CN109534802B - Far infrared autogenous glaze porcelain with high utilization of desert materials and preparation process thereof - Google Patents
Far infrared autogenous glaze porcelain with high utilization of desert materials and preparation process thereof Download PDFInfo
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- CN109534802B CN109534802B CN201811583049.9A CN201811583049A CN109534802B CN 109534802 B CN109534802 B CN 109534802B CN 201811583049 A CN201811583049 A CN 201811583049A CN 109534802 B CN109534802 B CN 109534802B
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- autogenous
- desert
- glaze porcelain
- glaze
- far infrared
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- 239000000463 material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910052573 porcelain Inorganic materials 0.000 title claims description 76
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000004576 sand Substances 0.000 claims abstract description 37
- 229910052742 iron Inorganic materials 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 23
- 229910052903 pyrophyllite Inorganic materials 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 239000011777 magnesium Substances 0.000 claims abstract description 16
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 14
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000440 bentonite Substances 0.000 claims abstract description 13
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 13
- 239000003245 coal Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000007873 sieving Methods 0.000 claims abstract description 13
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 12
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims abstract description 12
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052642 spodumene Inorganic materials 0.000 claims abstract description 11
- 239000010456 wollastonite Substances 0.000 claims abstract description 11
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 11
- 229910052656 albite Inorganic materials 0.000 claims abstract description 9
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 238000003825 pressing Methods 0.000 claims abstract description 9
- 238000000498 ball milling Methods 0.000 claims abstract description 8
- 239000002023 wood Substances 0.000 claims abstract description 7
- 238000007493 shaping process Methods 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims description 19
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 16
- 238000010304 firing Methods 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 238000004061 bleaching Methods 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- 238000007885 magnetic separation Methods 0.000 claims description 5
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
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- 238000007670 refining Methods 0.000 claims 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 14
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 53
- 239000000919 ceramic Substances 0.000 description 20
- 229910010293 ceramic material Inorganic materials 0.000 description 13
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
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- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 2
- 244000038561 Modiola caroliniana Species 0.000 description 2
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- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- -1 iron ions Chemical class 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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Abstract
The invention relates to a far infrared autogenous glaze bone china and a preparation process thereof, which are made of desert materials and comprise the following raw materials in percentage by weight: sand grains taken from deserts: 50% -60%; pyrophyllite: 10% -20%; purple wood knots: 8% -15%; coal gangue: 10% -18%; magnesium bentonite: 2% -4%; potassium feldspar: 4% -8%; albite: 4% -8%; spodumene: 2% -5%; zirconium silicate: 3% -5%; wollastonite: 4% -6%; the production process of the bone china comprises the following steps: preparing materials according to a formula, ball milling, sieving, removing iron, filter pressing, performing primary pugging and secondary pugging, and shaping and sintering; the autogenous glaze bone china prepared by the method has the advantages of good toughness, high strength and good thermal stability, is suitable for a sharp cooling and heating environment, and simultaneously has good radiance and a wide frequency spectrum.
Description
Technical Field
The invention relates to the technical field of ceramics, in particular to a far infrared authigenic glazed porcelain with high utilization of desert materials and a preparation process thereof.
Background
With the continuous development of ceramic technology, people adopt different raw materials and different processes to manufacture ceramics, a plurality of new types of ceramics appear, and bone china and far infrared ceramics are two types which are hot. Bone china is a well-known high-grade porcelain, and dendrized jade porcelain is a remarkable representative of bone china, mainly takes animal bone ash as a main raw material, is added with a certain amount of kaolin, quartz, feldspar and the like to prepare soft porcelain, and has the advantages of fine porcelain quality, high whiteness, high transparency, smooth glaze surface, high mechanical strength and the like. The high-radiation infrared ceramic material in the last 80 th century is developed vigorously abroad, and the first-class Guangfu and Konghong in Japan adopt Fe3O4、MnO2Transition metal oxides such as CuO, CoO and the like are used as raw materials to prepare high-radiation infrared ceramic materials with normal full-wave-band radiance larger than 0.90; ParkerHolding, USA, is said to have adopted AB in its patent literature2O4The inorganic compound is used as infrared radiation material, where A is mainly Mg, Zn, Mn, Ni, Co, etc. and B is mainly Al, Cr, Mn, Fe, etc. The far infrared ceramics are prepared by sintering more than 20 inorganic compounds and trace metals or specific natural ores respectively in different proportions, and the production of the far infrared ceramics has larger dependence on non-renewable resources. The excessive utilization of high-quality resources accelerates the over-quick exhaustion of the resources and increases the production cost of the far infrared ceramics.
The desert occupies 10 percent of land area, the desertification land area of China is 172 ten thousand square kilometers, and the desertification land area occupies nearly 1/5 percent of the land area. At present, the most main approach of utilizing the desert lies in developing the photosynthesis industry and modern agriculture, and introducing sand grains in the desert into the traditional ceramic industry is a brand-new thought and development direction, so that the mining amount of mineral resources can be reduced, the energy consumption of the ceramic industry is reduced, the social development trend of energy conservation, emission reduction and ecological protection is met, and the development and reform of the ceramic industry are promoted. The light mineral content in the desert sand grains is high, generally more than 90 percent, the main components of the light mineral are quartz, feldspar and calcite, the light mineral can replace the quartz, feldspar and other materials in the ceramic production raw materials, and a scheme of replacing mineral resources by using the desert sand grains can be introduced into a desert area to provide a new sand control and prevention road.
The Chinese patent with the application number of 201410210975.7 discloses an iron tailing far infrared ceramic material and a preparation method thereof, and the specifically disclosed ceramic material mainly comprises 35-75% of iron tailings, 1-9% of clay, 11-25% of silicon dioxide, 11-25% of calcium carbonate and 2-6% of aluminum oxide, wherein the sum of the components is 100%, and the iron tailing, the clay, the silicon dioxide, the calcium silicate and the aluminum oxide are used as raw materials, and the iron tailing far infrared ceramic material is prepared by ball milling, sieving, blending, stirring, drying, mixing, dry pressing and sintering. The invention makes full use of iron tailings, reduces the production cost, but the prepared far infrared ceramic material is fragile, has poor toughness and narrower radiation wave band. The Chinese patent with the application number of 201410211126.3 discloses a rare earth-containing iron tailing far infrared ceramic material and a preparation method thereof, and the specifically disclosed ceramic material mainly comprises 35-75% of iron tailing, 1-7% of clay, 6-25% of silicon dioxide, 6-25% of calcium carbonate, 2-7% of aluminum oxide and 1-9% of rare earth, wherein the sum of the components is 100%, and meanwhile, the iron tailing, the clay, the silicon dioxide, the calcium silicate and the aluminum oxide are used as main raw materials, and the rare earth is used as an additive, and the rare earth-containing iron tailing far infrared ceramic material is prepared mainly through ball milling, sieving, batching, stirring, drying, mixing, dry pressing and sintering processes. The invention not only makes full use of the iron tailings, but also can improve the far infrared emission capability of the ceramic and radiate far infrared rays with high emissivity, but the prepared far infrared ceramic material has poor toughness and strength and poor thermal stability, and cannot be applied to the environment with rapid cooling and rapid heating.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a far infrared authigenic glaze porcelain with high utilization of desert materials and a preparation process thereof, desert sand grains are introduced into authigenic glaze porcelain pug to replace kaolin ores and quartz ores, the authigenic glaze porcelain with better toughness and higher strength can be prepared, the thermal stability is good, the enamel porcelain is suitable for being used in an environment with rapid cooling and rapid heating, and meanwhile, the enamel porcelain has better wide frequency spectrum and radiation rate.
The technical scheme of the invention is as follows:
a far infrared autogenous glaze porcelain with high utilization of desert materials comprises the following components in percentage by weight: sand grains taken from deserts: 45% -55%; pyrophyllite: 8% -10%; purple wood knots: 6 to 8 percent; coal gangue: 10% -13%; magnesium bentonite: 2% -4%; potassium feldspar: 4% -8%; albite: 3% -6%; micron-sized spodumene: 1% -3%; zirconium silicate: 2% -4%; wollastonite: 4 to 6 percent.
The self-generated glaze porcelain pug comprises the following chemical components in percentage by weight: SiO 22:60%~70%;Al2O3:15%~20%;CaO:2.0%~4.5%;ZrO2:3.5%~5.0%;Na2O+K2O:2.6%~4.6%;Fe2O3:1.2%~2.0%;MgO:2.8%~3.8%;LiO2:0.8%~1.5%;TiO2:0.5%~1.0%;P2O5:0.05%~0.2%。
Wherein, the sand grains from the desert need to be mixed with water and then are cleaned by ultrasonic waves to remove siliceous scales and siliceous films deposited on the surfaces of the sand grains from the desert.
The method comprises the following steps of smashing pulp, magnetic separation and bleaching.
A preparation process of far infrared autogenous glaze porcelain with high utilization of desert materials comprises the following process flows of proportioning according to a formula, ball milling, sieving, iron removal, filter pressing, first pugging, second pugging and shaping and firing; the self-generated glaze porcelain pug is calcined at a high temperature of 1200-1300 ℃ to form the self-generated glaze porcelain at one time, and the firing process of the one-time firing is as follows:
(1) slowly raising the temperature for 2-3 h to 200 ℃ at the normal temperature-200 ℃, and firing in an oxygen atmosphere at the temperature raising rate of 1-1.5 ℃/min;
(2) raising the temperature rise speed at 200-900 ℃, and keeping the temperature rise speed at 8-10 ℃/min;
(3) reducing the heating rate to 900-1200 ℃ to prevent the autogenous glaze porcelain from cracking, wherein the heating rate is 3-5 ℃/min;
(4) keeping the temperature within the range of 1200-1300 ℃ for 3-6 h, introducing nitrogen in the temperature range to create a nitrogen atmosphere and promote the stable formation of the crystal phase of the autogenous glaze porcelain;
(5) 1300-600 ℃, and a high-temperature rapid cooling stage, wherein the cooling rate is 16-18 ℃/min;
(6) naturally cooling to below 100 ℃.
Wherein the pH of the pug is adjusted to be 7-8 in the first pugging and the second pugging and is alkalescent; because the pug contains the rosewood knots which contain more carbon humus, the humus can be hydrolyzed to form protective colloid under the action of alkali liquor, and the pug forming performance is improved.
The invention has the following beneficial effects:
1. in the invention, sand grains are introduced into the autogenous glaze porcelain blank to replace clay, quartz, feldspar and other raw materials in part of the German jade porcelain blank, wherein the sand grains account for 50-60 percent of the raw materials and can replace clay minerals; the sand contains more than 90% of light minerals such as quartz, feldspar and calcite, and can be mixed with SiO in the autogenous enamel blank2、CaO、Al2O3、Na2O、K2O and other components, wherein most of clay raw materials of the German jade porcelain come from Longyan kaolin, sand grains are used for replacing all quartz ores, the use of the kaolin ores and hydroxyapatite is reduced, the mining cost of mineral resources is saved, the utilization of the mineral resources is greatly reduced, and the mineral resources are reducedThe mining and the waste of the coal mine are reduced, and the production cost is reduced. Meanwhile, the desert is fully utilized, and the method is a brand-new desert control thought and scheme, and accords with the development trend of ecological protection and circular economy.
2. The far infrared autogenous glaze porcelain prepared by the invention has better toughness and higher strength, and the fracture toughness is more than 12 MPa.m1/2The strength of the glaze surface is more than 580kg, f/mm2The bending strength is between 450-460MPa, the requirements of high toughness and high strength of the ceramic are met, the thermal stability is good, cracks do not appear in the self-generated glaze ceramic after multiple exchanges within the range of-20 ℃ to 180 ℃, the ceramic is suitable for the environment of rapid cooling and rapid heating, and the infrared radiance can be kept higher at the position of 5-20 mu m.
2. According to the invention, the self-glazed porcelain blank and the glaze are mixed into a whole, self-glazed is realized in the firing process, a glazing process is not required, the glaze is ensured to be uniform, and the defects of thin glaze, glaze lines, glaze rolling and glaze dirt on the surface of the finished self-glazed porcelain are prevented. Meanwhile, compared with the traditional production process flow of the self-growing glaze porcelain, the process of one-time firing is reduced by about half, the polishing process is not needed, and the dust emission is reduced; a 'water washing' process is not needed, so that the water resource consumption is reduced; does not need a large number of heating, cooling and drying procedures, saves energy, reduces energy consumption and 'three wastes' emission.
3. The main components of the pyrophyllite, the butcher's knot and the coal gangue are silicon dioxide and alumina, but the crystalline phase and the structure of the alumina in the three raw materials are different, under the condition of high-temperature calcination, alumina with different crystal phases is equivalent to be mutually added toughening crystal phases through an in-situ composite technology, no additional reinforcing agent or crystal seeds need to be introduced, three kinds of alumina crystal seeds can mutually permeate and grow into a wafer reinforcing body with large grain length-diameter ratio and uniformly distributed crystal whiskers, and the three kinds of alumina grains have different shapes but good compatibility, are connected with each other in a staggered way to form three-dimensional network distribution, and the toughness and the strength of the autogenous glaze porcelain are further enhanced, meanwhile, the three raw materials toughen by themselves to a certain extent, the incompatibility of a matrix phase and a toughening phase in physics or chemistry is eliminated, the thermodynamic stability of the matrix phase and the toughening phase is ensured, and the thermal stability of the autogenous glaze porcelain is further improved.
4. In the invention, magnesium-based bentonite is added into the autogenous glaze porcelain pug, and the magnesium-based bentonite contains Mg2+Can be reacted with Fe2+React to form solid solution of Mg & FeO and TiO2Reaction to produce MgO & TiO2,Fe2+And TiO2Can be precipitated, can weaken the adverse effect of iron and titanium on the whiteness of the autogenous glaze porcelain, and simultaneously introduces Mg into the magnesium-based bentonite2+Has opacifying function and is also beneficial to improving the whiteness of the body of the self-made glazed porcelain; meanwhile, when different pigments are added to prepare the colored self-growing glazed porcelain, the purity of the color can be improved.
5. In the invention, wollastonite powder, zirconium silicate and spodumene are added, wherein the zirconium silicate has good chemical stability and is not influenced by the firing atmosphere of the autogenous glaze porcelain, the separation performance of blank glaze of the autogenous glaze porcelain can be obviously improved, and the glaze hardness of the autogenous glaze porcelain is improved; meanwhile, zirconium silicate forms baddeleyite after the autogenous glaze porcelain is calcined at high temperature, so that the whitening effect can be achieved in the ceramic glaze, because the baddeleyite and the like are formed after the ceramic is calcined, incident light waves are scattered, and the opacifying and whitening effects are achieved; spodumene can enable the autogenous enamel to be capable of withstanding rapid cooling and heating environmental changes, and good thermal stability is guaranteed; the wollastonite powder can greatly reduce the firing temperature, shorten the firing time, greatly save fuel and obviously reduce the product cost; meanwhile, the mechanical property of the product is improved, cracks and warping of the product are reduced, the glaze luster of the glaze surface is increased, the strength of the blank is improved, and the qualification rate of the product is improved.
Detailed Description
The invention will be further described with reference to preferred embodiments.
Example 1
A far infrared autogenous glaze porcelain with high utilization of desert materials comprises the following components in percentage by weight: taking 50% of sand grains from desert; 10% of pyrophyllite; 8% of purple wood knot; 10 percent of coal gangue; 2% of magnesium-based bentonite; 6 percent of potassium feldspar; 3% of albite; 3% of micron-sized spodumene; 2% of zirconium silicate; 6 percent of wollastonite.
Preferably, the self-generated glaze porcelain pug is chemicallyComprises the following components in percentage by weight: SiO 22:60%;Al2O3:20%;CaO:4.5%;ZrO2:5.0%;Na2O+K2O:4.6%;Fe2O3:1.2%;MgO:2.8%;LiO2:0.8%;TiO2:1.0%;P2O5:0.1%。
Preferably, the process flow of preparing the self-generated glazed porcelain by the self-generated glazed porcelain mud material sequentially comprises the following steps of preparing materials according to a formula, putting 50% of sand grains taken from desert, 10% of pyrophyllite, 8% of mauve knot, 10% of coal gangue, 2% of magnesium-based bentonite, 6% of potassium feldspar, 3% of albite, 3% of micron-sized spodumene, 2% of zirconium silicate and 6% of nano wollastonite into a ball mill for mixing and grinding, wherein the materials are as follows: ball: water is 1:1.5:0.5, and evenly mixed pug is prepared; and then, sequentially sieving the uniformly mixed pug, removing iron, performing filter pressing, performing first pugging, performing second pugging and shaping and sintering, and finally sieving the pug by a 350-mesh sieve.
Preferably, the sand grains taken from the desert need to be mixed with an aqueous solution and then subjected to ultrasonic cleaning to remove the siliceous scales and siliceous films deposited on the surfaces of the sand grains in the desert, and after the sand grains in the desert are weathered for a long time, siliceous deposited layers such as the siliceous scales and the siliceous films are widely existed on the surfaces of the sand grains, so that the material adsorption energy Europe and the charge carrying capacity of the sand grains can be changed.
Preferably, the lignum sappan is pretreated by sequentially carrying out the process flows of pulping, magnetic separation and bleaching.
Wherein, the pH value of the pug is adjusted to be 7 and the pug is alkalescent in the first pugging and the second pugging; because the pug contains the rosewood knots which contain more carbon humus, the humus can be hydrolyzed to form protective colloid under the action of alkali liquor, and the pug forming performance is improved.
Example 2
A far infrared autogenous glaze porcelain with high utilization of desert materials comprises the following components in percentage by weight: 55% of sand grains taken from desert; 8% of pyrophyllite; 6 percent of purple wood knot; 11% of coal gangue; 3% of magnesium-based bentonite; 4% of potassium feldspar; 4% of albite; micron-sized spodumene 1%; 4% of zirconium silicate; 4 percent of wollastonite.
Preferably, the self-generated glaze porcelain pug comprises the following chemical components in percentage by weight: SiO 22:65%;Al2O3:18%;CaO:3%;ZrO2:4%;Na2O+K2O:3.2%;Fe2O3:1.8%;MgO:3.2%;LiO2:1%;TiO2:0.75%;P2O5:0.05%。
Preferably, the process flow of preparing the self-glazed porcelain from the self-glazed porcelain pug comprises the following steps of sequentially mixing and grinding 55% of sand grains from desert, 8% of pyrophyllite, 6% of mauveria, 11% of coal gangue, 3% of magnesium-based bentonite, 4% of potassium feldspar, 4% of albite, 1% of micron-sized spodumene, 4% of zirconium silicate and 4% of nano-wollastonite in a ball mill according to a formula, wherein the materials are as follows: ball: water is 1:1.5:0.5, and evenly mixed pug is prepared; and then, sieving, deironing, filter pressing, first pugging, second pugging and shaping and sintering the uniformly mixed pug, and finally sieving the pug by a 350-mesh sieve.
Preferably, the sand grains taken from the desert need to be mixed with water and then are cleaned by ultrasonic waves to remove the siliceous scales and siliceous films deposited on the surfaces of the sand grains in the desert, and after the sand grains in the desert are weathered for a long time, siliceous deposited layers such as the siliceous scales and the siliceous films are widely existed on the surfaces of the sand grains, so that the material adsorption energy Europe and the charge carrying capacity of the sand grains can be changed.
Preferably, the lignum sappan is pretreated by sequentially carrying out the process flows of pulping, magnetic separation and bleaching.
Preferably, the pH value of the pug is adjusted to be 8 and the pug is weakly alkaline in the first pugging and the second pugging; because the pug contains the rosewood knots which contain more carbon humus, the humus can be hydrolyzed to form protective colloid under the action of alkali liquor, and the pug forming performance is improved.
Example 3
A far infrared autogenous glaze porcelain with high utilization of desert materials comprises the following components in percentage by weight: 45% of sand grains taken from desert; 9% of pyrophyllite; 7% of purple wood knot; 13 percent of coal gangue; 4% of magnesium-based bentonite; 8% of potassium feldspar; 4% of albite; 2% of micron-sized spodumene; 3% of zirconium silicate; 5 percent of wollastonite.
Preferably, the self-generated glaze porcelain pug comprises the following chemical components in percentage by weight: SiO 22:70%;Al2O3:15%;CaO:2.0%;ZrO2:3.5%;Na2O+K2O:2.6%;Fe2O3:2.0%;MgO:3.5%;LiO2:0.8%;TiO2:0.5%;P2O5:0.1%。
Preferably, the process flow of preparing the self-generated glazed porcelain by the self-generated glazed porcelain mud material sequentially comprises the following steps of preparing materials according to a formula, putting 45% of sand grains taken from desert, 9% of pyrophyllite, 7% of mauve knot, 13% of coal gangue, 4% of magnesium-based bentonite, 8% of potassium feldspar, 4% of albite, 2% of micron-sized spodumene, 3% of zirconium silicate and 5% of nano-wollastonite into a ball mill for mixing and grinding, wherein the materials are as follows: ball: water is 1:1.5:0.5, and evenly mixed pug is prepared; and then, sieving, deironing, filter pressing, first pugging, second pugging and shaping and sintering the uniformly mixed pug, and finally sieving the pug by a 350-mesh sieve.
Preferably, the sand grains taken from the desert need to be mixed with water and then are cleaned by ultrasonic waves to remove the siliceous scales and siliceous films deposited on the surfaces of the sand grains in the desert, and after the sand grains in the desert are weathered for a long time, siliceous deposited layers such as the siliceous scales and the siliceous films are widely existed on the surfaces of the sand grains, so that the material adsorption energy Europe and the charge carrying capacity of the sand grains can be changed.
Preferably, the lignum sappan is pretreated by sequentially carrying out the process flows of pulping, magnetic separation and bleaching.
Preferably, the pH value of the pug is adjusted to be 8 and the pug is weakly alkaline in the first pugging and the second pugging; because the pug contains the rosewood knots which contain more carbon humus, the humus can be hydrolyzed to form protective colloid under the action of alkali liquor, and the pug forming performance is improved.
The autogenous glaze porcelain pug prepared according to the raw material proportion of the embodiment 1-3 is calcined at a high temperature of 1200-1300 ℃ to form the autogenous glaze porcelain, and the process of one-time firing is as follows:
(1) slowly raising the temperature for 2-3 h to 200 ℃ at the normal temperature-200 ℃, and firing in an oxygen atmosphere at the temperature raising rate of 1-1.5 ℃/min; slowly heating to prevent the formed blank from cracking, removing free water in the formed blank and bound water on the surface of the pug, and stably putting the pug into the stages of dehydration, drying and consolidation;
(2) raising the temperature rise speed at 200-800 ℃, and keeping the temperature rise speed at 8-10 ℃/min; during the temperature, hydroxyl in pyrophyllite in the self-generated glaze porcelain pug is continuously removed, organic impurities and humus in rosewood knots, coal gangue and magnesium bentonite are gradually decomposed at high temperature, and the self-generated glaze porcelain pug is fired and consolidated in the temperature interval; meanwhile, in the temperature range, the occurrence state of iron in the pyrophyllite is continuously changed along with the continuous rise of the temperature, under the condition of high-temperature oxidation, oxygen atoms in the environment diffuse into crystals of the pyrophyllite along vacancies, the valence state and the energy level of impurity iron ions in crystal lattices are changed, the pyrophyllite powder is gradually changed into snow white, the whiteness of the mud is increased, and meanwhile, the crystal form of the pyrophyllite begins to be changed into the pyrophyllite and amorphous SiO2And cristobalite;
(3) sintering and shrinkage molding process of the autogenous glaze porcelain pug is carried out at 800-1200 ℃ and the heating rate of 3-5 ℃/min; in the temperature range, pyrophyllite, butcher's-stone and coal gangue in the autogenous enamel mud gradually generate reverse-normal crystal phase transformation and crystal seed growth, and alumina with different crystal phases in the three raw materials generates in-situ composite reaction, which is a key period of phase change toughening, and at the moment, the reduction of the temperature rise rate can prevent the autogenous enamel from cracking;
(4) keeping the temperature within the range of 1200-1300 ℃ for 3-6 h, introducing nitrogen in the temperature range, creating a nitrogen atmosphere, avoiding the interference of external gas, simultaneously prolonging the heat preservation time, jointly promoting the three-dimensional network crystalline phase structure formed in the autogenous glaze porcelain pug to gradually tend to be stable, and further improving the toughness of the autogenous glaze porcelain after being formed;
(5) 1300-600 ℃, and a high-temperature rapid cooling stage, wherein the cooling rate is 16-18 ℃/min; in the temperature range, the self-generated glaze porcelain needs to be quenched to prevent low-valence iron elements contained in the formed self-generated glaze porcelain from being oxidized into high-valence iron again to cause the self-generated glaze porcelain to turn yellow and become opaque;
(6) naturally cooling to below 100 ℃.
Comparative example 1:
a high-toughness high-strength far infrared ceramic material comprises the following ceramic components in percentage by mass: 5% of SiC toughening crystal whisker; nano ZrO2(2Y) precursor 15%; and the proportion of MgO as a framework material is 15 percent; the balance of nano alpha-Al2O3(ii) a The nano ZrO2(2Y) is a zirconium oxide precursor doped and coated with 2% of rare earth yttrium; the MgO is submicron powder with the granularity of 0.1-1 μm; the alpha-Al2O3The purity is more than 99 percent, and the granularity is 50-200 nm; the length of the SiC whisker is 200-500 mu m.
Comparative example 2
A far infrared ceramic material of rare earth-containing iron tailings and a preparation method thereof are disclosed:
A. putting the iron tailings into a ball mill for ball milling for 30min, and after ball milling, sieving the iron tailings with a 350-mesh sieve to obtain iron tailing powder;
B. taking 35 wt% of the iron tailing powder obtained in the step A, adding 7 wt% of clay, 25 wt% of silicon dioxide, 25 wt% of calcium carbonate, 7 wt% of alumina, 1 wt% of lanthanum nitrate and 15 wt% of water, mixing and continuously stirring for 30 min;
C. drying the mixture in the step B for 1h at the temperature of 100 ℃;
D. c, ball-milling and mixing the dried mixture in the step C for 60min, and sieving the mixture by a 120-mesh sieve;
E. and D, pressing and forming the mixed material in the step D under the conditions that the forming pressure is 30MPa and the pressure is maintained for 1.5min to obtain a ceramic blank, and then sintering the blank in a sintering furnace to finally obtain the rare earth-containing iron tailing far infrared ceramic material.
The performance test of the autogenous glaze porcelain with high utilization of desert materials comprises the following steps:
table 1 shows the results of normal total emissivity test
Inspection item | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
Normal full radiance | 0.88 | 0.90 | 0.91 | 0.80 | 0.85 |
As can be seen from the above table, the self-grown enamel prepared by the invention maintains the infrared radiance at a higher level even after being processed at the temperature of more than 800 ℃, and the infrared radiance at the position of 5-20 μm can reach more than 0.90.
TABLE 2 comprehensive mechanical Properties test results
As can be seen from the above table, the strength and toughness of the self-glazed porcelain prepared by the present invention can meet the standards of high strength and high toughness as obtained in comparative example 1, and at the same time, the water absorption is low, the transmittance is good, the thermal stability and the stability under rapid cooling and rapid heating state change of the self-glazed porcelain are improved, and if a pigment is required to be added to prepare a colored self-glazed porcelain, the whiteness is high, and the purity of the color of the colored self-glazed porcelain can be improved.
In conclusion, the infrared radiance of the autogenous glaze porcelain prepared by the method can reach more than 0.90 on average, and the autogenous glaze porcelain has good mechanical property, good thermal stability, high whiteness and high transmittance.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (4)
1. The far infrared autogenous glaze porcelain with high utilization of desert materials is characterized in that: the self-produced glaze porcelain pug comprises the following components in percentage by weight: sand grains taken from deserts: 45% -55%; pyrophyllite: 8% -10%; purple wood knots: 6 to 8 percent; coal gangue: 10% -13%; magnesium bentonite: 2% -4%; potassium feldspar: 4% -8%; albite: 3% -6%; micron-sized spodumene: 1% -3%; zirconium silicate: 2% -4%; wollastonite: 4% -6%;
the self-generated glaze porcelain pug comprises the following chemical components in percentage by weight: SiO 22:60%~70%;Al2O3:16%~20%;CaO:2.5%~4.5%;ZrO2:3.5%~5.0%;Na2O+K2O:2.6%~4.6%;Fe2O3:1.2%~2.5%;MgO:2.8%~3.8%;Li2O:0.8%~1.5%;TiO2:0.5%~1.0%;P2O5:0.1%~0.2%;
The preparation process of the far infrared autogenous glaze porcelain with high utilization of desert materials comprises the following process flows of proportioning according to a formula, ball milling, sieving, iron removal, filter pressing, first mud refining, second mud refining and shaping firing, wherein the autogenous glaze porcelain pug is fired at a high temperature of 1200-1300 ℃ to form the autogenous glaze porcelain, and the firing process of the one-time firing is as follows:
(1) slowly raising the temperature for 2-3 h to 200 ℃ at the normal temperature-200 ℃, and firing in an oxygen atmosphere at the temperature raising rate of 1-1.5 ℃/min;
(2) raising the temperature rise speed at 200-900 ℃, and keeping the temperature rise speed at 8-10 ℃/min;
(3) reducing the heating rate to 900-1200 ℃ to prevent the autogenous glaze porcelain from cracking, wherein the heating rate is 3-5 ℃/min;
(4) keeping the temperature within the range of 1200-1300 ℃ for 3-6 h, introducing nitrogen in the temperature range to create a nitrogen atmosphere and promote the stable formation of the crystal phase of the autogenous glaze porcelain;
(5) 1300-600 ℃, and a high-temperature rapid cooling stage, wherein the cooling rate is 16-18 ℃/min;
(6) naturally cooling to below 100 ℃.
2. The far infrared autogenous glaze porcelain with high utilization of desert material as claimed in claim 1, wherein: the sand grains from the desert need to be mixed with water and then are cleaned by ultrasonic waves to remove siliceous scales and siliceous films deposited on the surfaces of the sand grains from the desert.
3. The far infrared autogenous glaze porcelain with high utilization of desert material as claimed in claim 1, wherein: the purple wood knots need to be pretreated through the process flows of pulping, magnetic separation and bleaching in sequence.
4. The process for preparing far infrared autogenous glaze porcelain with high utilization of desert material as claimed in claim 1, wherein: and adjusting the pH value of the pug to be 7-8 in the first pugging and the second pugging to be alkalescent.
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