CN102875121A - Blank ceramic tile and production method thereof - Google Patents

Blank ceramic tile and production method thereof Download PDF

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CN102875121A
CN102875121A CN2012104391363A CN201210439136A CN102875121A CN 102875121 A CN102875121 A CN 102875121A CN 2012104391363 A CN2012104391363 A CN 2012104391363A CN 201210439136 A CN201210439136 A CN 201210439136A CN 102875121 A CN102875121 A CN 102875121A
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inferior
black
weight
slag
low
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苟文吉
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HUILI COUNTY ZIYUAN MINING CO Ltd
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HUILI COUNTY ZIYUAN MINING CO Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes

Abstract

The invention relates to a blank ceramic tile which comprises the following components in part by weight: 20 to 30 parts of aegirine-augite mineral slag, 15 to 20 parts of low-quality clay, 50 to 60 parts of low-quality quartz and 5 to 10 parts of low-quality talc. The blank interior wall brick is pure in color, stable in color generation, and low in cost. The invention further provides a production method of the blank ceramic tile, which reduces the production cost and the environmental pollution and protects the ecological environment.

Description

Black vitrified brick and production method thereof
Technical field:
The invention belongs to building material technical field, what relate to is a kind of vitrified tile and production method thereof, particularly be a kind of black vitrified brick and production method thereof.
Background technology:
Black ceramic goods Yin Seze is deep, dignified, have characteristic and very popular.International building circle is looked black for serious, luxurious current color, and black porcelain has good physicochemical property, makes it become a kind of new ceramics building material product.Porcelain brick is the building and ornament materials that grow up in the later stage eighties, is taken the lead in producing by Italy, imports China the beginning of the nineties into.Porcelain brick is divided polishing and is not polished two kinds.Polished tile is splendid, and the light elegance of the vitrified tile that does not polish is widely used on the finishing of senior building and Modern Residence, and black vitrified tile wherein is very popular, and good market outlook are arranged.But in traditional darky system colorant, in order to obtain comparatively pure black tone, usually to add the very expensive oxidation of price and bore, so that the black pigment cost is high, restrict the development of black ceramic product.Body stain mainly refers to the colorant that uses in the high temperature base substrate, its kind is few, but consumption is very large.
At present, the preparation method of pottery body stain is divided into two large classes basically: traditional solid sintering technology, the chemical coprecipitation of non-traditional Technology, sol-gel method, hydrothermal method, microemulsion method, certainly spread the preparation high-performance ceramic colorants such as synthetic, microwave heating method, mechanochemical synthesis, sonochemistry method, low-temp liquid-phase sintering method, so that the manufacturing technology of ceramic pigment and performance have had new breakthrough.Raw material from the colorant preparation, (cost is high) of using the preparation of AG nano-powder arranged, (cost is higher) of using the preparation of technical grade industrial chemicals also arranged, more utilize natural mineral and mine tailing, industrial residue the like waste to prepare environment-friendly ceramic pigment (cost is low), its production cost has a long way to go, effect and performance are also uneven.From the mode that ceramic pigment adds, there is each component that will form colorant directly to be added in the base substrate first, at high temperature sintering reaction and color reaction carry out simultaneously to make base substrate; Also have first the synthetic finished product colorant evenly to make an addition to again base substrate, after carry out high temperature sintering.
Xie Chunbo, the development of Pure Black Glaze [J] Hebei pottery, 1997,25 (3): 7, Fe-Cr series pigments is studied, following proportioning (oxide compound industrial chemicals) has been proposed: ferric oxide 34.4,51.2 chromic oxide 65.6,48.8, will burn till under 1280 ℃-1300 ℃ reducing flame after the raw material mixing.Proposing simultaneously the black prescription of vanadium is: Vanadium Pentoxide in FLAKES: 41.67%, and oxalic acid: 16.66%, quartz: 41.67%.This pigment burns till under 1280 ℃-1300 ℃ of reducing flames, but the black goods slightly brown transfer, color development is pure not.
Li Chunwen etc., Ni-Cr-Mn-Fe are synthetic and colour generation [J] pottery of mineral black, 1998,2:41, and having selected satisfied prescription is (oxide compound industrial chemicals): Ni 2O 36g, Cr 2O 319g, MnO 28g, Fe 2O 311g.This pigment begins to occur solid state reaction about 1080 ℃, 1350 ℃ liquid phase occurs and lump, for making the pigment resultant velocity fast, react completely, synthesis temperature 1250 ℃ more suitable, finally obtained the more stable spinel type black material of color development.
Qiao Yan, the chromite application [J] in beramic color. Shandong pottery, 1998,21(2): 35, in black pigment production, should be used as detailed description for chromite, it is (mineral and industrial chemicals) than rational proportion: chromite 30%, Cr 2O 330%, Fe 2O 340%, firing temperature: 1280 ℃, soaking time: 30min, this black pigment high-temperature stable, colour generation is pure, and the monochrome and the color dot that are applicable to vitrified tile are decorated, but are used for coloured glaze, and tone is partially red, must add CuO, CoO, Ni 2O 3, MnO 2Modulate Deng oxide compound.
Liu Yu etc. utilize the synthetic cheap black pigment [J] of industrial waste. ceramic research, and 1993,8(1): 13, utilize the industrial waste and the rare earth compound synthesizing black beramic color that contain coloring element, industrial waste is crossed 250 mesh sieves, with technical pure Cr through wet ball mill 2O 3, MnO 2, Ni 2O 3, Fe 2O 3Mix by a certain percentage with it, its satisfied proportioning is as follows: Cr 2O 38%, Pr-NdO8%, MnO 218%, industrial waste 45%, Ni 2O 35%, Fe 2O 310%.Be characterized in when utilizing industrial waste, introduced a certain amount of industrial pure material.
Yu Kangtai, glaze materials decorate introduction [M]. press of Wuhan Polytechnical Univ, and 1997, set forth the formation mechanism of the two kinds of three-part system Fe-Cr that contains cobalt-Co, Fe-Mn-Co, point out that they are at Fe-Cr, the CoO that induces one on Fe-Mn basis makes.Its color development is black, and its ratio is different, and the color development blackness has difference.
He Daiying etc., the production of black ceramic colorant and application [J]. Foshan Ceramic, 2002,61(4): 4-5, adopt technical pure Fe 2O 3, Cr 2O 3, MnO 2Oxide compound through dry mixed, the spinel type black pigment that high-temperature calcination is synthetic.This is that colorant can be widely used in color glazed brick, artistic porcelain glaze, Glaze for chinaware etc.Especially in the base substrate of vitrified tile, paving tile, stone better this of coloring effect be colorant low with cost, be colour-stable and have higher economic benefit.But its preparation cost is higher.
Chinese patent discloses " a kind of method of preparing black zirconia ceramics at low temperature " (Si Wenjie, application number: 200910241594.4), use respectively homogeneous precipitation method synthesis of nano tinting material, coprecipitation method synthesis of nano Zirconium powder adopts Fe-Co-Ni-Mn as tinting material.In Zirconium powder, do not add any sintering aid, only add a small amount of tinting material, at 1150-1350 ℃ of sintering, obtain the beautiful black zirconia ceramics of color of excellent performance.
Chinese patent discloses " a kind of black nanophase ceramics pigment and preparation method thereof " (Wei Kun, application number: 200910214232.6), mix with chromium nitrate, manganous nitrate, iron nitrate and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES again after ammonium oxalate, ammonium formiate, ammonium acetate, propionic acid ammonium is water-soluble, 400-500 ℃ of heating, burning does not namely make described black nanophase ceramics pigment to there being gas to emit.Prepared black nano pigment color development is black, high temperature resistant, stable performance, good dispersity, but preparation cost is slightly high.
Chinese patent discloses " a kind of manufacture method and goods thereof of black ceramic goods raw material ", and (hair is founded the state, application number: 93106260.8), with black antimony ore slag as main tinting material, add the Mn assistant toner and be equipped with unselected clay and produce black ceramic goods raw material, adopt common process and device fabrication black ceramic goods.The premium propertiess such as its goods tool water-intake rate is little, void content is low, and intensity is large, look black.
Zhao Feng etc. utilize industrial tailings to prepare the research [J] of black pigment. Shandong pottery, 1997,20 (2): 26.They have used following process system with the industrial tailings that adopts: tailings sieve (18 order), ball milling, sieve (300 order), spray drying granulation, fire and (mix drawing the black particle that made by tailings for 1190 ℃-1210 ℃, 50-60min) and vitrification range, the coefficient of expansion of base substrate base-material must be complementary with the openpore base-material, otherwise can affect the weight of finished product.
Deng Jianguo, the nepheline application [J] in the glazed polishing brick. pottery, 2003,163(3): 50-51. with 13% nepheline Substitute For Partial feldspar, utilizes sintering process, and achievement is prepared: percent of firing shrinkage 9.5%-10%; Water-intake rate＜0.2%; Folding strength 40 MPa; 10 circulation flawlesses of resistance to thermal shocks; Resistance to acids and bases A level; Surface Mohs' hardness 〉=6 grades; Resistance to soiling 〉=2 grade; Product percent of pass〉90% white glazed polishing brick.
Chinese patent CN86104984A and CN106447lA provide and have utilized tailings in vanadium extraction or pyrite cinder and chromium slag industrial waste; add or do not add additive and be method that raw material prepares ceramic powder and the common wet ball mill of tailings in vanadium extraction and clay, press filtration are become mud pellet or powder process granulation; add mineral substance or trade waste additive, be pressed into the tabular method of then making artificial granite sheet material with techniques such as half dry-pressing.
Chinese patent application CN85202464, CN86102966 discloses the technical scheme of this respect, it is to utilize industrial vanadium tailing soil, pyrite slag, the ferrotungsten slag, silicon manganese slag, the silicochromium slag, the ferrotianium slag, the nickel metallurgy Iron-ore Slag, copper ashes, the chromium slag, the steel rolling iron scale, the iron and steel corrosion, common iron ore, titanomagnetite stone, chromite ore etc. are made ceramic powder, contained nonferrous metal oxides Ti in the above-mentioned slag, V.Cr, Mn, Fe sum large dried 20% or Ti, V, Cr, the Mn sum is done greatly 3% tailings in vanadium extraction or pyrite slag and chromium slag industrial waste and unselected clay or china clay, the conventional Production of Ceramics method of the employings such as silica sand is produced black ceramic goods raw material and goods thereof.The black of its goods mainly produces a kind of mixed black chromatic effect by nonferrous metal oxides Ti, V in the slag, Cr, Mn, Fe mutually in high temperature.
Chinese patent application CN01114777.6, polished marble tile and preparation method thereof, its blank comprises white base-material that high, medium and low temperature sand, mud forms, three kinds of toners of preparation by a certain percentage, and technological process is: various mill base → spraying dryings → first time batch mixing → second time batch mixing → micro mist → grinding → multitube cloth → secondary material distributing → moulding → drying → burn till → polish.It is characterized in that adopting ultra-fine micropowder secondary material distributing moulding process, the natural-like stone grain pattern is finished naturally by press, and color is through colour mixture repeatedly, and product has the characteristics such as glossiness is high, water-intake rate is low, resistance to soiling is strong, planeness is good.Its raw materials for production have all adopted raw mineral materials, and colorant adopts finished product pigment.Processing condition are harsh, complicated, can be handling not strong.
Along with going deep into of research, the black ceramic colorant is mainly towards three future developments: the one, improve the quality that has colorant now as far as possible, by modification, modification, interpolation colour generation accessory agent with use the means such as multiple mineralizer, its best composition, optimum process condition etc. are done comprehensive research, improve stability and the tinting strength of colorant; The 2nd, manage to utilize industrial waste and natural matter to make cheap colorant, the painted and coloured glaze decoration for base substrate is to reduce production costs and to increase the black pigment kind; The 3rd, development of new black ceramic colorant is as wrapping up carbon black etc.
At present, utilize natural mineral raw or ore dressing slag, trade waste, low-cost preparation color development is pure, be colour-stable black pigment becomes the main research tendency of body stain, for realizing this goal, different natural mineral raws or ore dressing slag, trade waste in the porcelain body prescription, have been introduced, reduced to a certain extent production cost, improved the color development pure of porcelain body, but the stable aspect of color development is also unsatisfactory.For this reason, the researchist has carried out the trial of mass efficient.But up to now, find yet to utilize mine tailing after the nepheline ore dressing-aegirine augite slag to make the report of raw material production black vitrified brick ceramic.
Summary of the invention:
The objective of the invention is provides a kind of color development pure in order to overcome above deficiency, is colour-stable, black vitrified brick with low cost.
Another object of the present invention is to reduce production costs in order to provide a kind of, the production method of environmental contamination reduction, the black vitrified brick of preserving the ecological environment.
The object of the present invention is achieved like this:
Black vitrified brick of the present invention comprises following component by weight:
Aegirine augite slag 20-30,
Low-quality clay 15-20,
Quartz 50-60 inferior,
Talcum 5-10 inferior,
Above-mentioned aegirine augite slag is by weight by SiO 240-50, Al 2O 315-20, CaO0.2-1, MgO0.1-0.5, Fe 2O 320-25, TiO 20.5-1.5, K 2O 2-4, Na 2O 7-9, Co 2O 30.3-1.5, MnO 20.5-1.5 form, wherein Fe 2O 3, TiO 2, Co 2O 3, MnO 2Nonferrous metal oxides weight part sum is 21.3-29.5; Low-quality clay is by weight by SiO 260-75, Al 2O 315-25, CaO2-4, MgO2-4, Fe 2O 33-8, TiO 20.5-1.5, K 2O 2-4, Na 2O 0.5-1.5 forms; Quartz inferior is by weight by SiO 278-86, Al 2O 312-18, Fe 2O 31-2, TiO 20.5-1.5, K 2O 0-0.5, Na 2O 0-0.5 forms; Talcum inferior is by weight by SiO 260-75, Al 2O 31-2, CaO2-4, MgO20-30, Fe 2O 31-3, TiO 20-0.5, K 2O 0-0.5, Na 2O 0.2-1 forms.
The production method of black vitrified brick of the present invention may further comprise the steps.
(1) quartz inferior, Low-quality clay, talcum inferior are crushed to the particulate that granularity is 0.9-2.0mm, it is stand-by that the aegirine augite slag is crossed 10 mesh sieves;
(2) get respectively aegirine augite slag after sieving, the particulate Low-quality clay, inferior quartzy, talcum inferior, aegirine augite slag by weight: Low-quality clay: inferior quartzy: talcum inferior=(20-30): (15-20): (50-60): the proportioning of (5-10) is mixed to get compound and compound is put into ball mill and adds the wet-milling of water mixing, wet-milling is to utilize the alumina balls masonry to be grinding medium, the control abrading-ball, the weight ratio of compound and water is (2-2.5): l: (0.3-0.4), adding simultaneously weight is 0.15% methylcellulose gum of compound weight and 0.2% tripoly phosphate sodium STPP, milling time is 0.5h-3h, form mixing mud, mixing mud is crossed 200 mesh sieves;
(3) mixing mud after will sieving adopts the spray-drying tower granulation, the spray-drying tower inlet temperature is 300 ℃-500 ℃, and hot-blast furnace temperature is 600 ℃-800 ℃, and temperature of outgoing air is 80 ℃-95 ℃, mud pressure is 1.2Mpa-1.5Mpa, and the particle of formation is crossed 20 mesh sieves;
(4) particle that will cross 20 mesh sieves places the pressure forming machine mould, compression moulding under the pressure of 35MPa, and water ratio is 5%-8% in the molding biscuit;
(5) biscuit is placed in the globars resistance furnace; rate of heating with 5 ℃/min-10 ℃/min is warming up to 800 ℃ from room temperature, is warming up to 1150 ℃-1180 ℃ with the rate of heating of 5 ℃/min-7 ℃/min, insulation 30min; with taking out behind the stove naturally cooling, namely get black vitrified tile product.
The nepheline ore deposit is a kind of emerging non-metallic minerals, and there is distribution more than 30 countries and regions in the world.But only have in the world at present Canada and Norway two countries in scale operation, a year volume of production and marketing reaches 1,500,000 tons, for the raw material of European and American developed countries as glass, pottery and Chemical Manufacture.China is from explored mineral deposit, and reserves are abundant, and are widely distributed.In areas such as Huili, Sichuan, Nan Jiang, Jinzhai County, Anhui, Area, Gejiu District, Yunnan Province, Suizhou, hubei, Linxian County, Shanxi Province, Jilin Yongsheng, Zhou Kou Dian, Hebei, Earthquake of Anyang station in Henan, Wan Xi the nepheline syenite ore deposit is arranged.The occurring in nature nepheline is present in the syenite, and general nepheline content is nepheline syenite at the rock more than 15%.But most of mineral deposit iron-holder is more than 5%, will inevitably not affect use in Ceramic production if do not do special processing.The gordian technique of nepheline mineral products production is the reasonable classification of work in-process and high intensity magnetic separation deironing, drop to iron-holder in the raw ore 〉=2% in iron-holder≤0.2%, and granularity could adapt to the large industrial standards such as glass, pottery at 200 orders-30 order.At present, only about 50%, Utilization Rate of Mineral Resources is low for the general concentrate rate of recovery, and the wasting of resources is large, and the slag of formation is many, has correspondingly also increased environmental protection pressure.
Nepheline (Nepheline) is a kind of lagoriolite (Na, K) (AlSiO 4), nepheline can decompose the silica gel that generates the rosy clouds shape, therefore named nepheline in acid.It often contains potassium, and sneaks into CaO, Fe 2O 3, H 2O, the similar albite of its character, but cost of winning is low, compares 80-50 yuan of cost-saved expenses per ton with the feldspar price.Nepheline has the characteristics such as high alumina, potassium, sodium simultaneously, when part replaces feldspar in ceramic batch, makes its melting behaviour far be better than potassium, albite, K in the potassium felspar sand 2The content of O is 16.9%, Na in the albite 2The content of O is 11.8%, and K in the nepheline 2O+Na 2O content is 19.86%, CaO+MgO content is generally 1--5%, the amount that contains solubility promoter in 1 part of nepheline is equivalent to 1.2 parts of potassium felspar sands, 1.7 parts of albites, therefore if when in ceramic batch, partly or entirely replacing feldspar with nepheline, nepheline syenite, present stronger flux effect, allocate 20%-50% nepheline syenite in the pottery into, firing temperature can reduce by 50-100 ℃.Can significantly reduce firing temperature, enlarge firing range, reduce percent of firing shrinkage, shorten firing period.Owing to containing 40.02% SiO in the nepheline 2, and being in undersaturated condition, the part quartz of its melting improves melt viscosity, prevents distortion thereby Heat stability is good.In addition, Al in the nepheline syenite 2O 3Content higher than potash feldspar, generally about 23%, therefore be conducive to improve the physical strength of goods, be difficult for caving in when base substrate is burnt till.Nepheline is columnar structure, when pulverizing, can improve grinding efficiency, shortens Ball-milling Time, reduce production costs.It is present in the rock with irregular particulate state or long column shape, and the nepheline mineral have carried out more deep research abroad as ceramic raw material, and for the production of.Generally induce one nepheline as flux raw material in states such as Canada, Russia, Brazil, Norway, the U.S., for the production of tableware, tea set, coffee service, coffee set, sanitary china, electroceramics, decorative ceramic, mosaic, chemical stoneware etc.
After the fragmentation of nepheline raw ore process and the rod milling, pass through again size classification, granularity〉0.1mm through vacuum filtration, multi-stage magnetic separation, select respectively one-level, secondary, three grades, level Four nepheline fine powder, the magnetic separation of carrying out again aegirine augite with separate, the waste residue that stays at last is the aegirine augite slag, contains Fe in the aegirine augite slag 2O 3, TiO 2, Co 2O 3, MnO 2Be 20-30 Deng nonferrous metal oxides weight sum, the aegirine augite slag is the ceramic raw material inferior of a standard.The concept of " poor quality " refers to that main ingredient content is low in the composition of raw material in the raw material, and the foreign matter contents such as iron, titanium, manganese, cobalt are high, do not meet national standard, can't use in white or light ceramic body.Aegirine augite is for containing ferrosilicate (Na, Ca) (Fe + 3, Fe + 2, Mg, Al) and [Si 2O 6], aegirine augite is the pin column and is embedded among nepheline mineral, the potash feldspar thing in secondary rainbow rosy clouds syenite ore deposit.Aegirine augite content is 5-10% in the nepheline raw ore.
According to ligand field theory, material is painted mainly to be because electronics is caused at different transition between the energy levels and ion pair Optical Absorption and scattering.The transition metals such as cobalt, chromium, iron, nickel, copper, manganese, their ion outermost orbit is the d track, is non-spherically symmetrical orbitals.When these ions are in the difform ligand field, the coordination negative ion produces splitting of energy levels to the energy change of each track, and four d tracks that so original energy level is identical become different energy levels under the coordination ion effect, namely produce ligand-field effect, formed the spinel type rock steady structure.Electronics transition between the d of different energy levels track absorbs the light of certain wavelength, and its transition energy is between 1ev-4ev, and just corresponding optical range is visible region.
Ni 2+, Fe 3+, Cr 3+, Co 3+Deng containing unpaired electronics on the transition metal ion outermost layer, their ground state and excited energy are more approaching, generation absorbs the strong selectivity of visible light, its spectral absorption can suppress the light transmission rate of its ion mutually, when their ionic concn cooperate to be adjusted when suitable, can complementary visible light after their curve of spectrum stack all absorb and present black.When multiple spinel crystal mixing effect that chromium, cobalt, iron, nickel, copper, manganese form, the mixing principle of losing lustre according to color, in the situation that the crystal ratio is fit to, the various ion out-shell electron transition that is in different valence state and ligand field environment all absorbs 7 kinds of monochromatic ray in the visible light basically, makes sample present black.
The hue range of spinel type colorant is quite wide, and the compositional system of common black pigment sees Table 1.Can find out: even the oxide compound of transition metal is not in the situation that there is cobalt can become black according to certain ratio yet, and the pure black of color development generally is to need to introduce the cobalt oxide component.As long as have A in the proportioning 2+And B 3+Oxide compound, just can form the structure of spinel type, such as Fe 2O 3Cr 2O 3MnO 2These three kinds of oxide compounds are mixed in proportion calcining, form respectively Fe 2O 3-Cr 2O 3, MnO 2-Fe 2O 3And MnO 2-Cr 2O 3The sosoloid of three kinds of spinel structures.Chromohercynite is dark-brown, and ferrojacobsite is garnet, and the chromium galaxite is sap green, because their proportional quantity is different, three kinds of mineral quantity of generation are also different, its complementary colors.The main chemical compositions of aegirine augite slag is SiO 2, Al 2O 3, Fe 2O 3, TiO 2, K 2O, Na 2O, other contains a certain amount of Co 2O 3, MnO 2, P 2O 5Etc. component.Aegirine augite slag vitrified tile base substrate, the colorant building-up reactions under the high temperature mainly contains:
Fe 2O 3+ Co 2O 3→ CoFe 2O 4(black)
TiO 2+ Co 2O 3→ TiCo 2O 4(green)
MnO 2+ Co 2O 3→ MnCo 2O 4(scarlet)
Al 2O 3+ Co 2O 3→ CoAl 2O 4(blueness)
Fe 2O 3+ MnO 2→ MnFe 2O 4(Dark grey)
MnO 2+ Al 2O 3→ MnAl 2O 4(brown color)
Fe 2O 3+ MgO → MgFe 2O 4(orange-brown)
Black+green → dark green
Dark red+dark-grey → dark red
Blueness+orange+orange brown → dark brown
Dark green+dark red+dark brown → black,
Therefore, the vitrified tile ceramic take the aegirine augite slag as major ingredient, high temperature solid state reaction forms stable spinel in base substrate, and the complementation stack by the spinel crystal color is painted to have formed distinct stable black.
The moiety of table 1 black pigment and crystalline structure
Title Form Crystalline structure
Without cobalt black Cr—Fe FeCr 2O 4Spinel
Without cobalt black Cr—Fe (Fe、Cr) 2O 3Corundum, hematite-type
Cobalt black Co—Cr—Fe Spinel
Cobalt black Co—Mn—Fe Spinel
Gorgeous black Co—Mn—Cr—Fe Spinel
Cobalt black Co—Ni—Cr—Fe Spinel
Cobalt black Co—Ni—Mn—Cr—Fe Spinel
Cobalt black Co—Cu—Mn—Cr—Fe Spinel
Cobalt black Co—Mn—Ti—Fe—Al—Mg Spinel
Cobalt black Co—Ni—Cr—Fe—Si Spinel
Without cobalt black Ni—Cr—Fe Spinel
Without cobalt black Ni—Cr—Fe—Mn Spinel
Without cobalt black Ni—Cr—Fe—Cu Spinel
Without cobalt black Ni—Cr—Fe—Mn—Cu Spinel
Without cobalt black Ni—Cr—Fe—Mn—Cu—Al Spinel
The present invention prepares black vitrified brick with the aegirine augite slag as the mass-tone material.The slag mineral composition is take aegirine augite, albite, potash feldspar, perthite, magnetite, rhombohedral iron ore, fluorite, phosphatic rock, aspidelite, biotite, white mica etc. as main.The aegirine augite slag embodies at composition: poor silicon, aluminium, high ferro, titanium, manganese, potassium, sodium, and Fe 2O 3, TiO 2, Co 2O 3, MnO 2Be 20-30 Deng nonferrous metal oxides weight sum, showing in nature the feature of natural one-tenth porcelain.Under the high temperature; aegirine augite slag both alternative feldspar plays the flux effect; effectively reduce the low eutectic point of compound; the porcelain body sintering temperature is reduced; and with the new glassy phase that forms of other component interaction; be filled in and emit gas or crystalline form because of pyroreaction and transform in the formed pore of volumetric expansion; optimized ceramic structure; improved the intensity of vitrified tile; reduced the contraction of burning till of ceramic product; particularly owing to having introduced aegirine augite; at the modern calcining system of the base substrate fine adaptation of energy " low temperature fast firing ", and produce " certainly releasing glaze " phenomenon in the sintering process, this " certainly releasing glaze " is inferior optical transparency shape; with this vitrified tile decorative ground, have unique texture and light sensation.On the other hand, provide again high temperature synthesizing stable spinel required transitional pigment element, the spinel of different tones makes base substrate present the effect of black by complementary colors and stack.
The present invention adopts that levels of transition metals is higher, Fe 2O 3, TiO 2, Co 2O 3, MnO 2Be 20-30, form complicated, with low cost aegirine augite slag Deng nonferrous metal oxides weight sum, with it as the mass-tone material, be aided with common Production of Ceramics raw material inferior (quartz, clay, talcum etc.), theoretical and mechanism is applied among the vitrified tile raw material with the beramic color color development, and a kind of low-cost prescription for preparing the black vitrified brick pottery is provided; Providing simultaneously a kind of is the mass-tone material with the aegirine augite slag; adding common quartz inferior, clay etc. is raw material; utilize the ceramic, solid-phase sintering theory; generate a large amount of black crystals by the solid state reaction original position; reduced firing temperature; burn till fast the middle porcelain of realizing base substrate, using conventional Production of Ceramics method and production unit to prepare the processing method of color development black vitrified tile product pure, with low cost.The present invention does not change existing technique, does not increase any equipment, and the technical indicator of its product and use properties meet ceramic industry GB/T4100-2006 national standard fully.
Utilize discarded aegirine augite slag and common Production of Ceramics raw material inferior to produce the black vitrified brick pottery as batching; compared with prior art; the present invention is not additionally adding under the prerequisite of any external colorant; the industrial waste that originally was difficult to utilize has been carried out effective processing; obtained having the black vitrified brick pottery of higher practicality and economic worth; change the conventional black pottery and will introduce the way of expensive colorant colour generation; obtain stable black vitrified brick pottery with less production cost, solved the waste material stacking and taken a large amount of soils; the problem that surrounding enviroment are polluted.The used batching of the present invention is tailing waste thing or industrial raw material inferior, and wide material sources are with low cost, has realized the recycling of solid waste resource, and implementation result is desirable.
Advantage of the present invention is as follows:
(1) the used main raw material of the present invention is the aegirine augite slag of discarding, and this slag has poor silicon, aluminium, and potassium, sodium content are high, and iron, titanium foreign matter content are large, contain Fe 2O 3, TiO 2, Co 2O 3, MnO 2Be 20-30 characteristics Deng nonferrous metal oxides weight sum, not only help to save natural resource, reduce production costs, also help environment protection.
(2) utilize the aegirine augite slag, be equipped with common Production of Ceramics raw material inferior, just can produce the black vitrified brick ceramic through high temperature sintering, started one for comprehensive development and utilization aegirine augite slag and turned harm into good and practicable approach.
(3) adopt conventional equipment to produce, need not to increase or change any optional equipment.
(4) the black vitrified brick ceramic of making has the premium propertiess such as firing temperature is low, water-intake rate is little, void content is low, and intensity is large, look black.Black aegirine augite slag vitrified tile sample is carried out the main performance index analysis, the results are shown in Table 2, the contrast discovery, this vitrified tile meets national GB/T 4100-2006 standards fully, and black is pure, color development is stable.
The performance comparison of table 2 aegirine augite slag black vitrified brick sample
Figure 47767DEST_PATH_IMAGE001
Embodiment:
Below aegirine augite slag among each embodiment by weight by SiO 245.79, Al 2O 316.43, CaO0.54, MgO0.18, Fe 2O 323.50, TiO 20.91, K 2O 2.76, Na 2O 8.23, Co 2O 30.45, MnO 21.21 form, wherein Fe 2O 3, TiO 2, Co 2O 3, MnO 2Nonferrous metal oxides weight part sum is 26.07; Low-quality clay is by weight by SiO 263.46, Al 2O 318.54, CaO3.45, MgO2.80, Fe 2O 36.85, TiO 20.75, K 2O 3.11, Na 2O 1.03 forms; Quartz inferior is by weight by SiO 282.02, Al 2O 315.09, Fe 2O 31.44, TiO 21.05, K 2O 0.19, Na 2O 0.21 forms; Talcum inferior is by weight by SiO 264.64, Al 2O 31.44, CaO2.43, MgO28.42, Fe 2O 31.99, TiO 20.25, K 2O 0.28, Na 2O 0.54 forms.
EXAMPLE l:
(1) quartz inferior, Low-quality clay, talcum inferior are crushed to the particulate that granularity is 1.0mm, it is stand-by that the aegirine augite slag is crossed 10 mesh sieves;
(2) get respectively aegirine augite slag after sieving, the particulate Low-quality clay, inferior quartzy, talcum inferior, aegirine augite slag by weight: Low-quality clay: inferior quartzy: talcum inferior=30: 15: 50: 5 proportioning is mixed to get compound and compound is put into ball mill and adds the wet-milling of water mixing, wet-milling is to utilize the alumina balls masonry to be grinding medium, the control abrading-ball, the weight ratio of compound and water is 2: l: 0.35, adding simultaneously weight is 0.15% methylcellulose gum of compound weight and 0.2% tripoly phosphate sodium STPP, milling time is 2h, form mixing mud, mud is crossed 200 mesh sieves;
(3) will sieve rear mud adopts the spray-drying tower granulation, and the spray-drying tower inlet temperature is 350 ℃, and hot-blast furnace temperature is 700 ℃, and temperature of outgoing air is 85 ℃, and mud pressure is 1.2MPa, and the particle of formation is crossed 20 mesh sieves;
(4) particle that will cross 20 mesh sieves places the pressure forming machine mould, compression moulding under the pressure of 35MPa, and water ratio is 8% in the molding blank;
(5) biscuit is placed in the globars resistance furnace, be warming up to 800 ℃ with the rate of heating of 5 ℃/min from room temperature, be warming up to 1150 ℃ with the rate of heating of 7 ℃/min, insulation 30min with taking out behind the stove naturally cooling, namely gets black vitrified tile product.
Embodiment 2:
(1) quartz inferior, Low-quality clay, talcum inferior are crushed to the particulate that granularity is 0.9mm, it is stand-by that the aegirine augite slag is crossed 10 mesh sieves;
(2) get respectively aegirine augite slag after sieving, the particulate Low-quality clay, inferior quartzy, talcum inferior, aegirine augite slag by weight: Low-quality clay: inferior quartzy: talcum inferior=22: 15: 55: 8 proportioning is mixed to get compound and compound is put into ball mill and adds the wet-milling of water mixing, wet-milling is to utilize the alumina balls masonry to be grinding medium, the control abrading-ball, the weight ratio of compound and water is 2.2: l: 0.3, adding simultaneously weight is 0.15% methylcellulose gum of compound weight and 0.2% tripoly phosphate sodium STPP, milling time is 1h, form mixing mud, mud is crossed 200 mesh sieves;
(3) will sieve rear mud adopts the spray-drying tower granulation, and the spray-drying tower inlet temperature is 300 ℃, and hot-blast furnace temperature is 800 ℃, and temperature of outgoing air is 80 ℃, and mud pressure is 1.3MPa, and the particle of formation is crossed 20 mesh sieves;
(4) particle that will cross 20 mesh sieves places the pressure forming machine mould, compression moulding under the pressure of 35MPa, and water ratio is 7% in the molding biscuit;
(5) biscuit is placed in the globars resistance furnace, be warming up to 800 ℃ with the rate of heating of 8 ℃/min from room temperature, be warming up to 1160 ℃ with the rate of heating of 7 ℃/min, insulation 30min with taking out behind the stove naturally cooling, namely gets black vitrified tile product.
Embodiment 3:
(1) quartz inferior, Low-quality clay, talcum inferior are crushed to the particulate that granularity is 1.5mm, it is stand-by that the aegirine augite slag is crossed 10 mesh sieves;
(2) get respectively aegirine augite slag after sieving, the particulate Low-quality clay, inferior quartzy, talcum inferior, aegirine augite slag by weight: Low-quality clay: inferior quartzy: talcum inferior=20: 20: 55: 5 proportioning is mixed to get compound and compound is put into ball mill and adds the wet-milling of water mixing, wet-milling is to utilize the alumina balls masonry to be grinding medium, the control abrading-ball, the weight ratio of compound and water is 2.5: l: 0.4, adding simultaneously weight is 0.15% methylcellulose gum of compound weight and 0.2% tripoly phosphate sodium STPP, milling time is 2h, form mixing mud, mud is crossed 200 mesh sieves;
(3) will sieve rear mud adopts the spray-drying tower granulation, and the spray-drying tower inlet temperature is 400 ℃, and hot-blast furnace temperature is 600 ℃, and temperature of outgoing air is 83 ℃, and mud pressure is 1.5MPa, and the particle of formation is crossed 20 mesh sieves;
(4) particle that will cross 20 mesh sieves places the pressure forming machine mould, compression moulding under the pressure of 35MPa, and water ratio is 6% in the molding biscuit;
(5) biscuit is placed in the globars resistance furnace, be warming up to 800 ℃ with the rate of heating of 6 ℃/min from room temperature, be warming up to 1170 ℃ with the rate of heating of 7 ℃/min, insulation 30min with taking out behind the stove naturally cooling, namely gets black vitrified tile product.
Embodiment 4:
(1) quartz inferior, Low-quality clay, talcum inferior are crushed to the particulate that granularity is 1.5mm, it is stand-by that the aegirine augite slag is crossed 10 mesh sieves;
(2) get respectively aegirine augite slag after sieving, the particulate Low-quality clay, inferior quartzy, talcum inferior, aegirine augite slag by weight: Low-quality clay: inferior quartzy: talcum inferior=20: 20: 50: 10 proportioning is mixed to get compound and compound is put into ball mill and adds the wet-milling of water mixing, wet-milling is to utilize the alumina balls masonry to be grinding medium, the control abrading-ball, the weight ratio of compound and water is 2.3: l: 0.3, adding simultaneously weight is 0.15% methylcellulose gum of compound weight and 0.2% tripoly phosphate sodium STPP, milling time is 1.5h, form mixing mud, mud is crossed 200 mesh sieves;
(3) will sieve rear mud adopts the spray-drying tower granulation, and the spray-drying tower inlet temperature is 500 ℃, and hot-blast furnace temperature is 760 ℃, and temperature of outgoing air is 88 ℃, and mud pressure is 1.2MPa, and the particle of formation is crossed 20 mesh sieves;
(4) particle that will cross 20 mesh sieves places the pressure forming machine mould, compression moulding under the pressure of 35MPa, and water ratio is 5% in the molding biscuit;
(5) biscuit is placed in the globars resistance furnace, be warming up to 800 ℃ with the rate of heating of 9 ℃/min from room temperature, be warming up to 1170 ℃ with the rate of heating of 7 ℃/min, insulation 30min with taking out behind the stove naturally cooling, namely gets black vitrified tile product.
Embodiment 5:
(1) quartz inferior, Low-quality clay, talcum inferior are crushed to the particulate that granularity is 2.0mm, it is stand-by that the aegirine augite slag is crossed 10 mesh sieves;
(2) get respectively aegirine augite slag after sieving, the particulate Low-quality clay, inferior quartzy, talcum inferior, aegirine augite slag by weight: Low-quality clay: inferior quartzy: talcum inferior=20: 15: 60: 5 proportioning is mixed to get compound and compound is put into ball mill and adds the wet-milling of water mixing, wet-milling is to utilize the alumina balls masonry to be grinding medium, the control abrading-ball, the weight ratio of compound and water is 2.4: l: 0.33, adding simultaneously weight is 0.15% methylcellulose gum of compound weight and 0.2% tripoly phosphate sodium STPP, milling time is 3h, form mixing mud, mud is crossed 200 mesh sieves;
(3) will sieve rear mud adopts the spray-drying tower granulation, and the spray-drying tower inlet temperature is 430 ℃, and hot-blast furnace temperature is 630 ℃, and temperature of outgoing air is 90 ℃, and mud pressure is 1.4MPa, and the particle of formation is crossed 20 mesh sieves;
(4) particle that will cross 20 mesh sieves places the pressure forming machine mould, compression moulding under the pressure of 35MPa, and water ratio is 6% in the molding biscuit;
(5) biscuit is placed in the globars resistance furnace, be warming up to 800 ℃ with the rate of heating of 7 ℃/min from room temperature, be warming up to 1170 ℃ with the rate of heating of 7 ℃/min, insulation 30min with taking out behind the stove naturally cooling, namely gets black vitrified tile product.
Above-described embodiment is that foregoing of the present invention is further described, but this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to above-described embodiment.All technology that realizes based on foregoing all belong to scope of the present invention.

Claims (2)

1. black vitrified brick comprises following component by weight:
Aegirine augite slag 20-30,
Low-quality clay 15-20,
Quartz 50-60 inferior,
Talcum 5-10 inferior,
Above-mentioned aegirine augite slag is by weight by SiO 240-50, Al 2O 315-20, CaO0.2-1, MgO0.1-0.5, Fe 2O 320-25, TiO 20.5-1.5, K 2O 2-4, Na 2O 7-9, Co 2O 30.3-1.5, MnO 20.5-1.5 form, wherein Fe 2O 3, TiO 2, Co 2O 3, MnO 2Nonferrous metal oxides weight part sum is 21.3-29.5; Low-quality clay is by weight by SiO 260-75, Al 2O 315-25, CaO2-4, MgO2-4, Fe 2O 33-8, TiO 20.5-1.5, K 2O 2-4, Na 2O 0.5-1.5 forms; Quartz inferior is by weight by SiO 278-86, Al 2O 312-18, Fe 2O 31-2, TiO 20.5-1.5, K 2O 0-0.5, Na 2O 0-0.5 forms; Talcum inferior is by weight by SiO 260-75, Al 2O 31-2, CaO2-4, MgO20-30, Fe 2O 31-3, TiO 20-0.5, K 2O 0-0.5, Na 2O 0.2-1 forms.
2. the production method of black vitrified brick may further comprise the steps:
(1) quartz inferior, Low-quality clay, talcum inferior are crushed to the particulate that granularity is 0.9-2.0mm, it is stand-by that the aegirine augite slag is crossed 10 mesh sieves;
(2) get respectively aegirine augite slag after sieving, the particulate Low-quality clay, inferior quartzy, talcum inferior, aegirine augite slag by weight: Low-quality clay: inferior quartzy: talcum inferior=(20-30): (15-20): (50-60): the proportioning of (5-10) is mixed to get compound and compound is put into ball mill and adds the wet-milling of water mixing, wet-milling is to utilize the alumina balls masonry to be grinding medium, the control abrading-ball, the weight ratio of compound and water is (2-2.5): l: (0.3-0.4), adding simultaneously weight is 0.15% methylcellulose gum of compound weight and 0.2% tripoly phosphate sodium STPP, milling time is 0.5h-3h, form mixing mud, mixing mud is crossed 200 mesh sieves;
(3) mixing mud after will sieving adopts the spray-drying tower granulation, the spray-drying tower inlet temperature is 300 ℃-500 ℃, and hot-blast furnace temperature is 600 ℃-800 ℃, and temperature of outgoing air is 80 ℃-95 ℃, mud pressure is 1.2MPa-1.5MPa, and the particle of formation is crossed 20 mesh sieves;
(4) particle that will cross 20 mesh sieves places the pressure forming machine mould, compression moulding under the pressure of 35MPa, and water ratio is 5%-8% in the molding biscuit;
(5) biscuit is placed in the globars resistance furnace; rate of heating with 5 ℃/min-10 ℃/min is warming up to 800 ℃ from room temperature, is warming up to 1150 ℃-1180 ℃ with the rate of heating of 5 ℃/min-7 ℃/min, insulation 30min; with taking out behind the stove naturally cooling, namely get black vitrified tile product.
CN2012104391363A 2012-11-07 2012-11-07 Blank ceramic tile and production method thereof Pending CN102875121A (en)

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Publication number Priority date Publication date Assignee Title
CN104003700A (en) * 2014-05-20 2014-08-27 陕西科技大学 Method for preparing environment-friendly ceramic vitrified brick by using waste slag
CN104591806A (en) * 2015-01-28 2015-05-06 广东宏陶陶瓷有限公司 Pure black glazed tile produced by using waste glaze slip and preparation method of pure black glazed tile
CN104844156A (en) * 2015-04-27 2015-08-19 英德市奥胜新材料有限责任公司 Preparation method for fired brick
CN106675098A (en) * 2016-12-26 2017-05-17 深圳市丁鼎陶瓷科技有限公司 Preparation technology of black pigment for zirconia ceramics
CN107500740A (en) * 2017-09-30 2017-12-22 佛山欧神诺陶瓷股份有限公司 A kind of environment-friendly black Ceramic Tiles and preparation method thereof
CN108384279A (en) * 2018-03-07 2018-08-10 武汉科技大学 A kind of no cobalt black pigment and preparation method thereof
CN108996512A (en) * 2018-07-25 2018-12-14 广西驰胜农业科技有限公司 A kind of method of whitening of albite in powder
CN113582665A (en) * 2021-08-19 2021-11-02 湖南华联瓷业股份有限公司 Antique iron crude pottery fired by oxidizing flame and preparation method thereof
CN115403268A (en) * 2022-08-17 2022-11-29 四川省银河化学股份有限公司 Method for synthesizing color ceramic particle material by using chromium slag

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102617116A (en) * 2012-03-28 2012-08-01 陕西科技大学 Method for preparing ceramic black materials by utilizing industrial slag

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102617116A (en) * 2012-03-28 2012-08-01 陕西科技大学 Method for preparing ceramic black materials by utilizing industrial slag

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
《建材地质》 19931231 徐杰等 "利用霞石正长岩选矿尾砂研制彩釉面砖" , 第2期 *
徐杰等: ""利用霞石正长岩选矿尾砂研制彩釉面砖"", 《建材地质》, no. 2, 31 December 1993 (1993-12-31) *

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CN104003700A (en) * 2014-05-20 2014-08-27 陕西科技大学 Method for preparing environment-friendly ceramic vitrified brick by using waste slag
CN104003700B (en) * 2014-05-20 2015-11-25 陕西科技大学 A kind of method utilizing abandoned mine slag to prepare environment-friendly ceramic vitrified tile
CN104591806A (en) * 2015-01-28 2015-05-06 广东宏陶陶瓷有限公司 Pure black glazed tile produced by using waste glaze slip and preparation method of pure black glazed tile
CN104591806B (en) * 2015-01-28 2016-06-08 广东宏陶陶瓷有限公司 Utilize ater glazed tile of useless glaze slip manufacture and preparation method thereof
CN104844156A (en) * 2015-04-27 2015-08-19 英德市奥胜新材料有限责任公司 Preparation method for fired brick
CN106675098A (en) * 2016-12-26 2017-05-17 深圳市丁鼎陶瓷科技有限公司 Preparation technology of black pigment for zirconia ceramics
CN107500740A (en) * 2017-09-30 2017-12-22 佛山欧神诺陶瓷股份有限公司 A kind of environment-friendly black Ceramic Tiles and preparation method thereof
CN107500740B (en) * 2017-09-30 2020-06-16 佛山欧神诺陶瓷有限公司 Environment-friendly black ceramic tile and preparation method thereof
CN108384279A (en) * 2018-03-07 2018-08-10 武汉科技大学 A kind of no cobalt black pigment and preparation method thereof
CN108384279B (en) * 2018-03-07 2020-07-24 武汉科技大学 Cobalt-free black pigment and preparation method thereof
CN108996512A (en) * 2018-07-25 2018-12-14 广西驰胜农业科技有限公司 A kind of method of whitening of albite in powder
CN113582665A (en) * 2021-08-19 2021-11-02 湖南华联瓷业股份有限公司 Antique iron crude pottery fired by oxidizing flame and preparation method thereof
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