powder, 20-40 parts of magnesium oxide nano powder, 8-16 parts of a water reducing agent, 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 process are utilized, so that the sintering rejection rate is reduced, and the sintering strength and the density are improved. Patent application CN201010281144.0 discloses a preparation method of high-density magnesium oxide ceramic, which comprises the steps of calcining nanoscale high-purity basic magnesium carbonate to prepare nano magnesium oxide powder, and sintering at 1300 ℃ for 180min through 800MPa pressure forming and 10 ℃/min heating rate to prepare the magnesium oxide ceramic with the relative density of 98.2%. The production process is too complex; although the two methods can prepare the relatively compact magnesia ceramics, the two methods have various raw materials, strict requirements on the raw materials and complex operation process, and are not beneficial to industrial production. Both methods show the mechanical properties of the magnesia ceramic, and the compact magnesia ceramic has lower bending strength and smaller hardness.
The mainstream substrate in the current market is still an alumina ceramic substrate, and magnesia ceramic has higher thermal conductivity coefficient compared with the alumina ceramic substrate, so that the magnesia ceramic substrate is very beneficial to the substrate, and the mechanical property of the magnesia ceramic is improved under the condition of not influencing the dielectric property and the thermal conductivity of the magnesia ceramic so as to meet the requirement of a high-frequency dielectric microminiature integrated substrate material, which is a practical requirement in the field, and related reports are not available at present.
Disclosure of Invention
The invention aims to provide a titanium dioxide whisker reinforced magnesium oxide ceramic substrate material and a preparation method thereof, overcomes the defects of the prior art, and utilizes TiO whisker to reinforce the magnesium oxide ceramic substrate material 2 (w) improvement of mechanical Properties of MgO ceramics, tiO 2 The crystal whisker and the MgO crystal grain are subjected to chemical reaction to generate a new phase which is uniformly distributed at the MgO crystal boundary, the MgO ceramic composite material is sintered best, and various mechanical properties reach the maximum. The invention has the advantages of available raw materials, simple production process, no toxicity and no pollution of used medicines, meets the requirements of industrial production and microminiature integrated substrate materials, and is suitable for mass production.
In order to realize the purpose, the invention adopts the following technical scheme:
the technical scheme is as follows: the titanium dioxide whisker reinforced magnesium oxide ceramic substrate material is characterized by being a mixture of inorganic components and organic components according to the weight parts of 9The machine component is composed of 82-97 wt% of magnesium oxide micropowder and 3-18 wt% of TiO 2 The crystal whisker is mixed, and the organic component is polyvinyl butyral (PVB).
Furthermore, the granularity of the magnesium oxide micro powder is 0.5-1.0 μm, the content of magnesium oxide is more than or equal to 98.5 percent, and the water content is less than or equal to 1.0 percent.
Further, the TiO 2 The length of the crystal whisker is 15-30 μm, the diameter is 1-3 μm, the length-diameter ratio is more than 10 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 ester is prepared by mixing polyvinyl butyral and absolute ethyl alcohol according to the weight ratio of 1:9, shaking by an ultrasonic shaking machine at room temperature and stirring for 10 to 20 minutes by a glass rod to ensure that the polyvinyl butyral is completely dissolved in the absolute ethyl alcohol.
Further, the inorganic components include magnesium oxide micropowder and TiO 2 The weight percentage of the whisker is 94, 91.
Furthermore, the substrate material has the bending strength of 165-221 MPa, the Vickers hardness of 585-1048 Hv, the dielectric constant of 10.6-11.9 (300 kHz), and the dielectric loss of less than 2.44 multiplied by 10 -4 。
The second technical proposal is as follows: a preparation method of a titanium dioxide whisker reinforced magnesium oxide ceramic substrate material is characterized by comprising the following preparation steps:
1) Pre-burning, namely pre-burning the raw material magnesium oxide micro powder for 2 to 4 hours at the temperature of 900 to 960 ℃ to decompose magnesium hydroxide into magnesium oxide;
2) Ball milling, weighing MgO: tiO 2 2 (w) putting an ethanol grinding medium into a ball milling tank, mixing the raw materials and 1g of ethanol according to the mass volume ratio of the raw materials to 1g of ethanol, ball milling for 6 hours at the rotating speed of 450-550 r/min, and performing ball milling to obtain a particle size of 200 meshes;
3) Drying and grinding, wherein the ball-milled material in the step 2) is dried and ground, drying is carried out by adopting a drying box device, the water content after drying is less than or equal to 0.1%, grinding is carried out by adopting a corundum mortar, and the granularity of the ground mixture is more than 300 meshes;
4) Mixing, namely adding the mixture obtained in the step 3) into PVB with the formula amount and continuously mixing uniformly;
5) Pressing and forming, namely pressing and forming the mixture obtained in the step 4) in a mould, then putting the green body into a cold isostatic press, keeping the pressure at 200MPa for not less than 30 seconds, and demoulding to obtain the green body;
6) Sintering, namely performing binder removal sintering on the green body in the step 5) in an air atmosphere, preserving heat for 1-3 hours at the temperature of 600-650 ℃, and then heating 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 utilize TiO 2 (w) improvement of mechanical Properties of MgO ceramics, tiO 2 The crystal whisker and MgO crystal grain are chemically reacted to generate new phase which is uniformly distributed at the MgO crystal boundary and is in contact with the traditional TiO 2 The addition of the micro powder into the MgO is different, and a new phase generated by the reaction is not at the boundary of a plurality of crystal grains, but is uniformly distributed at the crystal boundary of any two adjacent crystal grains. The structure is just like building by piling bricks, any two adjacent bricks need to be bonded together by cement, the mechanical property of the MgO ceramic is greatly improved, the process is simple, the raw materials are cheap, and the MgO ceramic is very suitable for industrial production.
Compared with the prior art, the invention has the beneficial effects that:
1) TiO of the present 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 being TiO 2 2 When the addition amount of the crystal whisker is 12wt%, the MgO ceramic composite material is best sintered, and various mechanical properties reach the maximum.
2) The invention has the advantages of easily obtained raw materials, simple production process, nontoxic and pollution-free raw material components, capability of meeting the requirements of industrial scale production and microminiature integrated substrate materials and popularization value.
Drawings
FIG. 1 shows 12wt% of TiO added in example 4 of the present invention 2 Ceramic powder XRD pattern of whiskers;
FIG. 2 shows the contents of 12wt% of TiO in example 4 of the present invention 2 SEM image of ceramic surface of whisker;
FIG. 3 shows the contents of 12wt% of TiO in example 4 of the present invention 2 SEM image of ceramic fracture of whisker;
FIG. 4 shows MgO grains and Mg in example 4 of the present invention 2 TiO 4 Schematic representation of grain boundaries.
Detailed description of the preferred embodiment
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. Thus, the following detailed description of the embodiments of the present 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 derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention.
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other embodiments can be obtained according to the description without creative efforts for those skilled in the art. Thus, the following detailed description of the embodiments of the present invention, 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 magnesium oxide ceramic substrate material, whichThe raw material components by weight percentage are: 90wt% (97%) MgO, 3% TiO 2 Whiskers), 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 an ethanol bath of a ball mill, and mixing and ball-milling the raw materials and ethanol at a ratio of 1g to 3.5ml for 6 hours at a rotating speed of 450r/min; placing the ball-milled materials in a drying box, preserving heat for 1 hour at 100 ℃, adding PVB after drying, and uniformly mixing; pressing and molding the mixed materials under the axial pressure of 5MPa, demoulding to obtain a green body, and performing cold isostatic pressing on the green body at 200MPa; and (2) carrying out binder removal and sintering on the prepared green body in an air atmosphere, raising the temperature to 600 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 1 hour, raising the temperature to 1100 ℃ at the heating rate of 4 ℃/min, raising the temperature to 1450 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 3 hours, and cooling with the furnace temperature to obtain a ceramic sample, wherein various properties of the ceramic sample are shown in table 1.
Example 2
The embodiment provides a titanium dioxide whisker reinforced magnesium oxide ceramic substrate material, which comprises the following components: raw materials: 90wt% (94% MgO, 6% TiO) 2 Whiskers), PVB:10wt%.
The procedure of this example was the same as in example 1.
Example 3
The embodiment provides a titanium dioxide whisker reinforced magnesium oxide ceramic substrate material, which comprises the following components: raw materials: 90wt% (91% MgO, 9% TiO) 2 Whiskers), PVB:10wt%.
The procedure of this example was the same as in example 1.
Example 4
The embodiment provides a titanium dioxide whisker reinforced magnesium oxide ceramic substrate material, which comprises the following components: raw materials: 90wt% (88% MgO, 12% TiO) 2 Whiskers), PVB:10wt%.
The procedure of this example was the same as in example 1.
Example 5
The embodiment provides a titanium dioxide whisker reinforced magnesium oxide ceramic substrate material, which comprises the following components: raw materials: 90 wt.%(85％MgO、15％TiO 2 Whiskers), PVB:10wt%.
The procedure of this example was the same as in example 1.
Example 6
The embodiment provides a titanium dioxide whisker reinforced magnesium oxide ceramic substrate material, which comprises the following components: raw materials: 90wt% (82% MgO, 18% TiO) 2 Whiskers), PVB:10wt%.
The procedure of this example was the same as in example 1.
The properties of the ceramic samples of inventive examples 1-6 are compared in table 1.
TABLE 1
Referring to fig. 1-4, there are shown related drawings of preferred embodiment 4 of the present invention. Wherein FIG. 1 is TiO 12wt% 2 Ceramic powder XRD pattern of whiskers demonstrating TiO 2 The crystal whisker does react with MgO to generate a new phase Mg 2 TiO 4 (ii) a FIG. 2 shows the addition of 12wt% of TiO 2 SEM image of the ceramic surface of the whisker, from which the "stacked" structure of the invention belongs; FIG. 3 shows the addition of 12wt% of TiO 2 SEM images of ceramic fractures of whiskers. 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 grains, but is uniformly distributed at the grain boundary of any two adjacent grains. The structure is just like building by piling bricks, any two adjacent bricks need to be bonded together by cement, and the mechanical property of the base plate material is greatly improved due to the structure. The normal alumina ceramic substrate has the dielectric constant of 9.7 and the dielectric loss of 4 multiplied by 10 < -4 >, the thermal conductivity of the magnesia is higher than that of the magnesia, and the lower the dielectric loss is, the higher the thermal conductivity is, the better the substrate performance is.
The above description is only a limited example of the substrate material made of titania whisker reinforced magnesia ceramic and the preparation method of the present invention, and is not intended to limit the technical scope of the present invention, and any modifications or equivalent changes made to the above examples according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (8)
1. A titanium dioxide whisker reinforced magnesium oxide ceramic substrate material is characterized by being a mixture of an inorganic component and an organic component according to the weight portion ratio of 9 to 1, wherein the inorganic component is 82 to 97 weight percent of magnesium oxide micro powder and 3 to 18 weight percent of TiO micro powder 2 The crystal whisker is mixed, and the organic component is polyvinyl butyral (PVB).
2. The titanium dioxide whisker reinforced magnesium oxide ceramic substrate material according to claim 1, wherein the particle size of the magnesium oxide micro powder is 0.5-1.0 μm, the content of magnesium oxide is not less than 98.5%, and the water content is not more than 1.0%.
3. The titanium dioxide whisker reinforced magnesium oxide ceramic substrate material as claimed in claim 1, wherein the TiO is selected from the group consisting of 2 The length of the crystal whisker is 15-30 μm, the diameter is 1-3 μm, the length-diameter ratio is more than 10 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.
4. The titanium dioxide whisker reinforced magnesium oxide ceramic substrate material according to claim 1, wherein the polyvinyl butyral ester is prepared by mixing polyvinyl butyral and absolute ethanol in a weight ratio of 1:9, shaking by an ultrasonic shaking machine at room temperature and stirring for 10 to 20 minutes by a glass rod to ensure that the polyvinyl butyral is completely dissolved in the absolute ethyl alcohol to prepare the polyvinyl butyral.
5. The titanium dioxide whisker reinforced magnesium oxide ceramic substrate material as claimed in claim 1, wherein the inorganic component comprises magnesium oxide micropowder and TiO micropowder 2 The weight percentage of the whisker is 94, 91.
6. A two-layer film according to claim 1The titanium oxide whisker reinforced magnesium oxide ceramic substrate material is characterized in that the bending strength of the substrate material is 165-221 MPa, the Vickers hardness is 585-1048 Hv, the dielectric constant is 10.6-11.9 under the condition of 300kHz, and the dielectric loss is less than 2.44 multiplied by 10 -4 。
7. A preparation method of a titanium dioxide whisker reinforced magnesium oxide ceramic substrate material is characterized by comprising the following preparation steps:
1) Pre-burning, namely pre-burning the raw material magnesium oxide micro powder for 2 to 4 hours at the temperature of 900 to 960 ℃ to decompose magnesium hydroxide into magnesium oxide;
2) Ball milling, weighing MgO and TiO with formula amount 2 (w) putting the mixture and ethanol into a ball milling tank, mixing the raw materials and the ethanol 1g in a mass volume ratio of 3.5ml, carrying out ball milling for 6 hours, wherein the rotating speed of the ball mill is 450-550 r/min, and sieving the milled particles through a 200-mesh sieve;
3) Drying and grinding, wherein the ball-milled material in the step 2) is dried and ground, drying is carried out by adopting a drying box device, the water content after drying is less than or equal to 0.1%, grinding is carried out by adopting a corundum mortar, and the granularity of the ground mixture is more than 300 meshes;
4) Mixing, namely adding the mixture obtained in the step 3) into PVB with the formula amount and continuously mixing uniformly;
5) Pressing and forming, namely pressing and forming the mixture obtained in the step 4) in a mould, then putting the green body into a cold isostatic press, keeping the pressure at 200MPa for not less than 30 seconds, and demoulding to obtain the green body;
6) Sintering, namely performing binder removal sintering on the green body in the step 5) in an air atmosphere, preserving heat for 1-3 hours at the temperature of 600-650 ℃, and then heating to 1450-1550 ℃ for 3-6 hours.
8. The method for preparing a titanium dioxide whisker reinforced magnesium oxide ceramic substrate material according to claim 7, wherein the drying temperature in the step 2) 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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| CN108424124A (en) * | 2018-04-08 | 2018-08-21 | 凤阳爱尔思轻合金精密成型有限公司 | Magnesium oxide-based crucible of a kind of magnesia crystal whisker fabricated in situ spinelle enhancing and preparation method thereof |
| 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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