CN117586005A - Large-size zirconia ceramic and preparation method thereof - Google Patents
Large-size zirconia ceramic and preparation method thereof Download PDFInfo
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- CN117586005A CN117586005A CN202311469534.4A CN202311469534A CN117586005A CN 117586005 A CN117586005 A CN 117586005A CN 202311469534 A CN202311469534 A CN 202311469534A CN 117586005 A CN117586005 A CN 117586005A
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 169
- 239000000919 ceramic Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000011575 calcium Substances 0.000 claims abstract description 36
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 33
- 239000004576 sand Substances 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 22
- 238000000498 ball milling Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005245 sintering Methods 0.000 abstract description 11
- 239000007791 liquid phase Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 238000005336 cracking Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 4
- 230000008646 thermal stress Effects 0.000 abstract description 4
- 239000011230 binding agent Substances 0.000 abstract description 3
- 230000035939 shock Effects 0.000 description 14
- 229910000831 Steel Inorganic materials 0.000 description 13
- 239000010959 steel Substances 0.000 description 13
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 11
- 239000000292 calcium oxide Substances 0.000 description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- 241000276425 Xiphophorus maculatus Species 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 239000000395 magnesium oxide Substances 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- -1 aluminum zirconium carbon Chemical compound 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- RWDBMHZWXLUGIB-UHFFFAOYSA-N [C].[Mg] Chemical compound [C].[Mg] RWDBMHZWXLUGIB-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- 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
- C04B35/48—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 zirconium or hafnium oxides, zirconates, zircon or hafnates
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- 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
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- 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
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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- 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
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
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- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
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Abstract
The invention relates to a large-size zirconia ceramic and a preparation method thereof, wherein the zirconia ceramic comprises 91-95% of monoclinic zirconia, 0-1% of lanthanum trioxide and 3-8% of magnesia-calcium sand by weight percentage, the preparation process adopts a wet ball milling process, powder after ball milling and drying is pressed and molded under 120-180 MPa, and the large-size zirconia ceramic is obtained after sintering at 1600-1700 ℃. The invention uses MgO and CaO in the natural magnesia-calcium sand to stabilize zirconia, micro-impurity in the magnesia-calcium sand is in liquid phase at high temperature, which can promote sintering and reduce sintering temperature; and the thermal stress is relieved at a small amount of liquid phase high temperature, the cracking of the large-size zirconia ceramic is prevented, and the yield is improved. In addition, the magnesia-calcium sand is hydrated to generate a small amount of Mg (OH) 2 And Ca (OH) 2 And the binding effect is achieved without adding any binding agent. The zirconia ceramic prepared by the method has the advantages of low energy consumption, low cost, stable volume and the like.
Description
Technical Field
The invention belongs to the technical field of refractory materials, and particularly relates to a large-size zirconia ceramic and a preparation method thereof.
Background
In the steel smelting process, the sliding gate is an important key functional element for continuous casting, is a flow control system of molten steel, and accurately controls the molten steel to flow from a ladle to a tundish and the tundish to a crystallizer. In recent years, china focuses on the smelting of high-quality steel, but the smelting of high-quality steel has serious corrosion to refractory materials, such as: when casting calcium treated steel, the calcium vapor therein is very easy to be mixed with Al in the skateboard 2 O 3 、SiO 2 The low-melting-point phase (2CaO.Al) is generated by the waiting reaction 2 O 3 •SiO 2 (1539 ℃) and 12CaO.7Al 2 O 3 (1392 ℃) are seriously damaged by molten steel flushing. Therefore, the current common aluminum carbon and aluminum zirconium carbon sliding plates have very low service life due to the corrosion of calcium steam, and have potential safety hazards of steel leakage. The magnesium carbon sliding plate has excellent erosion resistance, but the magnesium carbon sliding plate has poor thermal shock resistance due to the larger thermal expansion coefficient of the magnesia, is easy to crack and even crack when being impacted by high-temperature molten steel, has low service life and has potential safety hazard. Current skateboards for casting calcium-treated steel are very challenging.
The zirconia material has high melting point and excellent performance of resisting calcium steam corrosion, is an ideal material for smelting calcium treated steel, and is prepared into a sliding plate for casting the calcium treated steel by adopting a method of embedding zirconia rings or zirconia plates with larger size at present. However, zirconia undergoes monoclinic phase transformation to tetragonal and cubic phases at high temperatures, and the transformation is accompanied by a volume effect, so that the zirconia product is cracked. At present, high-purity oxides such as MgO, caO, lanthanum oxide and the like are used as stabilizers to partially stabilize zirconia, and for small-size zirconia products, the method for partially stabilizing zirconia can reduce, even eliminate product cracking caused by phase change. However, for large-sized zirconia rings or zirconia plates, thermal stress is generated due to uneven temperatures at different parts of the product during high-temperature firing. In addition, the volume effect of the phase change of the zirconia can cause cracks, even cracking, of the burned zirconia ring or zirconia plate, and the yield is low.
In addition, the stabilizing agents used at present are all high-purity oxides, so that the price is high, the sintering temperature of zirconia products is higher than 1700 ℃, the energy consumption is high, and the production period is long. The low yield and high sintering temperature of the zirconia ring or zirconia plate lead to high price, limit the application of the zirconia ring or zirconia plate in a large amount and further influence the smelting of high-quality steel. Thus, there is an urgent need for a low-cost and stable large-size zirconia ceramic.
Disclosure of Invention
The invention aims to provide a preparation method of large-size zirconia ceramics, which adopts low-cost natural raw materials of magnesium-calcium sand and trace lanthanum trioxide as stabilizers to prepare the large-size zirconia ceramics. The technical innovation is that: mgO and CaO in natural magnesia-calcium sand are utilized to stabilize zirconia, micro impurities in the magnesia-calcium sand are in a liquid phase at high temperature, sintering can be promoted, and sintering temperature is reduced; and the thermal stress is relieved at a small amount of liquid phase high temperature, the cracking of the large-size zirconia ceramic is prevented, and the yield is improved. In addition, the magnesia-calcium sand is hydrated to generate a small amount of Mg (OH) 2 And Ca (OH) 2 And the binding effect is achieved without adding any binding agent. The zirconia ceramic prepared by the method has the advantages of low energy consumption, low cost, stable volume and the like.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the large-size zirconia ceramic comprises 91-95% of monoclinic zirconia, 0-1% of lanthanum oxide and 3-8% of magnesia-calcium sand by weight percentage.
The zirconia ceramic prepared by the method is of a platy structure, and generally has the length of more than 200mm, the width of more than 100mm and the thickness of about 18-20 mm.
Further, the grain size of the monoclinic zirconia is less than or equal to 0.044mm, the grain size of the lanthanum trioxide is less than or equal to 0.075mm, and the grain size of the magnesia-calcia sand is less than or equal to 0.075mm.
Further, in the chemical composition of the monoclinic zirconia, zrO 2 ＞99.5wt%。
Further, in the chemical composition of the lanthanum oxide, la 2 O 3 ＞99.9wt%。
Further, in the chemical composition of the magnesia-calcium sand, the MgO content is 60 to 66 weight percent, the CaO content is 31 to 35 weight percent, and the SiO is 2 ≤1.5wt%、Al 2 O 3 ≤1.2wt%、Fe 2 O 3 ≤1.5wt%。
The preparation method of the large-size zirconia ceramic comprises the following steps:
(1) Weighing monoclinic zirconia, lanthanum oxide, magnesium calcium sand according to a proportion, taking water as a ball milling medium, and uniformly mixing in a planetary ball mill by adopting a wet ball milling process;
(2) After ball milling, drying the powder, crushing and sieving;
(3) Compacting and molding the obtained powder under 120-180 MPa to obtain a blank;
(4) Placing the green body into a drying box;
(5) Calcining the dried green body in an electric furnace at the temperature rising rate of 1-10 ℃/min, the calcining temperature of 1600-1700 ℃ and the heat preservation time of 1-5 h.
Further, the wet ball milling process is that the rotational speed of the ball mill is 250-300 r/min, and the ball milling time is 12-24 h.
Further, the step (2) is dried at 100-110 ℃ for 6-12 h.
Further, in the step (4), the drying temperature is 100-120 ℃ and the drying time is 12-24 hours.
Advantageous effects
1. The invention adopts the magnesia-calcium sand as the stabilizer, utilizes MgO and CaO in the natural magnesia-calcium sand to stabilize zirconia, and ensures that micro-impurities in the magnesia-calcium sand are in liquid phase at high temperature, thereby promoting sintering and reducing sintering temperature.
2. The invention relieves the thermal stress at high temperature by using a small amount of liquid phase generated, prevents the cracking of the large-size zirconia ceramic, and improves the yield.
3. The invention utilizes the hydration of natural magnesia-calcium sand to generate a small amount of Mg (OH) 2 And Ca (OH) 2 Has binding effect without adding binder
4. The zirconia ceramic prepared by the invention has the advantages of low energy consumption, low cost, stable volume and the like.
Drawings
FIG. 1a is a scanning electron microscope image of a cross section of a zirconia ceramic prepared in example 3 of the present invention;
FIG. 1b is an EDS spectrum of a zirconia ceramic section prepared in example 3 of the present invention;
FIG. 2 is a scanning electron microscope image of the zirconia ceramic prepared in example 3 of the present invention after surface polishing.
Description of the embodiments
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples, mgO in the magnesia-calcium sand was 63.8wt%, caO was 32.2wt%, and SiO 2 1.5wt% of Al 2 O 3 The proportion by weight is 1.2 percent, fe 2 O 3 The proportion is 1.3wt%.
Example 1
The large-size zirconia ceramic comprises 93% of monoclinic zirconia powder, 0.5% of lanthanum oxide and 6.5% of magnesia-calcium sand in percentage by weight;
the preparation method comprises the following steps:
(1) Weighing monoclinic zirconia, lanthanum oxide and magnesia-calcium sand according to a proportion, uniformly mixing in a planetary ball mill by adopting a wet ball milling process, wherein the rotating speed of the ball mill is 280r/min, and the ball milling time is 12h;
(2) After ball milling, drying the powder for 12 hours at 105 ℃, crushing and sieving;
(3) Pressing and molding the obtained powder under 150MPa to obtain a blank;
(4) Placing the green body into a drying oven, wherein the drying temperature is 110 ℃, and the drying time is 12 hours;
(5) Calcining the dried green body in an electric furnace, preserving the temperature at 1650 ℃ for 3 hours, wherein the heating rate at 0-1000 ℃ is 5 ℃/min, the heating rate at 1000-1400 ℃ is 3 ℃/min, and the heating rate at 1400-1650 ℃ is 2 ℃/min.
(6) The sintered blank is respectively tested according to national standards GB/T3001-2007, GB/T30758-2014 and metallurgical standard YB/T376.2-1995 for normal temperature flexural strength, elastic modulus and thermal shock stability of the test sample.
The prepared zirconia ceramic has a platy structure, the length is 400mm, the width is 200mm, and the thickness is 20mm.
The normal temperature flexural strength of the product obtained by the embodiment is 67.7MPa, the elastic modulus is 9.5GPa, the thermal shock strength retention rate is 77.1%, 100 products are fired at one time, 98 products are produced, and the yield reaches 98%.
Example 2
The large-size zirconia ceramic comprises 92.5 weight percent of monoclinic zirconia powder, 0.5 weight percent of lanthanum oxide and 7 weight percent of magnesia-calcium sand;
the preparation method comprises the following steps:
(1) Weighing monoclinic zirconia, lanthanum oxide and magnesia-calcium sand according to a proportion, uniformly mixing in a planetary ball mill by adopting a wet ball milling process, wherein the rotating speed of the ball mill is 280r/min, and the ball milling time is 12h;
(2) After ball milling, drying the powder for 12 hours at 105 ℃, crushing and sieving;
(3) Pressing and molding the obtained powder under 150MPa to obtain a blank;
(4) Placing the green body into a drying oven, wherein the drying temperature is 110 ℃, and the drying time is 12 hours;
(5) Calcining the dried green body in an electric furnace, preserving the temperature at 1650 ℃ for 3 hours, wherein the heating rate at 0-1000 ℃ is 5 ℃/min, the heating rate at 1000-1400 ℃ is 3 ℃/min, and the heating rate at 1400-1650 ℃ is 2 ℃/min.
(6) The sintered blank is respectively tested according to national standards GB/T3001-2007, GB/T30758-2014 and metallurgical standard YB/T376.2-1995 for normal temperature flexural strength, elastic modulus and thermal shock stability of the test sample.
The prepared zirconia ceramic has a platy structure, the length is 500mm, the width is 150mm, and the thickness is 18mm.
The normal temperature flexural strength of the product obtained by the embodiment is 72.7MPa, the elastic modulus is 10.2GPa, the thermal shock strength retention rate is 78.7%, 100 products are fired at one time, 97 products are produced, and the yield reaches 97%.
Example 3
The large-size zirconia ceramic comprises 92% of monoclinic zirconia powder, 0.5% of lanthanum oxide and 7.5% of magnesia-calcium sand by weight percent.
The preparation method comprises the following steps:
(1) Weighing monoclinic zirconia, lanthanum oxide and magnesia-calcium sand according to a proportion, uniformly mixing in a planetary ball mill by adopting a wet ball milling process, wherein the rotating speed of the ball mill is 280r/min, and the ball milling time is 12h;
(2) After ball milling, drying the powder for 12 hours at 105 ℃, crushing and sieving;
(3) Pressing and molding the obtained powder under 150MPa to obtain a blank;
(4) Placing the green body into a drying oven, wherein the drying temperature is 110 ℃, and the drying time is 12 hours;
(5) Calcining the dried green body in an electric furnace, preserving the temperature at 1650 ℃ for 3 hours, wherein the heating rate at 0-1000 ℃ is 5 ℃/min, the heating rate at 1000-1400 ℃ is 3 ℃/min, and the heating rate at 1400-1650 ℃ is 2 ℃/min.
(6) The sintered blank is respectively tested according to national standards GB/T3001-2007, GB/T30758-2014 and metallurgical standard YB/T376.2-1995 for normal temperature flexural strength, elastic modulus and thermal shock stability of the test sample.
The normal temperature flexural strength of the product obtained by the embodiment is 75.1MPa, the elastic modulus is 10.4GPa, the thermal shock strength retention rate is 74.8%, 100 products are fired at one time, 98 products are produced, and the yield reaches 98%.
The prepared zirconia ceramic has a platy structure, the length is 450mm, the width is 200mm, and the thickness is 20mm.
Referring to FIG. 1, a Scanning Electron Microscope (SEM) image and EDS spectrum of a cross section of zirconia ceramic prepared in example 3 of the present invention are shown. As can be seen from FIG. 1, the grains inside the zirconia ceramic are well developed and tightly combined, and EDS energy spectrum shows that the surfaces of the grains contain Zr, mg and Ca elements, which indicates that MgO and CaO in the magnesia-calcia sand are dissolved into ZrO at high temperature 2 In the crystal grains, zrO 2 Grain growth and development.
Referring to FIG. 2, a scanning electron microscope image of the polished zirconia ceramic surface prepared in example 3 of the present invention is shown. As can be seen from fig. 2, the zirconia ceramic is sintered compactly, has fewer pores and smaller size, because the micro-impurities in the magnesia-calcia sand are in liquid phase at high temperature, thus promoting the sintering of the zirconia ceramic and improving the strength thereof.
Example 4
Substantially the same as in example 1, except that: the large-size zirconia ceramic comprises 91% of monoclinic zirconia powder, 1% of lanthanum oxide and 8% of magnesia-calcium sand in percentage by weight.
The sintered blank is respectively tested according to national standards GB/T3001-2007, GB/T30758-2014 and metallurgical standard YB/T376.2-1995 for normal temperature flexural strength, elastic modulus and thermal shock stability of the test sample.
The prepared zirconia ceramic has a platy structure, the length is 350mm, the width is 260mm, and the thickness is 18mm.
The normal temperature flexural strength of the product obtained in the embodiment is 76.5MPa, the elastic modulus is 10.5GPa, and the thermal shock strength retention rate is 70.2%. 100 products are fired at one time, 99 finished products are produced, and the yield reaches 99 percent.
Example 5
Substantially the same as in example 1, except that: the large-size zirconia ceramic comprises 95% of monoclinic zirconia powder, 0% of lanthanum oxide and 5% of magnesia-calcium sand in percentage by weight.
The sintered blank is respectively tested according to national standards GB/T3001-2007, GB/T30758-2014 and metallurgical standard YB/T376.2-1995 for normal temperature flexural strength, elastic modulus and thermal shock stability of the test sample.
The prepared zirconia ceramic has a platy structure, the length is 300mm, the width is 160mm, and the thickness is 19mm.
The product obtained in the embodiment has normal temperature flexural strength of 60.1MPa, elastic modulus of 8.4GPa and thermal shock strength retention rate of 67.8%. 100 products are fired at one time, the number of finished products is 95, and the yield reaches 95%.
Comparative example 1
Substantially the same as in example 5, except that: a large-size zirconia ceramic comprises 95% of monoclinic zirconia powder and 5% of lanthanum oxide by weight.
The sintered blank is respectively tested according to national standards GB/T3001-2007, GB/T30758-2014 and metallurgical standard YB/T376.2-1995 for normal temperature flexural strength, elastic modulus and thermal shock stability of the test sample.
The prepared zirconia ceramic has a platy structure, the length is 300mm, the width is 160mm, and the thickness is 19mm.
The product obtained in the embodiment has the normal temperature flexural strength of 25.6MPa, the elastic modulus of 3.7GPa and the thermal shock strength retention rate of 34.6%. 100 products are fired at one time, 56 products are produced, and the yield reaches 56%.
As can be seen from comparative example 1, the invention adopts magnesia-calcia sand to replace lanthanum oxide partially or completely to replace lanthanum oxide, can effectively improve the performance and yield of the product, and compared with example 5, the normal temperature flexural strength of the product is improved by 135%, the elastic modulus is improved by 127%, the thermal shock strength retention rate is improved by 96%, and the yield is improved by 70%. It can be seen that the magnesia-calcia sand can form stable calcium oxide and magnesia compound at high temperature, which is beneficial to the sintering process of zirconia ceramics and improves the mechanical property and high temperature resistance of the material.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.
Claims (9)
1. A large-size zirconia ceramic, characterized in that: comprises 91-95% of monoclinic zirconia, 0-1% of lanthanum oxide and 3-8% of magnesia-calcium sand by weight percentage.
2. A large size zirconia ceramic as set forth in claim 1 wherein: the grain diameter of monoclinic zirconia is less than or equal to 0.044mm, the grain diameter of lanthanum trioxide is less than or equal to 0.075mm, and the grain diameter of magnesia-calcium sand is less than or equal to 0.075mm.
3. A large size zirconia ceramic as set forth in claim 1 wherein: in the chemical composition of the monoclinic zirconia, zrO 2 ＞99.5wt%。
4. A large size zirconia ceramic as set forth in claim 1 wherein: in the chemical composition of the lanthanum oxide, la 2 O 3 ＞99.9wt%。
5. A large size zirconia ceramic as set forth in claim 1 wherein: in the chemical composition of the magnesia-calcium sand, the MgO content is 60 to 66 weight percent, the CaO content is 31 to 35 weight percent, and the SiO is 2 ≤1.5wt%、Al 2 O 3 ≤1.2wt%、Fe 2 O 3 ≤1.5wt%。
6. The preparation method of the large-size zirconia ceramic is characterized by comprising the following steps of:
(1) Weighing monoclinic zirconia, lanthanum oxide, magnesium calcium sand according to a proportion, taking water as a ball milling medium, and uniformly mixing in a planetary ball mill by adopting a wet ball milling process;
(2) After ball milling, drying the powder, crushing and sieving;
(3) Compacting and molding the obtained powder under 120-180 MPa to obtain a blank;
(4) Placing the green body into a drying box;
(5) Calcining the dried green body in an electric furnace at the temperature rising rate of 1-10 ℃/min, the calcining temperature of 1600-1700 ℃ and the heat preservation time of 1-5 h.
7. The method for preparing the large-size zirconia ceramic according to claim 6, wherein: the wet ball milling process is that the rotational speed of the ball mill is 250-300 r/min, and the ball milling time is 12-24 h.
8. The method for preparing the large-size zirconia ceramic according to claim 6, wherein: and (3) drying in the step (2) at 100-110 ℃ for 6-12 h.
9. The method for preparing the large-size zirconia ceramic according to claim 6, wherein: the drying temperature in the step (4) is 100-120 ℃ and the drying time is 12-24 h.
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