CN1050347C - High tonghness reinforced porcelain and producing method - Google Patents
High tonghness reinforced porcelain and producing method Download PDFInfo
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- CN1050347C CN1050347C CN94110907A CN94110907A CN1050347C CN 1050347 C CN1050347 C CN 1050347C CN 94110907 A CN94110907 A CN 94110907A CN 94110907 A CN94110907 A CN 94110907A CN 1050347 C CN1050347 C CN 1050347C
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- porcelain
- zro
- tonghness
- mullite
- corundum
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Abstract
The present invention relates to a reinforced porcelain with high toughness and a producing method thereof, which belongs to the technical field of the porcelain. A porcelain blank of the porcelain comprises the chemical compositions according to the proportion by weight: 38 to 50% of SiO2, 30 to 52% of Al2O3, 2.5 to 4.0% of K2O, 5 to 15% of ZrO2, 0.5 to 1.5% of CaO, 0.4 to 0.8% of MgO and 0.2 to 1% of Li2O, wherein the content of crystal phases in the porcelain blank is over 45%; the crystal phases are corundum, mullite and ZrO2 crystal grains; the proportion of the crystal phases of the corundum to the mullite is 3 to 1: 1 to 3; the content of the crystal phase of the corundum does not exceed 35% of that of the porcelain blank; the content of the crystal phase of the mullite is not less than 10%; the content of the crystal phase of the ZrO2 crystal grains is from 1% to 9%; the size of each corundum crystal grain is from 1 mu m to 2 mu m; the size of each ZrO2 crystal grain is from 1 mu m to 2 mu m, and the size of the mullite is not greater than 30 mu m. The mechanical strength of the porcelain quality is improved by the phase transition toughening principle of the ZrO2. The folding strength of the reinforced porcelain is greater than or equal to 2000 kg/cm<2>, and the impact-resisting toughness of the reinforced porcelain is greater than or equal to 5 kgf-cm/cm<2>.
Description
The invention belongs to the ceramic technology field, relate to a kind of high tonghness reinforced porcelain and production method.
Pottery is a kind of typical brittleness material, because the complicacy and the ununiformity of ceramic internal structure make the plastic deformation ability of pottery shortage as the metal, in breaking-down process, except that increasing new fracture surface energy, does not almost have the function of other energy-absorbing.People are adopting the whole bag of tricks and approach to improve the fragility of pottery always for a long time, improve toughness by improving intensity, but DeGrain.In recent years, employing ZrO is arranged
2The transformation toughening principle improves the toughness of pottery, but because ZrO
2Transformation toughening is by cubic phase ZrO
2(t-ZrO
2) change monocline phase ZrO into
2(m-ZrO
2) process realize, and consider how to increase contributive t-ZrO from technology
2Content, up to the present also still unresolved to reach transformation toughening, therefore use ZrO
2Come the production of toughening ceramic to be difficult to realize (" new ceramics " book P68-72).
The objective of the invention is to provide a kind of with ZrO
2High tonghness reinforced porcelain and production method thereof as toughner, make the technological process of production, equipment, facility that this high tonghness reinforced porcelain can enough traditional household chinas produce, can be adapted to machine washing and non-damageable requirement and be used for microwave oven, electric baking stove, cryogenic freezing (refrigerator) and not easy to crack.
The technical scheme that realizes the object of the invention is: the Chemical Composition of this high tonghness reinforced porcelain porcelain base contains SiO
238-50%, Al
2O
330-52%, K
2O 2.5-4.0%, ZrO
25-15%, CaO 0.5-1.5%, MgO 0.4-0.8%, Li
2O 0.2-1% (weight), the crystalline phase amount is greater than 45% (generally being advisable at 50-60%) in the porcelain body, and its crystalline phase is corundum, mullite, ZrO
2Crystal grain, the ratio of corundum and mullite crystalline phase amount is (3-1): (1-3), corundum crystalline phase amount is no more than 35% of porcelain body, and mullite crystalline phase amount is no less than 10%, ZrO
2Crystalline phase amount 1-9%, (weight), corundum grain-size 1-2 μ m, ZrO
2Crystal grain 1-2 μ m, mullite is a needle-like, fails to grow up in 30 μ m.Mullite crystalline substance and corundum are principal crystalline phase, ZrO
2Be paracrystalline phase, acicular mullite crystalline substance is woven into netted, becomes the crystalline framework of porcelain, corundum and ZrO
2Uniform crystal particles is distributed in the porcelain body.Since under differing temps, ZrO
2Exist with three kinds of paramorphs, i.e. isometric system, tetragonal system, oblique system, the conversion of oblique system and tetragonal system is attended by the volume change about 7%, during heating by monocline-ZrO
2(m-ZrO
2) change four directions-ZrO into
2(t-ZrO
2), volumetric shrinkage, during cooling by t-ZrO
2Change m-ZrO into
2Volumetric expansion.But this contraction does not occur in same temperature with expansion, and the former is about 1200 ℃, and the latter is about 1000 ℃.Therefore in order to obtain ZrO
2Transformation toughening, the lowest total of the melting point of chemical ingredients of the present invention will be higher than 1000 ℃, and firing temperature can guarantee ZrO like this more than 1200 ℃
2All change cubic phase (t-ZrO into
2), when temperature was reduced to 1000 ℃, the glassy phase in the porcelain body solidified, t-ZrO after burning till
2Crystal grain is the disperse shape and is distributed in the porcelain body, because both have different thermal expansivity, t-ZrO
2Different stressing conditions is then arranged, when it is subjected to the oppressive of matrix, ZrO around the crystal grain
2Transformation mutually also will be suppressed.So just can make t-ZrO
2Be retained in below the room temperature.In addition, ZrO
2Crystal grain is as far as possible little, ZrO
2Particle is littler, short grained t-ZrO
2To m-ZrO
2The temperature of conversion is low to help transformation toughening, therefore, make ZrO
2Crystal grain is the disperse shape and is distributed in the porcelain body.In the porcelain base chemical ingredients, control Fe
2O
3≤ 0.3%, Na
2O＜0.5%.
The basic chemical ingredients of the enamel that is complementary with the porcelain base among the present invention is: SiO
270-74%, Al
2O
314-15, CaO 0.5-1.5%, MgO 3.5-4.5%, Fe
2O
3≤ 0.1%, Li
2O 0.2-1% K
2O 4.0-8.8%, ZrO
20.2-0.6% (weight).
The production method of high tonghness reinforced porcelain of the present invention is: production process need be passed through raw material processing, batching, ball milling, takes out slurry, sieved, inhales iron, press filtration, old, pugging, blank forming, body drying, glazing, burn till etc., the invention is characterized in:
1, the blank composition of raw materials basic composition is: kaolin 40-60%, potassium felspar sand 10-25%, calcined material 20-40%, triphane 2-10% (weight), the calcined material in the prescription is that the powder by three kinds of raw materials of rhombspar of the commercial alumina of the zircon of 10-25%, 75-89%, 1-5% mixes at the 1400-1450 ℃ of material after the calcining down.
2, the glaze composition of raw materials basic composition is: clay 8-16% (wherein attaclay accounts for the 2-4% of glaze composition of raw materials), potassium felspar sand 30-50%, triphane 2-8%, talcum 8-12%, quartzy 20-25%, the useless ceramics 8-15% (weight) of this base.
When 3, blank prepares, be earlier with calcined material by the prescription ball milling of weighing earlier, reach the surplus rate of 10000-hole sieve≤0.1% after, weighing by prescription adds kaolin, potassium felspar sand, triphane ball milling and reaches the surplus rate of 10000-hole sieve≤0.2% again.
4, firing temperature 1300-1350 ℃.
Above-described calcined material is after 500-1000 purpose zircon and commercial alumina powder, the ground dolomite of crossing 250 mesh sieves are mixed by the proportioning of stipulating above, at the material of 1400-1450 ℃ of temperature lower calcination acquisition.In calcination process, utilize excessive Al
2O
3With zircon (ZrSiO
4) 1400-1450 ℃ of thermotonus, rhombspar generates zirconium white (ZrO as mineralizer and stablizer
2), mullite (3Al
2O
32SiO
2) and α-Al
2O
3Three kinds of crystalline phases of corundum.Calcined material and flux thing (potassium felspar sand, triphane), the kaolin ratio in accordance with regulations of gained are prepared, after steps such as ball milling, when base substrate is burnt till, because kaolin generates mullite and SiO at 1200-1300 ℃
2, make the mullite crystalline phase in the porcelain base be further increase, and corundum, zirconium white crystalline phase amount are relatively stable.Owing to introduce triphane, potassium felspar sand in the mineral prescription of base substrate, make base substrate when burning till, about 1200 ℃, produce liquid phase (lowest total of the melting point temperature), especially triphane has strong fusing assistant effect, in the time of firing temperature 1300-1350 ℃, make total amount of liquid phase about 50%, promote the base substrate body sintering of crystalline phase 〉=45% amount of this composition decision, simultaneously, the SiO that kaolin decomposites in triphane and the base substrate
2Reaction generates β-triphane Solid solution (Li
2OAl
2O
38SiO
2), can eliminate coarse particles quartz or cristobalite so greatly and bring reduction physical strength, it is excessive also to be simultaneously that each thermal expansion between mutually of control base substrate thermal expansion can differ from, and plays mitigate effects, the thermostability of favourable raising porcelain.In addition, base substrate in sintering process, have a spot of silicon-dioxide again can and ZrO
2The generation zircon reacts, and zircon is melted in the viscosity that has improved glassy phase in the glassy phase relatively, widening of the firing temperature of favourable porcelain, it is thick that the increase of viscosity has simultaneously suppressed the length of mullite crystal whisker, make mullite crystal remain the needle-like networking structure that interweaves, the crystalline framework base of porcelain distributes and homogenizes, and has improved intensity greatly.Because the lowest total of the melting point temperature is about 1200 ℃ in the base substrate, burn till the cubic phase ZrO that the disperse shape in the porcelain body of back distributes like this
2(t-ZrO
2) in process of cooling, in the time of 1000 ℃, face upward effect because of the pressure that is subjected to matrix, can not be converted into monocline phase ZrO
2(m-ZrO
2), like this, cool to room temperature, the ZrO in the porcelain body
2Crystalline phase all is t-ZrO basically
2, have good transformation toughening effect.With the porcelain that the present invention makes, physical strength improves greatly, folding strength 〉=2000Kg/cm
2, toughness 〉=5Kgf-cm/cm
2Be the embodiment that do not limit of the present invention below.
Embodiment: the production of high tonghness reinforced porcelain tableware
1, determine blank formulation (by weight):
Kaolin 50%, potassium felspar sand 15%, calcined material 30%, triphane 5%, the proportioning raw materials of calcined material is: zircon 17%, commercial alumina 80%, rhombspar 3%.When selecting raw material, introduce in the Chemical Composition of porcelain base control Fe
2O
3≤ 0.3%, Na
2O＜0.5%
2, glaze composition of raw materials (by weight):
Kaolin 10%, attaclay 3%, potassium felspar sand 42%, triphane 5%, talcum 10%, quartz 20%, the useless ceramics 10% of this base.
3, raw material processing: with the raw material powder of calcined material by proportioning mix 1400-1450 ℃ down calcining obtain calcined material, press the blank proportion of raw materials, calcined material elder generation ball milling reached the surplus rate of 10000-hole sieve≤0.1% after 15 hours after, add kaolin, potassium felspar sand, triphane ball milling 5-10 hour by prescription again, reach the surplus rate of 10000-hole sieve≤0.2%.
Glaze: make glaze slip according to a conventional method.
4, moulding: dish, dish, cup, bowl are all used roll forming.
5, biscuiting: the base substrate after the moulding carries out biscuiting, adopts oxydizing flame, temperature to be controlled at about 750 ℃ through after the drying treatment.
6, glazing: can carry out before the glazing decorating glazing then under the glaze.
7, glaze firing: in the long tunnel kiln of 70M, burn till 1320 ℃ of firing temperatures, high fiery soaking time 40 minutes.
8, inspection after construction packing.
The present invention utilizes ZrO
2The transformation toughening principle, be applied on traditional household china production technique, adopt zircon to introduce ZrO
2Greatly reduce production cost, it is high folding strength and resistance to impact shock that the porcelain of production has high tenacity.
Claims (6)
1, a kind of folding strength 〉=2000Kg/cm
2, toughness 〉=5Kgf-cm/cm
2High tonghness reinforced porcelain, it is characterized in that the Chemical Composition of the porcelain base of this porcelain contains SiO
238-50%, Al
2O
330-52%, K
2O 2.5-4.0%, ZrO
25-15%, CaO 0.5-1.5%, MgO 0.4-0.8%, Li
2O 0.2-1% (weight), the crystalline phase amount is greater than 45% in the porcelain body, and its crystalline phase is corundum, mullite, ZrO
2Crystal grain, the ratio of corundum and mullite crystalline phase amount is (3-1): (1-3), corundum crystalline phase amount is no more than 35% of porcelain body, and mullite crystalline phase amount is no less than 10%, ZrO
2Crystalline phase amount 1-9% (weight), corundum grain-size 1-2 μ m, ZrO
2Crystal grain 1-2 μ m, mullite is a needle-like.Fail to grow up in 30 μ m.
2,, it is characterized in that the basic chemical ingredients of the enamel that is complementary with the porcelain base is: SiO according to the described high tonghness reinforced porcelain of claim l
270-74%, Al
2O
314-15, CaO 0.5-1.5%, MgO 3.5-4.5%, Fe
2O
3≤ 0.1%, Li
2O 0.2-l% K
2O 4.0-8.8%, ZrO
20.2-0.6% (weight).
3, high tonghness reinforced porcelain according to claim 1 is characterized in that ZrO
2Crystal grain is the disperse shape and is distributed in the porcelain body.
4, high tonghness reinforced porcelain according to claim 1 is characterized in that in the porcelain base chemical ingredients, control Fe
2O
3≤ 0.3%, Na
2O (0.5%).
5, a kind of production method of high tonghness reinforced porcelain is through raw material processing, batching, ball milling, take out slurry, sieve, inhale iron, press filtration, old, pugging, blank forming, body drying, glazing, burn till.It is characterized in that:
(1), the blank composition of raw materials basic composition is: kaolin 40-60%, potassium felspar sand 10-25%, calcined material 20-40%, triphane 2-10% (weight), the calcined material in the prescription is that the powder by three kinds of raw materials of rhombspar of the commercial alumina of the zircon of 10-25%, 75-89%, 1-5% mixes at the 1400-1450 ℃ of material after the calcining down.
(2), the glaze composition of raw materials basic composition is: clay 8-16%, wherein attaclay accounts for the useless ceramics 8-15% (weight) of 2-4%, potassium felspar sand 30-50%, triphane 2-8%, talcum 8-12%, quartzy 20-25%, this base of glaze composition of raw materials.
(3), when blank prepares, be earlier with calcined material by the prescription ball milling of weighing earlier, reach the surplus rate of 10000-hole sieve≤0.1% after, weighing by prescription adds kaolin, potassium felspar sand, triphane ball milling and reaches the surplus rate of 10000-hole sieve≤0.2% again.
(4), firing temperature 1300-1350 ℃.
6, the production method of high tonghness reinforced porcelain according to claim 5, it is characterized in that calcined material is after 500-1000 purpose zircon and commercial alumina powder, the ground dolomite of crossing 250 mesh sieves are mixed by the proportioning of stipulating above, at the material of 1400-1450 ℃ of temperature lower calcination acquisition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94110907A CN1050347C (en) | 1994-03-31 | 1994-03-31 | High tonghness reinforced porcelain and producing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94110907A CN1050347C (en) | 1994-03-31 | 1994-03-31 | High tonghness reinforced porcelain and producing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1109454A CN1109454A (en) | 1995-10-04 |
| CN1050347C true CN1050347C (en) | 2000-03-15 |
Family
ID=5034824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94110907A Expired - Fee Related CN1050347C (en) | 1994-03-31 | 1994-03-31 | High tonghness reinforced porcelain and producing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1050347C (en) |
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| CN1061956C (en) * | 1997-11-04 | 2001-02-14 | 胡勇波 | Zirconium magnesium tempering porcelain |
| CN101618961B (en) * | 2009-07-23 | 2012-07-04 | 福州大学 | Corundum material prepared from waste activated alumina and preparation method thereof |
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| CN102085061A (en) * | 2010-11-19 | 2011-06-08 | 山东硅元新型材料有限责任公司 | Daily-use double-layer ceramic bowl and preparation method thereof |
| CN102249655B (en) * | 2011-06-13 | 2012-10-10 | 郑州市瑞沃耐火材料有限公司 | Ductile mullite brick for pipelines of hot blast stoves and manufacturing method thereof |
| CN102381883B (en) * | 2011-07-29 | 2014-02-19 | 兴化市华伦达铸钢有限公司 | Method for preparing ceramic inner cylinder hanging tile |
| CN102674808B (en) * | 2012-06-11 | 2013-07-24 | 大埔县富大陶瓷有限公司 | High-toughness composite matte ceramic product and manufacturing method thereof |
| CN104496509B (en) * | 2015-01-01 | 2015-10-28 | 陈星延 | A kind of ceramic substrate composition and being used for prepares purposes and the method for tangible family tree |
| CN106477885B (en) * | 2016-11-07 | 2019-05-31 | 广东易成陶瓷实业有限公司 | A kind of high hardness wear-resisting medium temperature semi-faience and preparation method thereof |
| CN109133954B (en) * | 2018-11-14 | 2021-10-26 | 福建省德化龙辉陶瓷有限公司 | High-toughness refractory domestic ceramic and preparation method thereof |
| CN111153679A (en) * | 2020-01-07 | 2020-05-15 | 湖南泰鑫瓷业有限公司 | Reinforced porcelain and preparation method thereof |
| CN113121128B (en) * | 2021-06-04 | 2023-03-17 | 嘉华特种水泥股份有限公司 | High-strength toughened cementing material and preparation method and application thereof |
| CN115196943B (en) * | 2022-07-07 | 2023-05-05 | 景德镇陶瓷大学 | Prestressed reinforced domestic ceramic taking zirconium silicate as reinforcing phase and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86100202A (en) * | 1985-01-18 | 1986-08-27 | 日本碍子株式会社 | High strength feldspathic porcelain and manufacture method thereof |
| CN1058009A (en) * | 1990-07-10 | 1992-01-22 | 湖南省陶瓷研究所 | Low-temp dolomite porcelain |
-
1994
- 1994-03-31 CN CN94110907A patent/CN1050347C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86100202A (en) * | 1985-01-18 | 1986-08-27 | 日本碍子株式会社 | High strength feldspathic porcelain and manufacture method thereof |
| CN1058009A (en) * | 1990-07-10 | 1992-01-22 | 湖南省陶瓷研究所 | Low-temp dolomite porcelain |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1109454A (en) | 1995-10-04 |
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