CN1289737A - Ceramics containing crystal of andalusite with rich aluminum content and manufacture thereof - Google Patents

Ceramics containing crystal of andalusite with rich aluminum content and manufacture thereof Download PDF

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CN1289737A
CN1289737A CN00130556A CN00130556A CN1289737A CN 1289737 A CN1289737 A CN 1289737A CN 00130556 A CN00130556 A CN 00130556A CN 00130556 A CN00130556 A CN 00130556A CN 1289737 A CN1289737 A CN 1289737A
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ash
ceramic
pottery
amorphous glass
weight
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CN1125790C (en
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堀见和広
佐野达雄
岩田美佐男
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Noritake Co Ltd
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Noritake Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
    • C04B35/185—Mullite 3Al2O3-2SiO2
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/13—Compounding ingredients
    • C04B33/132—Waste materials; Refuse; Residues
    • C04B33/135—Combustion residues, e.g. fly ash, incineration waste
    • C04B33/1355—Incineration residues
    • C04B33/1357—Sewage sludge ash or slag
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/56—Compositions suited for fabrication of pipes, e.g. by centrifugal casting, or for coating concrete pipes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62204—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products using waste materials or refuse

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Combustion & Propulsion (AREA)
  • Environmental & Geological Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Treatment Of Sludge (AREA)

Abstract

To provide a method for manufacturing a mullite crystal-containing ceramic, capable of inverting high strength to the ceramic, even when sewage sludge-incinerated ash is used as a raw material, and to provide a product composed of the same ceramic. This method for manufacturing the subject ceramic comprises (a) a process for charging the sewage sludge-incinerated ash, a clay mineral containing alumina in an amount of >= 20 wt.% based on the total, and a ceramic material, (b) a process for mixing the ash, the clay mineral and the ceramic material, and (c) a process for baking the mixture formed by the mixing process, wherein a crystal quartz phase and an amorphous glass phase are formed in the ceramic to be contained mainly in a matrix of the ceramic, and a crystalline phase comprising mullite is formed in the amorphous glass phase. Thus, the ceramic which has the matrix mainly comprising the crystal quartz phase and the amorphous glass phase, and the amorphous glass phase of which contains the crystalline phase comprising mullite is obtained.

Description

The pottery and the manufacture method thereof that contain crystal of andalusite with rich aluminum content
The present invention relates to pottery and manufacturing technology thereof, in more detail, relate to by the ash that burns that burnings such as downflow sludge back is produced and make the method for high-strength ceramic and the high-strength ceramic goods that obtain with this method.
With burn processing such as downflow sludges the time, can generate a large amount of ashes that burns as waste, therefore, people wish to effectively utilize these and burn ash.In the past, this class was burnt ash and was removed directly as the soil improvement agent etc., will burn grey fusion slagging earlier after, be crushed to suitable size, as terra cotta such as concrete aggregate or roadbed material and in addition utilization again.For example, put down in writing in the open communique of Japan special permission 1996 No. 225363,1997 No. 100151 that to burn ash etc. with downflow sludge be the pottery of raw material and the method for making thereof.
But with the ash that burns that makes with existing manufacture method is that the pottery of raw material can't obtain satisfied intensity.Therefore, burning ash etc. with these is that the ceramic of raw material can not need the ceramic of higher-strength as earthen-ware pipe etc., and be only limited to as watt, building materials and the engineering materials less high such as ceramic tile to requirement of strength.
The present invention is that the relevant problem of the pottery of raw material produces in order to solve above-mentioned in the prior art with burn ash with downflow sludge.The objective of the invention is, burn ash, provide a kind of and promptly use this to burn method and product thereof that ash also can obtain high-strength ceramic for further effectively utilizing downflow sludge etc.
For achieving the above object, the invention provides a kind of method that ash is made pottery of burning by downflow sludge or other mud, it comprises:
(a). supply with downflow sludge burn content that ash or other mud burns ash and aluminum oxide account for above clay material of 20 weight % of mineral substance total amount and stupalith step,
(b). described this downflow sludge burns ash or other mud burns ash and clay material and stupalith blended step; And
(c). the step of the mixture roasting that will in above-mentioned mixing step, obtain,
Main quartz crystals part and the amorphous glass part of generating generates the crystallising part of being made up of mullite in described amorphous glass part in matrix.
" stupalith " described in this specification sheets is meant the generalized ceramic-like inorganic materials that comprises cement, glass, brick etc.Ceramics powder minces and finished ground cement etc. is the representative instance of the stupalith described in this specification sheets.
In this manual, " clay material " is meant the inorganic materials of being made up of the various mineral substance that can constitute clay (various clay minerals, silicate minerals are typically arranged).The mineral parts of kaolin etc. having been removed the moisture in the clay is the exemplary of the clay material described in this specification sheets.
In the process for preparing ceramic of the invention described above, toward as trade waste and burning of a large amount of downflow sludges that generate or other mud infeeds clay material and stupalith and mix in the ash.Thus, there are high-load calcium component and phosphate composition even downflow sludge burns in ash etc., but in said mixture, the content of these compositions descended relatively.Thereby can improve the compactness of gained calcining matter (ceramic post sintering thing).
In process for preparing ceramic of the present invention, be feature with clay material (being the mineral substance aggregate) to use the mixing of alumina content more than 20 weight %.Thus, burn ash with raw material and compare, the alumina content in the said mixture has increased.Therefore, if use process for preparing ceramic of the present invention, can be in the matrix of gained calcining matter, become the quartz crystals part (phase) of key element and amorphous glass partly in (mutually) generating main thing, in this amorphous glass, make by the crystal formation crystallising part segregation of the mullite of high strength xln as it.Thus, can obtain intensity and be higher than existing pottery (that is, deriving from the pottery that downflow sludge burns ash).
As process for preparing ceramic of the present invention, be preferably, in above-mentioned (b) step, be that 30-40 weight %, above-mentioned stupalith are that the ratio of 30-40 weight % mixes them for 20-40 weight %, above-mentioned clay material in the ash that burns of downflow sludge or other mud.Ratio of mixture by this setting can make the compactness of gained pottery and intensity take into account on high level.
In addition, as process for preparing ceramic of the present invention, be more preferably, in above-mentioned (b) step, supply with and/or mix that above-mentioned downflow sludge burns ash or other mud burns ash and clay material and stupalith, the content that makes the P2O5 in the mixed mixture is below the 8 weight % of this amount of the mixture.Perhaps, in step (b), supply with and/or mix above-mentioned ash and clay material and the stupalith of burning, the CaO content in the mixed mixture is below the 3 weight % of this amount of the mixture.By such adjustment to raw materials mixed and ratio of mixture thereof, can obtain intensity bigger derive from the pottery that downflow sludge or other mud burn ash.
In addition, the another kind of better embodiment of process for preparing ceramic of the present invention is, in above-mentioned (a) step, the particle diameter of above-mentioned clay material and stupalith is adjusted to below the 150 μ m.Like this, the miscibility of each raw material can be improved, thereby the density of gained calcining matter can be improved.
In addition, the better embodiment of another of process for preparing ceramic of the present invention is, in above-mentioned (c) step, top temperature is chosen in 1050-1200 ℃ the scope.Be preferably, make to be warming up to top temperature institute's time spent from normal temperature and to be at least 8 hours.By setting such hyperthermic treatment condition, can improve the efficient of removing gas in the mixture from roasting, the result can obtain the sintered compact of high compactness.Under good especially hyperthermic treatment condition, per hour will be set at 125 ℃ or from the intensification of normal temperature to 500 ℃ than this heat-up rate more slowly.By setting such temperature rise rate, the carbon component that the organic composition that adds with clay material and/or mud can be burnt in the ash is burnt effectively, is removed.
For achieving the above object, the invention provides basically and partly contain the various ceramics (structure material, building material) that crystal of andalusite with rich aluminum content pottery partly constitutes by mainly containing (that is, the major part in the matrix is) quartz crystals part and amorphous glass part, this amorphous glass in the matrix.In addition, an exemplary as this type of pottery in the present invention, provides the earthen-ware pipe that is made of above-mentioned pottery basically.
Therefore earthen-ware pipe of the present invention, can reach high strength owing to have above-mentioned crystal of andalusite with rich aluminum content part.Thus, can be with it aptly as the earthen-ware pipe that needs high-intensity upper and lower water channel to use.
Earthen-ware pipe of the present invention should be made of the pottery that obtains with above-mentioned process for preparing ceramic of the present invention basically.Therefore the earthen-ware pipe that is obtained by such manufacture method can reach high strength owing to have above-mentioned crystal of andalusite with rich aluminum content part.Thus, can be aptly as the earthen-ware pipe that needs high-intensity upper and lower water channel to use.And, also help to make the ash that burns to obtain effectively utilizing again as the downflow sludge of trade waste.
Be preferably, the crystal of andalusite with rich aluminum content in the earthen-ware pipe of the present invention partly accounts for more than the 9 weight % of above-mentioned pottery, accounts for better more than the 15-17 weight %.The earthen-ware pipe that constitutes by such pottery have with three-point bending resistance intensity in 80Mpa (1Pa=1.01972 * 10 -5Kgf/cm 2) the above same or close intensity of ceramic phase.Such high strength earthen-ware pipe is suitable to the earthen-ware pipe that has the high-intensity upper and lower water course of special needs to use that is embedded in the soil and so on.
Better embodiment to process for preparing ceramic of the present invention describes below,
At first, above-mentioned steps (a) (raw material supplying step) is described.
In process for preparing ceramic of the present invention, used various downflow sludges are burnt the composition that ash or other mud burns ash do not have particular restriction.For example, from the angle of mineral substance, the ash that burns that derives from general downflow sludge is made of lime feldspar, phosphate cpd, quartz etc. usually, with SiO 2Be main component, also contain Al 2O 3, Na 2O, K 2O, MgO, Fe 2O 3, P 2O 5Deng, but their ratio of components is not had influence, in addition, also can utilize containing other trace ingredients person.
Generally, downflow sludge burns ash can be categorized into macromolecular and lime by this treatment process, and the two all can use.Macromolecular to burn ash good especially.
As long as the above-mentioned clay material that is used for process for preparing ceramic of the present invention is its aluminum oxide (Al 2O 3) content accounts for above get final product of 20 weight % of mineral substance total amount, no particular restriction, but preferred CaO, the P that becomes the reason of glassiness generation when roasting 2O 5The low clay material of content.The composition of such clay for example is preferably SiO 2: 57-67 weight %, Al 2O 3: 20-27 weight %, Fe 2O 3: less than 5 weight %, CaO: less than 1 weight %, MgO: less than 1 weight %, K 2O: less than 3 weight %, Na 2O: less than 1 weight %.On the other hand, if Fe 2O 3, CaO, MgO, K 2O and Na 2O surpasses the excessive existence of above-mentioned ratio of components, and then the ratio of the glassy phase in the gained ceramic substrate becomes too high, is difficult to guarantee desirable intensity.
As the above-mentioned clay material that uses in the process for preparing ceramic of the present invention, the clay material of alumina amount more than 25 weight % is good especially owing to generate crystal of andalusite with rich aluminum content composition (mullite phase) in a large number.It is comparatively suitable particularly to be with kaolinite that main clay constitutes the clay material or the poor clay material of feldspar of mineral.This class clay material can itself or provide with the form of the supply source (natural or artificial modulator) that contains this clay material.
As the supply source that contains this class clay material, be preferably plastic natural clay, in case of necessity also can be with these several mixing of class natural clay.In addition, during use, the plasticity-raw clay of available packages water content also availablely produces plastic dry clay when adding water.Under situation with the earthen-ware pipe extrusion molding, the most handy fat clay.
In addition, the above-mentioned stupalith as in the process for preparing ceramic of the present invention for example has ceramic ware material, cement, glass, brickbats etc. such as pottery, porcelain.As stupalith of the present invention, preferably has the material that prevents the effect of being detained in the low melting point amorphous glass that gas separates out in calcination steps.For example, the crushed material of the ceramic sintered bodies of brick clay grog, earthen-ware pipe chamotte and so on is all suitable to stupalith.Especially the stupalith (being ground into Powdered) that the ceramic sintered bodies that the preferred higher high-temperature zone of maturing temperature in the described process for preparing ceramic of the present invention than the back obtains is made.If use by the powder of making at the ceramic sintered bodies of so high sintering temperature as stupalith of the present invention, even then generate in the sintered compact that generates in the calcination steps of process for preparing ceramic of the present invention and derive from the low melting point amorphous glass that above-mentioned mud burns ash and clay material, described stupalith is still remaining with the form of particle.Its result can guarantee the outside pore of overflowing of the gas that will produce in this low melting point amorphous glass.And, by adding this type of stupalith, can improve the fire performance of the said mixture self in the manufacture method of the present invention.
Perhaps, by crystalloid SiO such as crystobalite, tridymite, quartz 2And/or mullite (typical composition formula: 3Al 2O 32SiO 2) powder that obtains through pulverizing of the good ceramic sintered bodies of resistivity against fire that constitutes also can be used very aptly.The stupalith that is formed by this class powder helps to improve the intensity of the pottery of the ash of must burning oneself to death that obtains with manufacture method of the present invention.
In process for preparing ceramic of the present invention, be preferably in and above-mentioned mud is burnt ash, clay material and stupalith carry out precomminution before mixing and handle, this clay material (or its supply source) and the particle diameter of stupalith are attenuated, especially the particle diameter of these two kinds of raw materials should be adjusted to respectively below the 150 μ m.Burn ash as the mud of raw material and be particulate (micro mist) state usually, carry out grain refined and handle but similarly also can burn ash to mud.
For example, when using various dry clay,, can obtain the Powdered dry clay of desired particle diameter by the sieve about #100 as above-mentioned clay material.In addition, when using raw clay as the supply source of argillaceous material, screening again after disperseing in water in advance can obtain the Powdered raw clay of desired particle diameter.
On the other hand, with various pulverizers such as roll crushing machine, impact mill, Lei Mengte shredder, vertical crushers with the stupalith grain refined.Be preferably, after the drying,, can obtain the powdered ceramic material of desired particle diameter with the sieve of the screening about #100.
Below above-mentioned steps (b) (raw material mixing step) is described.
Various raw materials through above-mentioned modulation, supply preferably mix in following ratio: above-mentioned mud burns ash (be typically downflow sludge and burn ash) 20-40 weight %, above-mentioned clay material 30-40 weight %, above-mentioned stupalith 30-40 weight %.When making pottery, the ratio of above-mentioned crystal of andalusite with rich aluminum content part in the gained pottery accounted for more than the 9 weight % of ceramic total amount by this ratio of mixture.
On the other hand, the mixture ratio that burns ash when above-mentioned mud is difficult to obtain fine and close pottery during significantly less than 20 weight % of total amount.And the mixture ratio that burns ash when above-mentioned mud has the excessively anxiety of generations of a large amount of low melting point amorphous glass during significantly greater than 40 weight % of total amount, and intensity may deficiency.
When the mixture ratio of stupalith significantly surpasses 40 weight % of total amount, be difficult to obtain fine and close pottery.And, then be difficult to guarantee the pore that above-mentioned gas is escaped when the ratio of mixture of stupalith during significantly less than 30 weight % of total amount.When the mixture ratio of clay material during, the anxiety of ceramics strength deficiency is arranged significantly less than 30 weight % of total amount.
Perhaps, when these three kinds of raw materials are mixed, preferably above-mentioned mud is burnt ash, clay material and stupalith and select and/or mix, make the P in the mixture 2O 5Content accounts for below the 8 weight % of this amount of the mixture.Perhaps, above-mentioned mud is burnt ash and clay material is selected and/or mixed, the CaO content in the mixture is accounted for below the 3 weight % of this amount of the mixture.With the P in such method minimizing mixture 2O 5Content and CaO content can prevent from excessively to generate glassy phase, avoid the ceramics strength deficiency.
Mixing means is not had particular restriction, but preferably use the mixing means of the thing that can be uniformly mixed.Can obtain the uniform mixture formed by above-mentioned 3 kinds of raw materials with mixing means such as the agitator mill of runner millings such as mixer-mill, ball mill etc., plate feeding machine, soil smelting machines.Especially preferred intermittent type kneading device.
Below above-mentioned steps (c) (calcination steps) is described.
Typically, in calcination steps,, comprise said mixture is configured as desired shape as its last stage.This shaping means are not had particular restriction, can use the whole bag of tricks of in the ceramic manufacturing process, using always so far.For example, can adopt the general moulding method, extrusion molding method, pressing mold moulding method (single shaft compression moulding, CIP moulding method etc.) of being cast into that said mixture is made molding.Wherein, good especially with usefulness extrusion molding method in the earthen-ware pipe of the invention described above is made.When use is cast into moulding method, extrusion molding method etc.,, then need before sintering processes, carry out drying if the moisture content of said mixture is too much.Especially preferably carry out drying treatment, make remaining amount of moisture below 2%.The danger of water vapor expansion or the explosion that causes thus in the time of so can eliminating sintering reaction.In addition, when above-mentioned mixing or shaping, be preferably in case of necessity and add suitable adhesive in the said mixture.
The visual mud of roasting top temperature in the process for preparing ceramic of the present invention burns the ratio of mixture of ash etc. and suitably changes, but is advisable with 1000-1300 ℃, is preferably 1050-1200 ℃.The typical hold-time in this top temperature is about below 1.5 hours or 1.5 hours.If the top temperature during roasting significantly is lower than the said temperature scope, then can not fully generates the crystal of andalusite with rich aluminum content part, thereby the anxiety that can not guarantee desired intensity is arranged.And, then can not fully generate the crystal of andalusite with rich aluminum content part if the roasting top temperature significantly is higher than the said temperature scope, cause guaranteeing desired intensity.
As for the heat-up rate in the calcination steps, the heating-up time that rises to above-mentioned top temperature from normal temperature should be set at least 1.5 hours.If heat-up rate is too fast, the anxiety that forms fine and close glassy phase at the sintered compact upper layer is rapidly arranged then.The formation of this densification glassy phase can impel the inner gas that takes place of sintered compact to be enclosed on the spot in inside, is unfavorable therefore.Because being enclosed, gas can cause strength degradation.
Especially preferably can make the heat-up rate slowly of above-mentioned heating-up time (for example above-mentioned heating-up time is 8-12 hour) more than 8 hours.Heat-up rate can improve the efficient of removing gas in the mixture from positive roasting so slowly, under the typical situation, can obtain the pottery of water-intake rate at the high compactness below 1%.Be more preferably, from the intensification of normal temperature to 500 ℃ so that per hour 125 ℃ or slower speed are carried out.(being contained in the supply source) organic composition that such heat-up rate can the clay material in mixture adds and/or mud burn carbon component contained in the ash and burn effectively, remove.
The pottery that is made by the process for preparing ceramic of the invention described above is looked raw materials used form and different, but it is characterized in that, have amorphous glass part and quartz crystals part, and comprise crystal of andalusite with rich aluminum content part (mullite phase) in the amorphous glass part as matrix main composition key element.This mullite typically is the column mullite that segregation is come out in the process of cooling behind low melting point amorphous glass sintering.And, around the crystal of andalusite with rich aluminum content of segregation in described glass, may produce the stress under compression field, thereby realize high strength owing to the difference of thermal expansivity.
Preferably also contain in this amorphous glass part by hematite (Fe 2O 3) crystallising part that forms.Like this, can improve compactness.Lime feldspar, soda feldspar and/or the lime feldspar that can contain in addition, some low melting point amorphous glass partial crystallizationization.
With the process for preparing ceramic of the present invention of illustrating above, can promptly burn ash from the residue of downflow sludge after burning disposal and make various ceramics as trade waste.Especially can obtain high-intensity goods with method of the present invention, thereby the pottery of making is applicable to various uses.For example, as the ceramic of being made by the inventive method, what can exemplify has interior trim or outer ornamental material of construction, building with material etc.For example, by in above-mentioned process for preparing ceramic of the present invention, suitably selecting, use existing various forming process means, also can make various ceramics (for example, electronic materials such as organism material, ceramic substrate such as the building materials such as ceramic tile used of internal and external ornament, artificial bone).
With the inventive method make an exemplary of excellent ceramic be the earthen-ware pipe that is used for upper and lower water course etc.Below to describing as earthen-ware pipe of the present invention by the exemplary of ceramic provided by the invention.
The feature of earthen-ware pipe of the present invention on constituting is that it constitutes by having the pottery that contains the crystal of andalusite with rich aluminum content part in quartz crystals part and amorphous glass part, the described amorphous glass in the matrix basically.Described crystal of andalusite with rich aluminum content part preferably accounts for more than the 9 weight % of gross weight of the pottery that constitutes earthen-ware pipe.As the water-supply line pipe or the sewer pipe that are embedded in the soil, preferred basically by three-point bending resistance intensity more than 80MPa pottery or have the earthen-ware pipe that the pottery with suitable intensity constitutes.Earthen-ware pipe of the present invention with these performances can make with above-mentioned process for preparing ceramic of the present invention, also can be with reference to method of the present invention, for example with preparation in advance with will be above-mentioned the artificial raw material of high purity that equates of the constituent of three kinds of raw materials when mixing replace mud to burn the method that ash is a feature, the equal pottery of product of manufacturing and process for preparing ceramic of the present invention.
When making earthen-ware pipe of the present invention, except above-mentioned (a) raw material supplying step, (b) raw material mixing step with (c) the calcination steps with process for preparing ceramic of the present invention; Also can use the technology same, no particular restriction with existing ceramic process.
Typically, when having a certain size, add said mixture in the extrusion shaping machine (auger type) of the nozzle of shape the mixture of tackiness agent etc. (or added again), mixture being extruded, obtain having the tubulose molding of global sections shape from nozzle.Calcination process after this tubulose molding passes through suitable drying treatment as mentioned above, under the temperature condition of the invention described above can obtain having the earthen-ware pipe of the present invention of desired shape.
The mechanism and the working method of used extrusion shaper all are that this area is known in above-mentioned extrusion molding technology itself and this extrusion molding method, and the present invention is characterization therefrom not, therefore, is described in more detail no longer at this point.
Illustrate in greater detail the present invention with several embodiment below, but the present invention is not only for these embodiment.
Table 1 (unit: weight t%)
Downflow sludge burns ash Clay material Stupalith
SiO 2Al 2O 3Fe 2O 3TiO 2CaO MgO K 2O Na 2O P 2O 5IgLoss 38.37 15.46 9.59 0.71 6.16 2.72 2.44 1.39 17.15 2.98 59.48 25.31 2.78 1.06 0.41 0.57 1.48 0.10 - 8.56 70.39 20.01 3.86 0.81 0.39 0.72 2.36 0.53 - 0.44
Table 2 (unit: the weight % that is converted into dry powder)
Sample No.1 No.2 No.3 No.4 No.5 No.6 No.7 No.8 No.9
Downflow sludge burn grey clay material stupalith maturing temperature (℃) 26 37 37 1100 28 36 36 1100 30 35 35 1075 32 34 34 1075 34 33 33 1075 36 32 32 1075 38 31 31 1050 40 30 30 1030 50 25 25 1020
Table 3 (unit: weight %)
Sample No.1 No.2 No.3 No.4 No.5 No.6 No.7 No.8 No.9
SiO 2Al 2O 3Fe 2O 3TiO 2CaO MgO K 2O Na 2O P 2O 5 58.03 20.79 4.95 0.88 1.90 1.18 2.06 0.59 4.46 57.50 20.64 5.08 0.87 2.01 1.22 2.07 0.62 4.80 56.97 20.50 5.20 0.87 2.13 1.27 2.08 0.64 5.15 56.43 20.36 5.33 0.86 2.24 1.31 2.09 0.66 5.49 55.90 20.21 5.45 0.86 2.36 1.35 2.10 0.68 5.83 55.37 20.07 5.58 0.85 2.47 1.39 2.11 0.70 6.17 54.84 19.92 5.70 0.85 2.59 1.43 2.12 0.72 6.52 54.31 19.78 5.83 0.85 2.70 1.48 2.13 0.75 6.86 51.65 20.79 6.46 0.82 3.28 1.68 2.18 0.85 8.58
The downflow sludge of forming shown in the use table 1 burns ash, clay material (usefulness is the dry clay powder that sculpture is used) and above-mentioned stupalith (usefulness is the earthen-ware pipe chamotte) here herein, implement process for preparing ceramic of the present invention, make the pottery that 9 kinds of compositions have nothing in common with each other altogether.
That is, above-mentioned 3 kinds of raw materials are mixed by the 9 kinds of ratio of mixture (being converted into the weight % of dry powder) that amount to shown in the No.1-No.9 in the table 2.With this ratio of mixture is that the middle mineral substance ratio of components that exists of each mixture (No.1-No.9) that benchmark is calculated is shown in table 3.
With Ishikawa formula mixing machine these raw materials are mixed.Then, each mixture is used respectively behind the single shaft press preliminary shaping at 1500 tons/cm 2Carrying out CIP under the condition of pressurization (hydrostaticpressure) is shaped.With downflow sludge burn the ash corresponding, roasting is 1 hour under the maturing temperature shown in the table 2.Heat-up rate from normal temperature to each maturing temperature is as follows: room temperature to 500 ℃ is per hour 100 ℃, and 500 ℃ are per hour 125 ℃ to each maturing temperature.
After calcination steps is finished, the gained pottery is cut into the anti-reflecting bending strength test sheet of 3 * 4 * 40L, (JIS R 1601) carries out 3 proof bend tests by well-established law.And carry out water-intake rate and assess.Behind the above-mentioned anti-reflecting bending strength test, each test film is pulverized, carried out powder x-ray diffraction analysis.The results are shown in table 4.No.1-No.9 in the table 4 is corresponding with the No. of said mixture.The result of the powder x-ray diffraction analysis of test film No.1 (XRD figure shape) is shown in Fig. 1, and the result of the X-ray diffraction analysis of test film No.2-No.8 (XRD figure shape) is shown in Fig. 2.
Table 4
Sample No.1 No.2 No.3 No.4 No.5 No.6 No.7 No.8 No.9
3 bending strengths (MPa) water-intake rates (%) 96.1 0.2 93.1 0.2 91.1 0.2 95.0 0.3 93.1 0.3 88.1 0.5 88.1 0.7 90.0 0.7 74.0 1.5
Crystallization phases Quartzy mullite hematite nepheline Quartzy mullite hematite nepheline Quartzy mullite hematite nepheline Quartzy mullite hematite nepheline Quartzy mullite hematite nepheline Quartzy mullite hematite nepheline lime feldspar Quartzy mullite hematite nepheline lime feldspar Quartzy mullite hematite nepheline lime feldspar Quartzy mullite hematite nepheline lime feldspar
From table 4 and Fig. 1, Fig. 2 as can be known, in surpassing the crystallization phases of No.1-No.5 test film (pottery) of 90MPa, 3 bending strengths all have quartzy (bullet among the figure), mullite (the white round dot among the figure), hematite (the black triangle among the figure), nepheline (the white triangle among the figure).The water-intake rate of these test films is also lower, is 0.2-0.3%, points out their structure very fine and close.On the other hand, in the crystallization phases of the No.6-No.8 test film (pottery) that 3 bending strengths are 80-90MPa, also there is lime feldspar (the Bai Si angle among the figure).The water-intake rate of this test film is 0.5-0.7%.
Downflow sludge burns 3 bending strengths of No.9 test film of the 25 weight % that ratio of mixture that the ratio of mixture of ash accounts for 50 weight %, clay material and the stupalith of total amount accounts for total amount respectively less than 80MPa.If by described ratio of mixture, CaO and P 2O 5Existence than surpassing 3 weight % and 8 weight % respectively.Water-intake rate is 1.5%.
Then, with electron microscope (TEM:40000 doubly) observe with above-mentioned No.1 the same terms under the pottery that makes.Gained TEM photo is shown in Fig. 3 and Fig. 4.These microphotographs show, the matrix of the pottery of the present invention that obtains by present embodiment mainly by quartz crystals part (part that the A among Fig. 3 represents) and amorphous glass (Si-Al-P-Ca-K-O system) partly (part that the B among Fig. 3 represents) constitute, the crystal of andalusite with rich aluminum content that described amorphous glass contains height ratio in partly is (part that the C among Fig. 4 represents) and hematite crystallising part (part that the D among Fig. 4 represents) partly.Specifically, mullite is 17 weight %, and hematite is 9 weight %, and quartz is 68 weight %, and nepheline is 6 weight %.
According to process for preparing ceramic of the present invention, promptly use downflow sludge to burn ash and make raw material and also can make high-intensity pottery.In addition, by this manufacture method, can burn ash by downflow sludge and make and have high-intensity earthen-ware pipe and other ceramics as trade waste.Therefore, can reach further ash is burnt in effectively utilization as the downflow sludge of trade waste purpose by the present invention.
Fig. 1 is the graphic representation of the x-ray diffractogram of powder shape (XRD figure shape) of the pottery of expression one embodiment of the invention.
Fig. 2 is the graphic representation of the x-ray diffractogram of powder shape (XRD figure shape) of the pottery of expression one embodiment of the invention.
Fig. 3 is the electron micrograph (TEM photo) of the microstructure of the pottery of expression one embodiment of the invention.
Fig. 4 is the electron micrograph (TEM photo) of the microstructure of the pottery of expression one embodiment of the invention.

Claims (4)

1. burn the method that ash is made pottery by downflow sludge, it comprises:
(a). supply with step that content that downflow sludge burns ash, aluminum oxide accounts for above clay material of 20 weight % of mineral substance total amount and stupalith,
(b). described this downflow sludge burns ash and clay material and stupalith blended step; And
(c). the step of the mixture roasting that will in above-mentioned mixing step, obtain,
Main quartz crystals part and the amorphous glass part of generating generates the crystallising part of being made up of mullite in described amorphous glass part in matrix.
2. process for preparing ceramic as claimed in claim 1, wherein, in above-mentioned steps (b), burning ash in downflow sludge is that 30-40 weight %, stupalith are that the ratio of 30-40 weight % is with these material mixing for 20-40 weight %, clay material.
3. earthen-ware pipe, it contains crystal of andalusite with rich aluminum content pottery partly in quartz crystals part and amorphous glass part, the described amorphous glass part and constitutes by mainly containing in the matrix basically.
4. earthen-ware pipe, it is made of the pottery with claim 1 or 2 described process for preparing ceramic manufacturings basically, and described pottery is mainly to contain the pottery formation that contains the crystal of andalusite with rich aluminum content part in quartz crystals part and amorphous glass part, the described amorphous glass portion in the matrix.
CN00130556A 1999-09-28 2000-09-28 Ceramics containing crystal of andalusite with rich aluminum content and manufacture thereof Expired - Fee Related CN1125790C (en)

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CN101709001B (en) * 2009-10-31 2012-08-22 华南理工大学 Method for firing porous filtering ceramic tiles with ceramic polishing scrap
CN105859090A (en) * 2016-04-11 2016-08-17 娈疯 Civil sludge comprehensive treatment process

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