CN1868970A - Fire-resistant raw material composition, fire-resistant material forming therefrom - Google Patents
Fire-resistant raw material composition, fire-resistant material forming therefrom Download PDFInfo
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- CN1868970A CN1868970A CN 200610091529 CN200610091529A CN1868970A CN 1868970 A CN1868970 A CN 1868970A CN 200610091529 CN200610091529 CN 200610091529 CN 200610091529 A CN200610091529 A CN 200610091529A CN 1868970 A CN1868970 A CN 1868970A
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Abstract
Refractories containing carbonaceous grains (A) selected from carbon black or graphite grains obtained by graphitizing carbon black and having a DBP absorption (x) of 80 ml/100 g or more, carbonaceous grains (B) selected from carbon black and graphite grains obtained by graphitizing carbon black and having a DBP absorption (x) of less than 80 ml/100 g, and a refractory filler.
Description
The application is that international filing date is on March 6th, 2002, international application no is PCT/JP02/02086, the China national application number is 02801131.7, and denomination of invention is divided an application for " raw material for refractory, its manufacture method and use the refractory materials of this raw material " application.
Technical field
The present invention relates to a kind of raw material for refractory of forming by graphite granule and the manufacture method of spendable graphite granule thereof.The present invention relates to a kind of raw material for refractory composition that contains this raw material again.Have, the present invention relates to a kind of raw material for refractory composition, described raw material for refractory composition multiplely is selected from carbon black and makes the specific carbon granules of the graphited graphite granule of carbon black and form by cooperating.Again, the present invention relates to a kind of refractory materials that described raw material for refractory composition is shaped and forms, particularly, relate to and a kind ofly have excellent erosion resistance, scale resistance and thermal shock resistance, be applicable to refractory materials as concise container inside lining.
Background technology
Carbon has and is difficult to be the wetting character of melts such as slag.For this reason, the refractory materials that contains carbon has excellent wearing quality.Therefore, in recent years, be widely used as the inner lining refractory of various molten metal containers.For example, when using magnesium oxide as fireproof refractory, find that nationality is by the characteristic of above-mentioned carbon and the corrosion resistance nature for melts that magnesium oxide had, the inner lining refractory of pretending to molten metal container has excellent wearing quality.
Yet along with the expansion that carbon containing refractory uses, the dissolving of the carbon in the refractory materials in ingot steel separated out, and the problem of so-called " carbon is separated out " takes place.Particularly, severeer to the high-qualityization requirement of steel in recent years, also surging to the carbon content requirement still less of refractory materials.On the other hand,, also wish to use the refractory materials of low heat conductivity, thus, wish to use the refractory materials of low carbon content from the consideration of inhibition that the heat of container is distributed and energy-conservation etc. environment protection.
In the past, be used for the carbon raw material of carbon containing refractory, the main use has flaky graphite.Pitch, coke, intermediary (meso) carbon etc.For obtaining the refractory materials of low carbon content,, then can produce the low problem of thermal shock resistance as only reducing the usage quantity of these carbon raw materials.For addressing this problem, the flat 5-301772 communique of Japanese Patent Publication Laid-Open proposes a kind of with the scheme of expanded graphite as the refractory materials of carbon raw material.Put down in writing in the embodiment, the raw material for refractory composition that mixes and be made up of sintered magnesia 95 weight parts, expanded graphite 5 weight parts and phenolic resin 3 weight parts after the press molding, 300 ℃ of following heat treated 10 hours, obtains the carbon magnesia brick.Compared with the occasion of the flaky graphite that uses same amount, described method has been improved the spalling resistance energy.
The flat 11-322405 communique of Japanese Patent Publication Laid-Open proposes a kind of scheme (claim 5) of low carbonaceous carbon containing resistivity against fire material.Described low carbonaceous carbon containing refractory is a kind of raw material title complex that contains refractory raw material and carbonaceous carbon raw material, it is characterized in that, the fixedly carbonaceousfuel component that described title complex contains above-mentioned carbon raw material for the hot residual component 100 weight % of this raw material title complex is 0.2-5 weight %, and at least a portion of described carbon raw material has been used carbon black.This communique explanation is because carbon black has the small particle size that is about 0.1 μ m, therefore, significantly improve for the dispersity in the refractory materials tissue, the aggregate particle surface can be covered by trickle carbon granules, at high temperature can interdict the contact between the aggregate particle for a long time, thereby, can suppress excessive sintering.In embodiment, then put down in writing in the fireproof refractory of forming by magnesium oxide 50 weight parts and aluminum oxide 50 weight parts, cooperate phenolic resin 2.5 weight parts, pitch 1 weight part and carbon black (pattern of fever) 1 weight part, form the raw material title complex, obtain refractory materials 120-400 ℃ of roasting.And shown to have excellent spalling resistance and resistance to oxidation damage performance.
Japanese Patent Publication Laid-Open 2000-86334 communique has been put down in writing a kind of sliding nozzle device brick, and described sliding nozzle device is 24m with brick system to the specific surface area of the plug-in interpolation 0.1-10 of the title complex of being made up of fireproof refractory and metal weight %
2The carbon black that/g is following adds organic binder bond again, mixes, and after the shaping, carries out heat treated under 150-1000 ℃ of temperature.
Owing to be the big particle diameter with particle diameter 80-500nm, specific carbon black (thermal level or thermal black kind) cooperation with spherical shape, its fillibility is good, brick dense structureization, void content is low, the carbon black self that uses also has excellent oxidation-resistance, can obtain having the refractory materials of excellent oxidation-resistance energy.Show among the embodiment, form the composition of forming by aluminum oxide 97 weight parts and aluminium 3 weight parts, phenolic resin 3 weight parts, silicone resin 3 weight parts and the cooperation of carbon black 3 weight parts, obtain refractory materials in the heating of the temperature below 500 ℃.Described refractory materials has shown to have the excellent oxidation-resistance energy.
The flat 7-17773 communique of Japanese Patent Publication Laid-Open proposes a kind of underdeveloped spherical carbon black of big particle diameter, structure with particle diameter 0.02-0.50 μ m, makes an addition to unshape refractory in the fireproof refractory with 0.1-3 weight %.Again, the flat 10-36177 communique of Japanese Patent Publication Laid-Open proposes a kind of carbon black 2-15 weight % of DBP absorbed dose below 100ml/100g and blast furnace iron notch occlusive materials of a certain amount of carbon raw material, silicon carbide, silicon nitride, refractory raw material and carbon containing grafting material of containing.Have, Japanese Patent Publication Laid-Open 2000-192120 communique proposes a kind of blast furnace iron notch occlusive materials of being made up of at carbon black, pitch and the binding agent of 15-80ml/100g fireproof refractory DBP absorbed dose again.
On the other hand, Japanese Patent Publication Laid-Open 2000-273351 communique proposes a kind ofly will to contain mixture that carbon black and greying promote material 2000-2500 ℃ of following heat treated, the manufacture method of graphitized carbon black.Nationality promotes material by heating the greying be made up of element or its compound of boron, silicon, aluminium, iron etc. simultaneously, and the about 2800 ℃ Heating temperature that carbon black greying in the past must be able to be used is reduced to about 2000-2500 ℃.
Yet, put down in writing as the flat 5-301772 communique of Japanese Patent Publication Laid-Open, use expanded graphite, then in its usage quantity is low carbonaceous refractory materials about 5 weight % as carbon raw material, compared with using occasion, can also obtain good thermal shock resistance with the flaky graphite of measuring.Yet because expanded graphite is the very large raw material of a volume, even use 5 weight %, the filling properties of its refractory materials also reduces, and is low for the erosion resistance of melts.It also is a very big problem that the oxidation of the carbon raw material during again, refractory materials uses disappears.
The flat 11-322405 communique of Japanese Patent Publication Laid-Open, spy open 2000-86334 communique, spy open flat 7-17773 communique, spy open flat 10-36177 communique and special open all to disclose on the 2000-192120 communique use the example of carbon black as carbon raw material.It is generally acknowledged that nationality can improve spalling resistance by the employing of carbon black, but its erosion resistance and scale resistance and insufficient.Again, employed carbon black is that specific surface area is 24m
2/ g is following, big, the underdeveloped spherule of structure of particle diameter, and its DBP absorbed dose perhaps is 15-80ml/100g below 100ml/100g.That is, in any case, be preferably the carbon black that DBP (dibutyl phthalate) absorbed dose is few, particle diameter is big., adopt described carbon black, the improvement of shock-resistance is still not enough.
For improving the compactness and the scale resistance of tissue, mainly be to adopt the monomer powders of adding aluminium, silicon, magnesium etc. or add norbide, silicon carbide etc. again, in the past; The method of the powder of the compound beyond the oxide compound.Yet described method must be used these additives in a large number as wishing to get abundant effect, its result, and the unfavorable condition that influences other characteristics is a lot, has to a certain extent compromise.
The greying that Japanese Patent Publication Laid-Open 2000-273351 communique has been put down in writing carbon black and boron etc. promotes that material carries out carrying out graphitizing method after the heat treated.But its purposes is the catalyzer carrier of phosphoric acid type fuel cell, and whether described graphited carbon black is useful as raw material for refractory, and record does not have any enlightenment yet.
The present invention does for solving above-mentioned problem, and the object of the invention is to provide a kind of refractory materials with excellent erosion resistance, scale resistance, thermal shock resistance, particularly, provides a kind of carbon content few carbon containing refractory.The carbon containing refractory that described carbon content is few is separated out few to the carbon in the ingot steel, few from the heat radiation of container, thereby useful.In addition, purpose of the present invention also is to provide a kind of raw material for refractory and raw material for refractory composition that obtains refractory materials.Other purposes of the present invention are, the manufacture method of the graphite granule that can be used in above-mentioned material is provided.Have again, the object of the present invention is to provide a kind of manufacture method of above-mentioned raw material for refractory composition.
Summary of the invention
Refractory materials is made of the particle of the multiple granularity of the micro mist below coarse grain to the 1 μ m from about 5mm, landfill between the larger particles gap, the polymer of micro mist that is called as matrix is very big to wearing quality influence.Have many pores and space on the matrix part, these have also played influence to the perviousness of melts such as the intensity of refractory materials, slag, the mitigate effects of thermal shocking etc.
The matrix granule granularity of refractory materials is usually below 44 μ m.But the present inventor notices, 10 μ m are following, be more preferably below the 1 μ m, that is, the performance of nano level ultrafine particle gives material very big influence.In carbon containing refractory, almost most of occasions are that carbon raw material is used as above-mentioned matrix part, and nationality, is studied with the overall performance of control refractory materials by the nano level control to carbon raw material for this reason.
When the present inventor was conceived to carbon raw material by nano level control, the method for control air hole structure was studied.The minimizing of pore amount is relevant with the erosion resistance raising, and in addition, the shape of pore (specific surface area) control and granular also have contribution to suitableization of dynamic elasticity rate and the raising of thermal shock resistance.So, nationality is improved thermal shock resistance and then is improved erosion resistance and scale resistance by the control of air hole structure.
As the carbon raw material of nano level particulate, known have a carbon black, and nationality is by the control to its granularity, can be controlled to a certain degree air hole structure.Yet when the substrate material, sometimes, erosion resistance, oxidation resistent susceptibility might not be abundant with carbon black.For this reason, the present inventor painstakingly studies granularity again for the erosion resistance of carbon black self, the improvement method of scale resistance.
That is, a first aspect of the present invention is a kind of raw material for refractory of being made up of the graphite granule of median size below 500nm.Because the crystal structure of graphite is than carbon black prosperity, so for a kind of oxidation starting temperature height, when having the excellent oxidation-resistance energy, also have the excellent big material of corrosion resistance nature, thermal conductivity.Nationality can be cut apart pore, when controlling its structure, be improved the corrosion resistance nature and the scale resistance of particle self by the use of nano level trickle graphite granule.As a result, can obtain having the refractory materials of excellent resistance to sudden heating, erosion resistance and scale resistance.
Again, a first aspect of the present invention is a kind of raw material for refractory of being made up of the graphite granule that the carbon black greying is obtained.Carbon black according to the purpose difference of particle diameter, polymerization state and condition of surface etc., can be buied the carbon black of various brands for the carbonaceous particulate of the present nano-grade size of buying easily.
In above-mentioned graphite granule, graphite granule is preferably and contains at least a above element that is selected from metal, boron and silicon.The graphite granule nationality is by containing described carbon element in addition, can nationality so-called by making " composite graphite particles ", improve the oxidation starting temperature of graphite granule self, improve oxidation resistent susceptibility and erosion resistance, and further improve the scale resistance and the erosion resistance of resulting refractory materials when making raw material with this composite graphite particles.
Contain the graphite granule that is selected from metal, boron, reaches at least a above element of silicon, preferably with carbon black be selected from least a above element monomer of metal, boron and silicon or contain the compound heating of this element and the graphite granule that obtains, be more preferably, with carbon black be selected from least a above element monomer heating of metal, boron and silicon and the graphite granule that obtains.
Again, the present invention is a kind of raw material for refractory composition of being made up of fireproof refractory and above-mentioned graphite granule.At this moment, be preferably the raw material for refractory composition of forming by fireproof refractory 100 weight parts and above-mentioned graphite granule 0.1-10 weight part.
Have, the present invention is characterized in that for a kind of containing is selected from metal, boron, and the manufacture method of the graphite granule of at least a above element of silicon again, with carbon black be selected from the alkoxide heating of at least a above element of metal, boron and silicon.Because the monomer heating is got angry easily, danger, and change alkoxide into, then handle the dust explosion risk minimizing easily.At this moment, self-evident as refractory materials the time as mentioned above by the graphite granule that the inventive method makes, can solve problem of the present invention, and this manufacture method also is a kind of utilizable method for other purposes.For this point, identical in following two kinds of manufacture method.
Again, the present invention is selected from metal, boron, and the manufacture method of the graphite granule of at least a element of silicon for a kind of containing, it is characterized in that, with the oxide compound of carbon black with at least a above element that is selected from metal, boron and silicon, and the METAL HEATING PROCESS of this oxide compound of reduction.Nationality is by described combination, and reduction constitutes the element of oxide compound easily, and it is contained in the graphite.
Have again, the present invention is a kind of manufacture method of graphite granule, described method ties up to carbon black and is selected from least a above element monomer of metal, boron and silicon or contains the compound heating of this element, obtains graphite granule, above-mentioned graphite granule is carried out again the manufacture method of oxide treatment.So, can further obtain scale resistance.
On the other hand, can control air hole structure to a certain degree, with control carbon black granularity.Yet as mentioned above, as only using the few carbon black of DBP absorbed dose, thermal shock resistance not enough.On the other hand, as only using the many carbon blacks of DBP absorbed dose, then as described later shown in the comparative example, its oxidation resistent susceptibility and erosion resistance are not enough.After a second aspect of the present invention was and painstakingly studies, its result reached the method for such problem that achieves a solution.
Promptly, a second aspect of the present invention is a kind of raw material for refractory composition of being made up of carbon granules (A), carbon granules (B) and fireproof refractory, described carbon granules (A) is for being selected from carbon black and carbon black being carried out the graphite granule that greying forms, and its DBP absorbed dose (x) is more than 80ml/100g; The graphite granule of described carbon granules (B) for being selected from carbon black and the carbon black greying being formed, its DBP absorbed dose (x) is less than 80ml/100g.Here, the value (ml/100g) of DBP absorbed dose (x) for measuring by the method for the method A defined of JIS K6217 the 9th [DBP absorbed dose].
Nationality can form very tiny air hole structure by being selected from carbon black and making the use of graphite granule that the carbon black greying obtains, carbon granules (A) that the DBP absorbed dose is big in the matrix of refractory materials, obtain suitable dynamic elasticity rate, improves thermal shock resistance.The dynamic elasticity rate is the index of thermal shock resistance, and its value is more little, and thermal shock resistance is excellent more.When actual use has the refractory materials of excellent thermal shock resistance, can suppress to peel off damage.But, only use carbon granules (A) then can not obtain sufficient oxidation resistent susceptibility and erosion resistance, and by then improving this with the little carbon granules of DBP absorbed dose (B), its result, the refractory materials that obtains having excellent thermal shock resistance, oxidation resistent susceptibility and erosion resistance.
At this moment, for the fireproof refractory of 100 weight parts, the total weight of carbon granules (A) and carbon granules (B) is the 0.1-10 weight part, and the weight ratio (A/B) of carbon granules (A) and carbon granules (B) is preferably 1/99-99/1.Again, the average primary particle diameter of carbon granules (A) is 10-50nm, and the average primary particle diameter of carbon granules (B) is 50-500nm.
Be preferably, the ratio (x/y) of the DBP absorbed dose (y) of the DBP absorbed dose (x) of carbon granules (A) and the compression sample of carbon granules (A) is more than 1.15.Here, the DBP absorbed dose (y) of the compression sample of carbon granules (A) is the value of being measured by the method for the 10th of JIS K6217 [the DBP absorbed dose of compression sample] defined (ml/100g).The carbon granules that DBP absorbed dose after the compression is low is the structure that the structure nationality of carbon granules is changed by squeeze operation.Particularly, enlightened primary particle polymeric polymer structure.Nationality can obtain excellent thermal shock resistance by so use of carbon granules (A).
At least one side of carbon granules (A) and carbon granules (B) is the graphite granule that the carbon black greying is formed, improvement from oxidation resistent susceptibility and erosion resistance, be suitable, be more preferably that two sides in carbon granules (A) and the carbon granules (B) are all the graphite granule that the carbon black greying is formed.Nationality can improve the erosion resistance and the oxidation resistent susceptibility of particle self by the use of graphite granule.Its result obtains having the refractory materials of excellent resistance to sudden heating, erosion resistance and oxidation resistent susceptibility.
At least one side of carbon granules (A) and carbon granules (B) is the graphite granule that the carbon black greying is formed, and this graphite granule contains at least a above element that is selected from metal, boron, silicon, and this is suitable from the improvement of oxidation resistent susceptibility and erosion resistance.Be more preferably, two sides in carbon granules (A) and the carbon granules (B) are all the graphite granule that the carbon black greying is formed, and this graphite granule contains at least a above element that is selected from metal, boron, silicon.Nationality contains described carbon element, so-called " composite graphite particles " in addition by graphite granule is made, and can further improve the beginning oxidizing temperature of graphite granule self, improves the erosion resistance and the oxidation resistent susceptibility of particle self.Having, is that the oxidation resistent susceptibility and the erosion resistance of the refractory materials of raw material also is improved with described composite graphite particles again.
When making above-mentioned raw material for refractory composition, carbon granules (A) is scattered in the organic binder bond in advance, then, mix with other raw materials.This method can be improved the dispersiveness of the carbon granules (A) in the matrix, the refractory materials that the result can obtain to improve resistance to sudden heating, scale resistance and erosion resistance, so preferably use.
In the raw material for refractory composition of the present invention aspect first and second, consider the useful purposes of the refractory materials of low carbon content, then be preferably, above-mentioned fireproof refractory is the raw material for refractory composition of being made up of magnesium oxide.Again, the present invention is a kind of refractory materials that makes above-mentioned raw material for refractory composition be shaped and obtain.
Description of drawings
Figure 1 shows that the mode chart that forms polymeric carbon black.
Figure 2 shows that the X-ray diffractogram of graphite granule C.
Embodiment
A first aspect of the present invention is the raw material for refractory of being made up of the graphite granule of median size below 500nm.Here, median size is important below 500nm.Because nationality can make the air hole structure in the refractory materials matrix tiny by the use of the graphite granule of this very tiny grain size.In the past, flaky graphite or its median size of expanded graphite of using as raw material for refractory all surpassed 1 μ m widely, can't realize the trickle air hole structure in the matrix, but the present invention used trickle graphite granule, had realized described air hole structure.
Median size is preferably below 200nm, is more preferably below 100nm.Again, median size more than 5nm, is preferably more than 10nm usually.Surpass 500nm as median size, then air hole structure can't be tiny, as less than 5nm, and difficult treatment then.Median size described here refers to the number average bead diameter of the primary particle of graphite granule.Therefore, for example, have the occasion of a plurality of primary particle paradigmatic structures, can be used as a plurality of primary particles that constitute this structure and calculate at particle.Described particle diameter can be recorded by electron microscope observation by nationality.
The manufacture method of graphite granule is also without particular limitation, the graphite of greater particle size can be carried out machinery or electric pulverizing, so that it becomes above-mentioned particle diameter.Yet it is very difficult will being crushed to the following very tiny particle of 500nm, and therefore, preferably the carbon granules to the particle diameter below the former 500nm carries out graphitizing method.
Again, the present invention is a kind of raw material for refractory of being made up of the graphite granule that the carbon black greying is obtained.Above-mentioned carbon black according to particle diameter, polymerization state condition of surface etc., according to the purpose difference, is buied various brands for the carbon particulate of present nano-scale particle sizes of buying easily easily.Carbon black self is as raw material for refractory, then illustrated and known as background technology one hurdle, and its erosion resistance, oxidation resistent susceptibility are not enough.By it is carried out greying, can make crystalline structure prosperity, oxidation starting temperature height, when having the excellent oxidation-resistance energy, also have the excellent high material of erosion resistance, thermal conductivity.
Carbon black as raw material is also without particular limitation.Be preferably the carbon black that uses the primary particle of diameter below 500nm to form.Particularly, can enumerate any in, acetylene black black, thermal black, dim, ケ Star チ エ Application (Japanese) carbon black etc. as furnace black, flue.
Preferably, can enumerate as extruding (Off ア-ス ト エ Network ス ト Le-デ イ Application ゲ) furnace black (FEF), super ablation (super ablation) furnace black (SAF) and senior ablation (high ablation) furnace black (HAF), thin (fine) thermal black (FT), medium (medium) thermal black (MT) fast, partly strengthening furnace black (SRF), general (general purpose) furnace black various carbon blacks such as (GPF).At this moment, also can cooperate multiple carbon black to use as raw material.
Make carbon black graphitizing method and without particular limitation.Can make its greying in heat under the inert atmosphere.Heating can make the carbon black greying under common temperature more than 2000 ℃.
After the greying, in X-ray diffraction method is measured, can observe peak value from crystalline structure.And, to carry out along with graphited, spacing of lattice is from shortening.002 diffracted ray of graphite and graphited wide-angle one side of shifting to simultaneously.Angle of diffraction 2 θ of this diffracted ray are corresponding from (centre plane at interval) with spacing of lattice.In the present invention, preferably use spacing of lattice from the graphite of d below 3.47_.From surpassing 3.47_, then greying is carried out insufficiently as spacing of lattice, and thermal shock resistance, oxidation resistent susceptibility and erosion resistance are not enough.
In above-mentioned graphite granule, graphite granule is preferably the graphite that contains at least a above element that is selected from metal, boron and silicon.Make and contain above-mentioned carbon element in addition in the graphite granule, promptly so-called " composite graphite particles " by making, can improve the oxidation starting temperature of graphite granule self more, improving oxidation resistent susceptibility and erosion resistance, is that the oxidation resistent susceptibility and the erosion resistance of the prepared refractory materials of raw material is improved so that make with this composite graphite particles.
Here, specifically give an example, can enumerate, as each elements such as magnesium, aluminium, potassium, titanium, chromium, cobalt, nickel, yttrium, zirconium, niobium, tantalum, molybdenum, tungsten, boron and silicon as at least a above element that is selected from metal, boron and silicon that graphite granule contains.Wherein, as can be used for improving the oxidation resistent susceptibility of refractory materials and the example of element preferably of erosion resistance can be enumerated boron, titanium, silicon, zirconium and nickel, and be the best with boron and titanium.
There is method and without particular limitation in each element in graphite granule, can be contained in granule interior, also can exist with the form of lining particle surface.Again, each element can its oxide compound, the form of nitride, boride or carbide contains, and is preferably, and exists with the compound form of oxide compound, nitride, boride or carbide, is more preferably, and exists with the form of carbide or oxide compound.Can illustration B as carbide
4C and TiC can illustration Al as oxide compound
2O
3
Carbide can be to contain with the carbon atom bonded form that constitutes suitable graphite in graphite granule.Yet, when its total amount is this carbide, because can not bring into play as the performance of graphite and undesirable, so must have the crystal structure of graphite.The state of above-mentioned graphite granule can be analyzed by X-ray diffraction.For example, except peak value, also can be observed as TiC or B corresponding to crystal structure of graphite
4The peak value of the crystal correspondence of the compound that C is such.
Make the method that contains at least a above element that is selected from metal, boron and silicon in the graphite granule also without particular limitation, but be preferably, to carbon black be selected from the monomer of at least a above element of metal, boron and silicon or the compound that contains this element heats and the method that obtains.Nationality, is made and contains above-mentioned element in the graphite-structure when greying is carried out by heating.
At this moment, be more preferably, the monomer of carbon black with at least a above element that is selected from metal, boron and silicon heated and the method for acquisition.Because, nationality by with the monomeric heating of element, can utilize the thermal value when generating to react by burning synthetic carbide.Particularly, preferably heat simultaneously with aluminium, potassium, titanium, zirconium, boron and silicon.Utilize this reaction heat, but nationality is synthesized by self combustion synthesis method.For utilizing id reaction heat, temperature in the stove can be reduced to lower than making the independent graphited occasion of carbon black.And, keep and surpass 2000 ℃ furnace temperature, on device, a lot of problems are also arranged on the expense.So this point is very important.
For example, the combustion synthesis reaction formula of boron and carbon, and the combustion synthesis reaction formula of titanium and carbon as follows respectively.
These reactions can all be exothermic reactions, and it is synthetic to carry out self burning.
As making the method that contains at least a above element that is selected from metal, boron and silicon in the graphite granule, the alkoxide of carbon black with at least a above element that is selected from metal, boron and silicon heated, also can utilize the heating of burning synthetic.So, the preferred use is to get angry easily because of the monomer heating, is a kind of element using method of danger, and alkoxide is then handled easily, the danger of minimizing dust explosion etc.
Here said alkoxide serve as reasons hydrogen at least a above element substitution alcoholic extract hydroxyl group that is selected from metal, boron and silicon and the salt that obtains.Can be expressed as M (OR) n.Here, M can use the 1-4 valency, be preferably the element of 2-4 valency, and unit for example have magnesium, aluminium, titanium, zirconium, boron, and silicon preferably.N is the valence mumber corresponding to element M, is the integer of 1-4, is preferably the integer of 2-4.Again, R so long as organic group get final product, and without particular limitation, be preferably the alkyl that carbonatoms is 1-10, can exemplify out as methyl, ethyl, propyl group, sec.-propyl, normal-butyl etc.Also can be only a kind of with these alkoxide, also can also use multiple alkoxide.In addition, also can be with element monomer, oxide compound etc. and alkoxide and usefulness.
Again, consider from utilizing burning synthetic heating angle, be preferably, as making the method that contains at least a above element that is selected from metal, boron and silicon in the graphite granule, can be with carbon black and the monomeric oxide compound of at least a above element that is selected from metal, boron and silicon and the method that this oxide compound reductive metal is heated.Nationality is by so combination, and the metallic reducing oxide compound can make the element that constitutes oxide compound be contained in the graphite.For example, when adding thermal black, aluminium and oxide compound, then at first boron oxide is reduced by aluminium, becomes the boron monomer, with the carbon black reaction, obtains norbide again.Its chemical formulation is as follows.
Chemical formulation when making carbon black, aluminium and titanium dioxide reaction again, is as follows.
These reactions also are exothermic reactions, and it is synthetic to burn, and also can not carry out greying even the interior temperature of stove does not make such height.
Have, be preferably, to graphite be selected from the monomer of at least a above element of metal, boron and silicon or the compound that contains this element heats, resulting graphite granule carries out oxide treatment again.By oxide treatment, main because can form oxide coating film on the graphite granule surface, therefore, have scale resistance more.
Method for oxidation and without particular limitation can exemplify out the method handled with oxidable high-temperature gas etc.Particularly, can enumerate the hot gas that makes after air and the fuel combustion and the so-called hot gas method of graphite granule reaction certain hour etc.At this moment, as long with the duration of contact of gas, the then whole oxidation of graphite, so, must impose a condition, can only make a part of oxidation.
Self-evident, according to the graphite granule of aforesaid method manufacturing.As mentioned above, the occasion using as raw material for refractory can solve problem of the present invention.But manufacture method of the present invention also can be used for other purposes.
The above-mentioned graphite granule that makes is cooperated with other compositions, make raw material for refractory composition of the present invention.Particularly, make the raw material for refractory composition of forming by fireproof refractory and above-mentioned graphite granule.
A second aspect of the present invention is one to contain the raw material for refractory composition of carbon granules (A) and carbon granules (B), and described carbon granules (A) is selected from carbon black and makes the graphited graphite granule of carbon black, its DBP absorbed dose (x) more than 80ml/100g; Described carbon granules (B) is selected from carbon black and makes the graphited graphite granule of carbon black, its DBP absorbed dose (x) less than 80ml/100g.
Carbon black is a kind of carbon particulate that is easy to the nanometer particle size of buying at present, according to the difference of particle diameter, polymerization state, condition of surface, purpose etc., can buy various brands easily.Can enumerate, acetylene black black, thermal black, dim, (ケ Star チ エ Application) carbon black etc. particularly as furnace black, flue.
The average primary particle diameter of carbon black is generally the following carbon granules of 500nm, and the graphite granule that its greying is formed also has roughly the same median size.Nationality can make the air hole structure in the refractory materials matrix tiny by the use of the carbon granules of this very tiny grain size.In the past, all substantially exceeded 1 μ m, can't realize the trickle air hole structure in the matrix, but the present invention used trickle carbon granules, realized trickle air hole structure as the widely used flaky graphite of the raw material of anti-condensation material the or its median size of expanded graphite.
Nationality can form very tiny air hole structure by the use of the carbon granules (A) of DBP absorbed dose (x) more than 80ml/100g in refractory materials matrix, reduce the dynamic elasticity rate, improves thermal shock resistance.Here, so-called DBP absorbed dose (x) is the measured value of method by the A defined of JIS K6217 the 9th [DBP absorbed dose].Be more preferably, the DBP absorbed dose of carbon granules (A) is more than 90ml/100g, and best is more than 100ml/100g.Usually, the DBP absorbed dose of carbon granules (A) is below 1000ml/100g.
The average primary particle diameter of above-mentioned carbon granules (A) is preferably at 10-50nm.As below 50nm, then just form very tiny air hole structure in the refractory materials matrix easily.Be more preferably below 45nm.Again,, more than 15nm, be advisable, be more preferably more than 20nm from handling easily and oxidation resistent susceptibility and the consideration of erosion resistance aspect.Average primary particle diameter can be recorded by electron microscope.At this moment, for example, in the occasion of particle, by containing calculating of a plurality of primary particles of constituting it with a plurality of primary particle polymeric structures.
Have, be preferably, in the carbon granules (A), the ratio (x/y) of the DBP absorbed dose (y) of the compression sample of DBP absorbed dose (x) and carbon granules (A) is more than 1.15.Here, the DBP absorbed dose (y) of the compression sample of carbon granules (A) is measured by the method for the 10th of JIS K6217 [the DBP absorbed dose of compression sample] defined.For under the pressure of 165MPa, carry out the DBP absorbed dose after the squeeze operation repeatedly 4 times.
Carbon black has: the carbon black of being made up of the globular single particle and the carbon black of primary particle mutual polymerization formation polymer (aggregate).Figure 1 shows that the mode chart that forms polymeric carbon black.Carbon granules of the present invention (A) is preferably to use and forms polymeric particle.The ratio (x/y) of the DBP absorbed dose (y) of the compression sample of so-called DBP absorbed dose (x) and carbon granules (A) promptly refers to more than 1.15, makes carbon black that to a certain degree above structural changes take place by squeeze operation.More specifically, distortion or ruined polymer increasing proportion during compression, for this reason, the DBP absorbed dose reduces more than the certain proportion.Above-mentioned ratio (x/y) is more preferably more than 1.2, is preferably in more than 1.3.Usually, (x/y) below 2.
Above-mentioned (x/y) ratio is big, and when illustrating as refractory materials, when being subjected to heat or mechanical stress, polymer deforms easily or be destroyed.That is, when using, in matrix, produce stress, at this moment, absorb energy, therefore, can relax above-mentioned stress owing to can or destroy by polymeric distortion as refractory materials.That is, the cracking that takes place in the matrix reaches when forming polymeric carbon black, its Arrested Development.Form the thermal shock resistance of the excellence of refractory materials thus.
Have, for example in the occasion of relevant nemaline polymer etc., this polymer self also can play the effect of the strongthener in the matrix again, and because good by polymeric heat conductivility, this point also can be improved thermal shock resistance.And under many occasions, the less carbon black multiform of average primary particle diameter becomes above-mentioned polymer, therefore, can obtain tinyization of the pore in the matrix simultaneously.That is, the result can control nano level very tiny pore, forms the excellent refractory materials of resistance to sudden heating.The relevant effect of bringing because of described polymeric formation as carbon granules (A), is not only carbon black, is using the graphited carbon granules occasion of carbon black too.
As the spendable carbon black of carbon granules (A) and without particular limitation.Particularly, can enumerate, as extruding (Off ア-ス ト エ Network ス ト Le-デ イ Application ゲ) furnace black (FEF), super ablation (super ablation) furnace black (SAF) and senior ablation (high ablation) furnace black (HAF) etc. fast.Make the carbon black greying as carbon granules (A) in use and during the graphite granule that forms, can make suitable graphite granule with described carbon black as raw material.Again, carbon granules (A) also can be the mixture of multiple carbon granules (A).
Yet, only described carbon granules (A) is being matched with in the raw material for refractory composition, though can improve the resistance to sudden heating that tinyization of pore causes, also there is the low tendency of oxidation resistent susceptibility and erosion resistance.For this reason, from the present invention, except carbon granules (A), also also with carbon granules (B).
By will improving the tamped density of refractory materials, improve oxidation resistent susceptibility and erosion resistance from carbon black and the selected DBP absorbed dose of the particle that the carbon black greying is formed in carbon granules (B) and carbon granules (A) and usefulness less than 80ml/100g.Be more preferably, the DBP absorbed dose of carbon granules (B) is more preferably below 40ml/100g below 60ml/100g.Again, usually, the DBP absorbed dose of carbon granules (B) is more than 10ml/100g.
The average primary particle diameter of carbon granules (B) is to be advisable at 50-500nm.More than 50nm, then the filling properties of refractory materials in matrix is good as the average primary particle diameter of carbon granules (B), and oxidation resistent susceptibility and erosion resistance are improved.Be more preferably more than 60nm.Again, if above-mentioned average primary particle diameter surpasses 500nm, then the pore size in the matrix too increases, and thermal shock resistance significantly reduces.Be more preferably below 200nm, best is below 100nm.
Above-mentioned carbon granules (B) is different with carbon granules (A), considers that from the filling properties viewpoint the mutual polymerization of primary particle forms polymeric situation seldom, is preferably, and many particles are made up of single spheroid.Therefore, DBP absorbed dose (x) is preferably use at the carbon granules below 1.15 with the ratio (x/y) of the DBP absorbed dose (y) of the compression sample of carbon granules (A).Be more preferably, above-mentioned ratio (x/y) is preferably in below 1.05 below 1.1.Carbon black only by mutually not polymeric independently ball form, the incomplete ruined occasion of its structure of compression back, this ratio (x/y) is 1 in theory.Yet, certain measuring errors is in fact often arranged.Therefore, as the ratio of measured value, (x/y) usually more than 0.9.By and be the carbon granules (A) of main body and in order to polymeric polymer structure so to heavens based on the carbon granules (B) of single spheroid, can when guaranteeing high filling ratio, realize very tiny air hole structure.
As the spendable carbon black of carbon granules (B) and without particular limitation.Particularly, can use, as fine thermal black (FT), medium (medium) thermal black (MT), partly strengthen furnace black (SRF), general (generalpurpose) furnace black (GPF) etc.The graphite granule that forms making the carbon black greying is as the occasion of carbon granules (B), and can make with above-mentioned carbon black is the graphite granule that is fit to of raw material.Again, carbon granules (B) also can be the mixture of multiple carbon granules (B).
The weight ratio (A/B) of carbon granules (A) and carbon granules (B) is preferably 1/99-99/1.Weight ratio (A/B) was less than 1/99 o'clock as described, and probably thermal shock resistance is not enough; Weight ratio (A/B) surpasses at 99/1 o'clock as described, and oxidation resistent susceptibility is not enough sometimes.Described weight ratio (A/B) is preferably more than 5/95, is more preferably more than 10/90.Again, weight ratio (A/B) below 90/10, is more preferably below 70/30 more fortunately.
At least one side in carbon granules (A) and the carbon granules (B) is the graphite granule that the carbon black greying is formed, and this is an ideal from improving scale resistance and erosion resistance.As for graphite granule, illustrated as above-mentioned first aspect.When making the carbon black greying, the DBP absorbed dose and the average primary particle diameter of DBP absorbed dose, compression sample change little usually.
In the present invention, good especially is the graphite granule of carbon granules (A) for the carbon black greying is formed.As the carbon black of carbon granules (A) compared with carbon black as carbon granules (B), its scale resistance and corrosion-resistant, so, but nationality overcomes this shortcoming by greying.Best example is, the graphite granule of carbon granules (A) for the carbon black greying is formed, and carbon granules (B) is a carbon black.At this moment, compare with common carbon black, because the graphite granule cost height that the carbon granules greying is formed, therefore, the use level of carbon granules (A) is reduced by at least in the use level of carbon granules (B) comparatively economical.
The present invention's example preferably is that any of carbon granules (A) and carbon granules (B) all is the graphite granule that the carbon black greying is formed.At this moment, any of employed carbon granules (A) and carbon granules (B) is compared with carbon black, and its scale resistance and erosion resistance are all good.As a result, can further improve its scale resistance and erosion resistance.
Again, at least a in carbon granules (A) and the carbon granules (B) is the graphite granule that the carbon black greying is formed, and this greying particle is preferably and contains at least a above element that is selected from metal, boron, the silicon.Not only only carbon black is carried out greying, and make and contain at least a above element that is selected from metal, boron, the silicon in the graphite granule.Take this, can further improve its scale resistance and erosion resistance.As for " composite graphite particles ", illustrated as above-mentioned first aspect.
At this moment, the graphite granule of carbon granules (A) for the carbon black greying is formed, this graphite granule contains at least a above element that is selected from metal, boron, the silicon, is because a side of carbon granules (A) compares erosion resistance with carbon granules (B), scale resistance is relatively poor, can remedy this shortcoming and just do like this.
At this moment one of example preferably is to make the carbon black greying and the graphite granule that constitutes carbon granules (A), and this graphite granule is to contain the graphite granule that is selected from least a above element in metal, boron and the silicon, and carbon granules (B) is not graphited carbon black.At this moment, compared with common carbon black, because the graphite granule that the carbon black greying is formed contains at least a above element that is selected from metal, boron, the silicon, so from manufacture method cost height, so, being preferably, the use level of carbon granules (A) is less than the use level of carbon granules (B).
One of another better example is, the graphite granule of carbon granules (A) for the carbon black greying is formed, this graphite granule contains at least a above element that is selected from metal, boron, the silicon, and carbon granules (B) is for making the graphited graphite granule of carbon black, and this graphite granule does not contain above-mentioned element.In the occasion that graphite granule compares each other, carbon granules (A) is compared with carbon granules (B), its scale resistance and corrosion-resistant, so, but nationality contains at least a above element that is selected from metal, boron, the silicon by the greying particle this shortcoming is compensated.
As best example of the present invention be, any in carbon granules (A) and the carbon granules (B) is all the graphite granule that the carbon black greying is formed, and this greying particle contains at least a above element that is selected from metal, boron, the silicon.At this moment, the both sides of employed carbon granules (A) and carbon granules (B) have excellent erosion resistance and scale resistance, and therefore, the result can obtain scale resistance and the very excellent refractory materials of erosion resistance.
As above illustrated carbon granules (A) and carbon granules (B) are cooperated other compositions, make raw material for refractory composition of the present invention.Particularly, make the raw material for refractory composition of forming by carbon granules (A) and carbon granules (B) and fireproof refractory.
In the raw material for refractory composition of first aspect present invention, with graphite granule blended fireproof refractory and without particular limitation.In addition, in the raw material for refractory composition of second aspect present invention, also without particular limitation with carbon granules (A) and carbon granules (B) blended fireproof refractory.In these raw material for refractory compositions, according to different purposes, require performance, can use various fireproof refractories as refractory materials.Can use the resistivity against fire oxide compound of magnesium oxide, calcium oxide, aluminum oxide, spinel, zirconium white etc.; Carbide as silicon carbide, norbide etc.; Boride as boronation potassium, chromium boride etc.; Nitride etc. are as fireproof refractory.Wherein, consider to hang down to contain the carbonaceous availability, be preferably and use magnesium oxide, aluminum oxide, spinel.Best is magnesium oxide.Can enumerate electric fusion or sintering oxidation MAG block as magnesium oxide.These fireproof refractories are used to regulate granularity.
In the raw material for refractory composition of a first aspect of the present invention, be advisable with the 0.1-10 weight part for the use level of the graphite granule of fireproof refractory 100 weight parts.In the raw material for refractory composition of a second aspect of the present invention, be advisable with the 0.1-10 weight part for the carbon granules (A) of fireproof refractory 100 weight parts and the total use level of carbon granules (B) again.Less than 0.1 weight part, then almost can't confirm these particulate additive effects, and often thermal shock resistance is not enough as above-mentioned use level.Be more preferably, above-mentioned use level is more than 0.5 weight part.On the other hand, surpass 10 weight parts as above-mentioned use level, separating out sharply of carbon then, distributing of heat from container is also remarkable, and erosion resistance is low simultaneously.Be more preferably, above-mentioned use level is below 5 weight parts.
Have, the binding agent as using in the raw material for refractory composition of the present invention can use common organic binder bond or mineral binder bond again.As the high binding agent of fire performance, be preferably, use phenolic resin or with the organic binder bond as main component such as pitch.From the wettability and the residual carbonaceous rate height of raw material for refractory, being preferably with the phenolic resin is the binding agent of main component.Organic binder bond also can contain solvent, when containing solvent and cooperate, can have suitable viscosity.So the content of organic binder bond is also without particular limitation, but is advisable for the 0.5-10 weight part with respect to fireproof refractory 100 weight parts, and the 1-5 weight part is better.
In the raw material for refractory composition of second aspect present invention, binding agent is matched with raw material for refractory method for compositions of the present invention and without particular limitation, but be preferably, carbon granules (A) is scattered in the organic binder bond in advance, the method for other raw materials of remix is advisable.Because carbon granules (A) average primary particle diameter is little, separates out polymer more, therefore, easy and other raw materials cooperate separates out aggregate.But nationality is scattered in the organic binder bond it by stirring simultaneously with organic binder bond in advance, cooperates other raw materials such as fireproof refractory again, and carbon granules (A) is scattered in the matrix better.
At this moment, carbon granules (A) and carbon granules (B) both sides are scattered in the organic binder bond, other raw material of remix, yet, since more with respect to the situation that the usage quantity of the organic binder bond of the total total amount of carbon granules (A) and carbon granules (B) is few, good distribution can't be made in advance.For this reason, only make to be difficult to dispersive carbon granules (A) and to be scattered in advance in the organic binder bond, then, cooperate with carbon granules (B) and fireproof refractory again, by this, carbon granules (A) is scattered in the matrix better.
The raw material for refractory composition of a first aspect of the present invention uses graphite granule as carbon raw material.Again, the raw material for refractory composition of a second aspect of the present invention uses carbon granules (A) and carbon granules (B) as carbon raw material.In arbitrary raw material for refractory composition, also can add other carbon raw material again.For example, can mix use with other graphite compositions of flaky graphite, expanded graphite etc.Also can mix use with pitch and coke etc.
Again, raw material for refractory composition of the present invention also can contain above-mentioned composition in addition in the scope that does not hinder spirit of the present invention.Metal-powder, powdered alloy and the Si powder etc. that for example, can contain aluminium, magnesium etc.When mixing, also can add suitable water or solvent again.
The raw material for refractory composition that mixes and obtain as mentioned above makes it to be shaped, and optionally heating thus, obtains refractory materials of the present invention.Here, during heating, also can at high temperature burn till.For example, in the occasion of using magnesia brick, only be to carry out roasting usually 400 ℃ of following temperature.
So-called atypic refractory materials is being following time of unsetting state, can be contained in the raw material for refractory composition of the present invention.Again, the form one of unshape refractory regularly also can be contained in the raw material for refractory composition of the present invention.For example, blow the shape that is attached to the furnace wall,, therefore also can be contained in the refractory materials of the present invention's shaping owing to have certain form even form.
The refractory materials that so obtains has excellent erosion resistance, oxidation resistent susceptibility and thermal shock resistance, so, as being extremely useful for obtaining the high-quality used stove material of metallurgical product.
The optimal morphology that carries out an invention
Below use embodiment, the present invention is described.
In an embodiment, various analytical procedures, evaluation method are carried out as follows.
(1) observational technique of average primary particle diameter
Use transmission electron microscope, under 100000 times multiplying power, sample is photographed.Several mean values from the photo calculated diameter that obtains.At this moment, during the aggregation of particles of sample, it is thought obtain its average primary particle diameter by the discrete particle.
(2) the graphite spacing of lattice from method of calculation
Use the powdered graphite of powder x-ray diffraction device mensuration as object.Measuring wavelength X is the 1.5418_ of the K alpha-ray wavelength of copper.In the peak crystallization that is recorded by the X-ray diffraction device, near the big peak of the value of 2 θ 26 ° is equivalent to the peak of 002 in graphite.Thus, calculate the graphite spacing of lattice from d (_) from following formula.
d＝λ/2sinθ
Apparent porosity and bulk specific gravity after (3) 1400 ℃ of heat treated
The sample that will be cut to 50 * 50 * 50mm is imbedded in the coke in the electric furnace, under carbon monoxide atmosphere, with 1400 ℃ of heat treated 5 hours.After sample after the processing is put and is chilled to room temperature, record apparent porosity and bulk specific gravity according to JIS R2205.
(4) dynamic elasticity rate
The sample of 110 * 40 * 40mm is imbedded in the coke in the electric furnace, under carbon monoxide atmosphere, with 1000 ℃ or 1400 ℃ of following heat treated 5 hours.After sample after will handling is put and is chilled to room temperature, use ultrasonic scope, measure hyperacoustic delivery time, try to achieve dynamic elasticity rate E by following formula.
E＝(L/t)
2·ρ
Here, L be the ultrasonic wave transmitting range (specimen length, mm), t is ultrasonic wave delivery time (μ sec), ρ is the bulk specific gravity of sample.
(5) resistance to oxidation test
The sample of 40 * 40 * 40mm is imbedded in the electric furnace (atmosphere), after 1400 ℃ keep 10 hours down, cut off,, calculate its mean value at the practical decarburized depth of measuring on the cut surface on 3 that remove downside.
(6) corrosion resistance test
With the sample of 110 * 60 * 40mm pack into the revolution corrosion testing apparatus in, at the basicity (CaO/SiO that remains in 1700-1750 ℃
2Kept in the slag of)=1 1 hour, and carried out the test of this operation 5 times repeatedly, record the size of corrosion on the cut surface after the test.
[synthesis example 1]
Graphite granule A's (carbon granules b) is synthetic
" the ニ テ ロ Application # 10 modification " of using Shinnitsuka Carbon KK's system is as carbon black raw material.This carbon black is a kind of carbon black that belongs to Off ア-ス ト エ Network ス ト Le-デ イ Application ゲ furnace black (FEF), its average primary particle diameter is 41nm, DBP absorbed dose (x) is 126ml/100g, and the DBP absorbed dose (y) of compression sample is 89ml/100g, is the carbon granules a that uses in the present embodiment.With its carbon stove (electric wave Industrial Co., Ltd of Fuji system, FVS-200/200/200, FRET-50) in, under the argon gas environment,, make it greying 2100 ℃ of heat treated 3 hours, obtain graphite granule A (carbon granules b).The particle that obtains is carried out X-ray diffraction measure, observe peak, judge to have generated graphite granule from graphite-structure.The spacing of lattice of calculating from the diffracted ray suitable with 002 interval of graphite is 3.40_.Described particulate average primary particle diameter is 38nm, and DBP absorbed dose (x) is 118ml/100g, and the DBP absorbed dose (y) of compression sample is 85ml/100g.
[synthesis example 2]
Graphite granule B's (carbon granules e) is synthetic
Except the raw material carbon black that change is used, other are as synthesis example 1, the synthetic graphite granule B (carbon granules e) that makes.The raw material carbon black uses " HTC#20 " of Shinnitsuka Carbon KK's system as carbon black raw material.This carbon black is the carbon black of a kind of so-called thermal black (FT), and its average primary particle diameter is 82nm, and DBP absorbed dose (x) is 29ml/100g, and the DBP absorbed dose (y) of compression sample is 30ml/100g, is the carbon granules d that uses in the present embodiment.The particle that obtains is carried out X-ray diffraction measure, observe peak, judge to have generated graphite granule from graphite-structure.The spacing of lattice of calculating from the diffracted ray suitable with 002 interval of graphite is 3.42_.Described particulate average primary particle diameter is 70nm, and DBP absorbed dose (x) is 28ml/100g, and the DBP absorbed dose (y) of compression sample is 28ml/100g.
[synthesis example 3]
Graphite granule C's (carbon granules c) is synthetic
Mixed carbon black " ニ テ ロ Application # 10 modification " and boron powder, the mol ratio that makes carbon and boron is 10: 4, and the silicon-dioxide system of packing into crucible puts graphite film above the crucible, and its two termination is with electrode.Counter electrode energising makes the graphite film heating, and said mixture is caught fire, and utilizes self combustion synthesis method of reaction heat when generating carbide, obtains graphite granule C (carbon granules c).The particle that obtains is carried out X-ray diffraction measure, observe peak, judge to have generated graphite granule from graphite-structure.The spacing of lattice of calculating from the diffracted ray suitable with 002 interval of graphite is 3.38_.Affirmation is from the peak value of 2 θ=37.8 of 021 diffracted ray of B4C °.X-ray diffraction is illustrated in Fig. 2.Described particulate average primary particle diameter is 40nm, and DBP absorbed dose (x) is 120ml/100g, and the DBP absorbed dose (y) of compression sample is 86ml/100g.
[synthesis example 4]
Graphite granule D's is synthetic
Except mixed carbon black " HTC#20 " and ti powder, the mol ratio that makes carbon and titanium elements is outside 10: 1, and other obtain graphite granule D as synthesis example 3.The particle that obtains is carried out X-ray diffraction measure, observe peak, judge to have generated graphite granule from graphite-structure.The spacing of lattice of calculating from the diffracted ray suitable with 002 interval of graphite is 3.44_.Affirmation is from the peak value of 2 θ=41.5 of 200 diffracted rays of TiC °.Described particulate average primary particle diameter is 71nm.
[synthesis example 5]
Graphite granule E's (carbon granules f) is synthetic
Except mixed carbon black " HTC#20 " and aluminium powder form, titania powder, the mol ratio that makes carbon and aluminium element, titanium elements is outside 10: 4: 3, and other obtain graphite granule E (carbon granules f) as synthesis example 3.The particle that obtains is carried out X-ray diffraction measure, observe peak, judge to have generated graphite granule from graphite-structure.The spacing of lattice of calculating from the diffracted ray suitable with 002 interval of graphite is 3.42_.Affirmation is from Al
2O
3113 diffracted rays 2 θ=43.4 ° peak value and from the peak value of 2 θ=41.5 of 200 diffracted rays of TiC °.Described particulate average primary particle diameter is 70nm.DBP absorbed dose (x) is 30ml/100g, and the DBP absorbed dose (y) of compression sample is 29ml/100g,
[synthesis example 6]
Graphite granule F's is synthetic
Except mixed carbon black " HTC#20 " and trimethoxy borine, the mol ratio that makes carbon and boron is outside 10: 1, and other obtain graphite granule F as synthesis example 3.The particle that obtains is carried out X-ray diffraction measure, observe peak, judge to have generated graphite granule from graphite-structure.The spacing of lattice of calculating from the diffracted ray suitable with 002 interval of graphite is 3.41_.Affirmation is from B
4The peak value of 2 θ=37.8 of 021 diffracted ray of C °.Described particulate average primary particle diameter is 72nm.
[synthesis example 7]
Graphite granule G's is synthetic
Resulting graphite granule C among the embodiment 3 is put into the pipe of stainless steel, the hot gas that imports that propane and oxygen mixed in 1: 8 by volume, obtains after the burning.Hot gas temperature is 1000 ℃, and the residence time was 5 seconds.Thereafter, spray water is cooled to 250 ℃, captures the graphite granule G that is generated by bag filter then.The spacing of lattice of calculating from the diffracted ray at 002 interval being equivalent to graphite is 3.40_.Affirmation is from B
2O
3The peak value of 2 θ=32.1 ° of 102 diffracted rays.Described particulate average primary particle diameter is 42nm.
More than, with regard to the resulting graphite granule A-G of synthesis example 1-7, gather its raw material, generate compound and average primary particle diameter, be shown in table 1-1.
Table 1-1
| Synthesis example 1 | Synthesis example 2 | Synthesis example 3 | Synthesis example 4 | Synthesis example 5 | Synthesis example 6 | Synthesis example 7 | ||
| Starting raw material * 1) | FET (ニ テ ロ | 10 | 10 | 10 | ||||
| FT(HTC#20) | 10 | 10 | 10 | 10 | ||||
| Boron powder | 4 | 4 | ||||||
| | 1 | |||||||
| Aluminium powder form | 4 | |||||||
| Titanium dioxide | 3 | |||||||
| The | 1 | |||||||
| Generate graphite granule | A | B | C | D | E | F | G | |
| Generate mineral | C | C | C B 4C | C TiC | C Al 2O 3 TiC | C B4 C | C B 2O 3 | |
| Average primary particle diameter (nm) | 38 | 70 | 40 | 71 | 70 | 72 | 42 | |
* 1) numeral is the mol ratio of raw material element cooperation.
[embodiment 1-1]
Mixing the purity of regulating granularity is 98% electroforming magnesium oxide 100 weight parts, graphite granule A2 weight part, phenolic resin (the line style phenolic resin being added the resin of solidifying agent) 3 weight parts that synthesis example 1 obtains, after mixing with kncading machine, be shaped by friction press, then, 250 ℃ of roastings 8 hours.The apparent porosity of its result after with 400 ℃ of heat treated is 9.2%, bulk specific gravity 3.10.Again, be 10.8GPa with the dynamic elasticity rate after 1000 ℃ of heat treated, be 12.4Gpa with the dynamic elasticity rate after 1400 ℃ of heat treated.Practical decarburized depth is 7.8mm, and corrosion is of a size of 11.0mm.
[embodiment 1-2～1-11, comparative example 1-1～1-7]
Except cooperating raw material as changing as described in table 1-2 and the 1-3, other make refractory materials as embodiment 1-1, estimate.It the results are shown in table 1-2 and table 1-3.
Table 1-2
| Embodiment 1-1 | Embodiment 1-2 | Embodiment 1-3 | Embodiment 1-4 | Embodiment 1-5 | Embodiment 1-6 | Embodiment 1- | Embodiment 1-8 | ||
| Cooperate raw material * 1) | Magnesium oxide | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| | 2 | ||||||||
| | 2 | ||||||||
| | 2 | 1 | |||||||
| | 2 | 7 | 12 | 2 | |||||
| FET (ニ テ ロ | 1 | ||||||||
| FT(HTC#20) | 1 | ||||||||
| Flaky graphite | |||||||||
| Phenolic resin | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | |
| Apparent porosity (%) after 1400 ℃ of thermal treatments | 9.2 | 8.8 | 8.8 | 8.9 | 9.3 | 9.6 | 8.8 | 9.0 | |
| Bulk specific gravity after 1400 ℃ of thermal treatments | 3.10 | 3.13 | 3.12 | 3.12 | 3.07 | 3.01 | 3.11 | 3.10 | |
| Dynamic elasticity rate (GPa) after 1000 ℃ of thermal treatments | 10.8 | 17.1 | 12.0 | 17.8 | 6.7 | 5.1 | 16.4 | 10.1 | |
| Dynamic elasticity rate (GPa) after 1400 ℃ of thermal treatments | 12.4 | 19.9 | 14.6 | 19.0 | 7.3 | 5.4 | 18.0 | 11.2 | |
| Practical decarburized depth (mm) | 7.8 | 6.1 | 5.2 | 4.9 | 7.1 | 8.2 | 5.7 | 5.4 | |
| Corrosion size (mm) | 11.0 | 10.4 | 9.5 | 8.8 | 12.7 | 13.5 | 10.0 | 9.3 | |
* 1) proportioning is a weight ratio.
Table 1-3
| Embodiment 1-9 | Embodiment 1-10 | Embodiment 1-11 | Comparative example 1-1 | Comparative example 1-2 | Comparative example 1-3 | Comparative example 1-4 | Comparative example 1-5 | Comparative example 1-6 | Comparative example 1-7 | ||
| Cooperate raw material * 1) | Magnesium oxide | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| | 2 | ||||||||||
| | 2 | ||||||||||
| | 2 | ||||||||||
| FET (ニ テ ロ | 2 | ||||||||||
| FT(HTC#20) | 2 | 7 | |||||||||
| Flaky graphite | 5 | 20 | |||||||||
| Expanded graphite | 5 | ||||||||||
| Phenolic resin | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | |
| Apparent porosity (%) after 1400 ℃ of thermal treatments | 8.7 | 8.9 | 9.1 | 10.1 | 8.7 | 12.6 | 9.2 | 10.2 | 12.4 | 9.2 | |
| Bulk specific gravity after 1000 ℃ of thermal treatments | 3.12 | 3.11 | 3.11 | 3.06 | 3.12 | 2.96 | 3.06 | 2.98 | 2.99 | 3.18 | |
| Dynamic elasticity rate (GPa) after 1400 ℃ of thermal treatments | 18.0 | 17.4 | 20.1 | 7.8 | 17.4 | 4.0 | 28.6 | 16.5 | 22.6 | 30.4 | |
| Dynamic elasticity rate (GPa) after 1400 ℃ of thermal treatments | 18.7 | 19.5 | 21.3 | 9.1 | 19.2 | 3.7 | 27.1 | 15.8 | 20.9 | 34.7 | |
| Practical decarburized depth (mm) | 4.7 | 4.5 | 4.2 | 9.7 | 8.0 | 13.7 | 10.9 | 11.9 | 11.2 | 11.8 | |
| Corrosion size (mm) | 9.3 | 8.9 | 8.4 | 13.2 | 11.1 | 24.0 | 17.8 | 21.1 | 19.0 | 18.4 | |
* 1) proportioning is a weight ratio.
Compare with cooperate the flaky graphite of 5 weight parts and the occasion of expanded graphite in the use shown in comparative example 1-4 and the 1-6 in the occasion of using the graphitized carbon black shown in embodiment 1-1 and the 1-2, can obtain its dynamic elasticity rate little, obtain excellent resistance to sudden heating with still less cooperation carbon amount, and littler practical decarburized depth and corrosion size and excellent oxidation-resistance energy, erosion resistance have been shown.The resistance to sudden heating of the same degree of the flaky graphite of cooperation 20 weight parts shown in the comparative example 1-5 only adds 2 weight parts here and gets final product.
Again, the not graphited carbon black use occasion shown in these embodiment and comparative example 1-1 and the 1-2 has relatively also shown littler practical decarburized depth and corrosion size and excellent oxidation-resistance energy, erosion resistance.
Thus, use as the superiority of the very tiny particle of nano level is that the superiority of greying particle has just been known.
In addition, shown in embodiment 1-3,1-4,1-9 and 1-10, use the occasion of the graphite granule that contains boron, titanium or aluminium, relatively use the embodiment 1-1 and the 1-2 of the graphite granule that does not contain these elements, recognize and have littler practical decarburized depth and corrosion size and further improved oxidation resistent susceptibility, erosion resistance.
Have again, use and shown in embodiment 1-11, to contain boron, and carry out the occasion of the graphite granule after the oxide treatment, compare, improved oxidation resistent susceptibility, erosion resistance with the embodiment 1-3 of occasion of graphite granule before using oxide treatment.
Secondly, carbon granules b, the c, e and the f that obtain respectively about synthesis example 1,3,2 and 5, and the carbon granules a and the d of the raw material carbon black that uses in these synthesis examples, this raw material, treatment process, DBP absorbed dose (x), compression sample DBP absorbed dose (y).Ratio (x/y) and average primary particle diameter gather to be shown in shows 2-1.
Table 2-1
| Carbon granules (A) | Carbon granules (B) | ||||||
| Carbon granules a | Carbon granules b | Carbon granules c | Carbon granules d | Carbon granules e | Carbon granules f | ||
| Starting raw material * 1) | FET (ニ テ ロ | 10 | 10 | 10 | |||
| FT(HTC#20) | 10 | 10 | 10 | ||||
| Boron powder | 4 | ||||||
| Aluminium powder form | 4 | ||||||
| Titanium dioxide | 3 | ||||||
| The carbon black treatment process | Non-processor | Synthesis example 1 | Synthesis example 2 | Non-processor | Synthesis example 3 | Synthesis example 4 | |
| DBP absorbed dose (x) (ml/100g) | 126 | 118 | 120 | 29 | 28 | 30 | |
| Compression sample DBP absorbed dose (y) (ml/100g) | 89 | 85 | 86 | 30 | 28 | 29 | |
| Ratio (x/y) | 1.42 | 1.39 | 1.4 | 0.97 | 1 | 1.03 | |
| Average primary particle diameter (nm) | 41 | 38 | 40 | 82 | 70 | 70 | |
* 1) numeral is the cooperation mol ratio of raw material element.
[embodiment 2-1]
Mixing as fireproof refractory, the purity of regulating granularity be 98% electroforming magnesium oxide 100 weight parts, (carbon granules is 0.5 weight part a) as the carbon black " ニ テ ロ Application # 10 modification " of carbon granules (A), carbon black " HTC#20 " (carbon granules d) 1.5 weight parts, phenolic resin (the line style phenolic resin that contains solvent being added the resin of solidifying agent) 3 weight parts as carbon granules (B), after mixing with kncading machine, be shaped by friction press, then, 250 ℃ of roastings 8 hours, obtain refractory materials.Apparent porosity after the evaluation result, 1400 ℃ of heat treated is 8.8%, and bulk specific gravity is 3.10.Again, be 11.3GPa with the dynamic elasticity rate after 1000 ℃ of heat treated, be 12.7GPa with the dynamic elasticity rate after 1400 ℃ of heat treated.Practical decarburized depth is 7.7mm, and corrosion is of a size of 10.8mm.
[embodiment 2-2～2-10, comparative example 2-1～2-5]
Except cooperating the change of raw material as table 2-2 and table 2-3 record, other make refractory materials as embodiment 2-1, estimate.It the results are shown in table 2-2 and table 2-3.
[embodiment 2-11]
Raw material is only used the material identical with embodiment 2-2 with identical amount, only change its blending means, test.At first.With carbon black " ニ テ ロ Application # 10 modification " (carbon granules a) 0.2 weight part with as employed identical phenolic resin 3 weight parts of embodiment 2-1, the omnipotent mixing and blending machine that drops into the ダ of Co., Ltd. Le ト Application system mixes.Mixture that obtains and carbon black " HTC#20 " (carbon granules d) 1.8 weight parts and the electroforming magnesium oxide 100 weight parts mixing of using as embodiment 2-1.After mixing with kncading machine, be shaped, then,, obtain refractory materials 250 ℃ of roastings 8 hours by friction press.Evaluation result to the refractory materials that obtained is shown in table 2-2 and table 2-3.
Table 2-2
| Embodiment 2-1 | Embodiment 2-2 | Embodiment 2-3 | Embodiment 2-4 | Embodiment 2-5 | Embodiment 2-6 | Embodiment 2-7 | Embodiment 2-8 | ||
| Cooperate raw material (weight ratio) | Magnesium oxide | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Carbon granules a | 0.5 | 0.2 | 1 | 1.8 | |||||
| Carbon granules b | 0.5 | 0.5 | |||||||
| Carbon granules c | 0.5 | 0.5 | |||||||
| Carbon granules d | 1.5 | 1.8 | 1 | 0.2 | 1.5 | 1.5 | |||
| Carbon granules e | 1.5 | 1.5 | |||||||
| Phenolic resin | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | |
| Apparent porosity (%) after 1400 ℃ of thermal treatments | 8.8 | 8.7 | 9.5 | 10.4 | 8.7 | 8.4 | 8.7 | 8.6 |
| Bulk specific gravity after 1400 ℃ of thermal treatments | 3.10 | 3.11 | 3.06 | 3.05 | 3.10 | 3.11 | 3.11 | 3.12 |
| Dynamic elasticity rate (GPa) after 1000 ℃ of thermal treatments | 11.3 | 13.6 | 10.1 | 8.0 | 11.5 | 11.8 | 11.6 | 11.7 |
| Dynamic elasticity rate (Gpa) after 1400 ℃ of thermal treatments | 12.7 | 15.7 | 10.5 | 8.9 | 12.9 | 13.0 | 13.2 | 13.5 |
| Practical decarburized depth (mm) | 7.7 | 7.9 | 7.9 | 8.5 | 7.4 | 6.5 | 6.9 | 5.5 |
| Corrosion size (mm) | 10.8 | 10.8 | 10.9 | 12.1 | 10.4 | 9.2 | 10.2 | 8.3 |
Table 2-3
| Embodiment 2-9 | Embodiment 2-10 | Embodiment 2-11 | Comparative example 2-1 | Comparative example 2-2 | Comparative example 2-3 | Comparative example 2-4 | Comparative example 2-5 | ||
| Cooperate raw material (weight ratio) | Magnesium oxide | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Carbon granules a | 4 | 0.2 | 2 | ||||||
| Carbon granules c | 0.5 | ||||||||
| Carbon granules d | 8 | 1.8 | 2 | ||||||
| Carbon granules f | 1.5 | ||||||||
| Flaky graphite | 5 | ||||||||
| Expanded graphite | 5 | ||||||||
| Phenolic resin | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | |
| Apparent porosity (%) after 1400 ℃ of thermal treatments | 8.5 | 12.8 | 8.5 | 10.1 | 8.7 | 9.2 | 9.2 | 12.4 | |
| Bulk specific gravity after 1400 ℃ of thermal treatments | 3.13 | 2.97 | 3.11 | 3.06 | 3.12 | 3.18 | 3.06 | 2.99 | |
| Dynamic elasticity rate (GPa) after 1000 ℃ of thermal treatments | 11.9 | 2.2 | 13.2 | 7.8 | 17.4 | 30.4 | 28.6 | 22.6 | |
| Dynamic elasticity rate (GPa) after 1400 ℃ of thermal treatments | 13.8 | 2.3 | 15.1 | 9.1 | 19.2 | 34.7 | 27.1 | 20.9 |
| Practical decarburized depth (mm) | 4.6 | 13.9 | 7.6 | 9.7 | 8.0 | 11.8 | 10.9 | 11.2 |
| Corrosion size (mm) | 7.4 | 20.2 | 10.5 | 13.2 | 11.1 | 18.4 | 17.8 | 19.0 |
Embodiment 2-1～2-4 has used, has cooperated the DBP absorbed dose to be the carbon black more than the 80ml/100g [carbon granules (A)] and the DBP absorbed dose carbon black [carbon granules (B)] less than 80ml/100g.Its result has shown low dynamic elasticity rate, obtains good resistance to sudden heating.Again, practical decarburized depth is also little, and when showing good oxidation resistent susceptibility, the corrosion size is also little, shows good dissolubility resistent energy.To this, in the comparative example 2-1 that only uses the DBP absorbed dose as the carbon black more than the 80ml/100g [carbon granules (A)], practical decarburized depth is big, and oxidation resistent susceptibility is low. and its corrosion size is also big, and dissolubility resistent can be low.In the comparative example 2-2 of the carbon black that only uses the DBP absorbed dose less than 80ml/100g [carbon granules (B)], the dynamic elasticity rate is big, poor thermal shock resistance again.
In the comparative example 2-2 that only uses carbon granules (B), along with relatively (A) and total amount (B) add up to the variation of the amount of being used of the carbon granules (A) of 10/100 (embodiment 2-2), 25/100 (embodiment 2-1) or 50/100 (embodiment 2-3), the dynamic elasticity rate is reduction greatly thereupon also.For example, in embodiment 2-2, only be used carbon granules (A) and total amount (B) are added up to a spot of carbon granules (A) of 10/100, its dynamic elasticity rate is reduced to 13.6GPa from 17.4GPa after 1000 ℃ of thermal treatment; After 1400 ℃ of thermal treatment, be reduced to 15.7GPa from 19.2GPa, have greatly improved.At this moment, it is shocking that in embodiment 2-1～2-3, not only practical decarburized depth, corrosion size use the comparative example 2-2 of carbon granules (B) little all more separately, thermal shock resistance improves significantly, and has excellent oxidation-resistance energy and dissolubility resistent.
On the other hand, for the comparative example 2-1 that only uses carbon granules (A), (A) and total amount (B) are used the embodiment 2-4 of the carbon granules (B) of 10/100 usage quantity, compare comparative example 2-1, its dynamic elasticity rate is greatly improved, and simultaneously, its oxidation resistent susceptibility and dissolubility resistent are as comparative example 2-1.That is,, cooperate a spot of carbon granules (A) promptly can obtain having the refractory materials of resistance to sudden heating, scale resistance and the dissolubility resistent energy of excellence compared with the occasion of only using carbon granules (B).
In mismatching the comparative example 2-3 that uses carbon granules, the thermal shock resistance significance difference, oxidation resistent susceptibility and corrosion resistance nature are bad simultaneously.Again, in the occasion of using flaky graphite (comparative example 2-4) or expanded graphite (comparative example 2-5) as carbon feedstock, even cooperate 5 weight parts more than 2 weight parts that add the carbon black usage quantity among embodiment 2-1～2-4, its thermal shock resistance still is worse than embodiment 2-1～2-4.At this moment, oxidation resistent susceptibility and dissolubility resistent can also be inferior to embodiment 2-1～2-4.
The graphite granule that carbon black after using greying obtains is as the occasion (embodiment 2-5) of carbon granules (A).Compared with using carbon granules (A) and (B), use carbon black occasion (embodiment 2-1) simultaneously, oxidation resistent susceptibility and corrosion resistance nature improve.Have again, as carbon granules (A), be the graphite granule that the carbon black greying is formed, when this graphite granule uses the graphite granule that contains at least a above element that is selected from metal, boron, silicon (embodiment 2-7), oxidation resistent susceptibility and corrosion resistance nature are further improved.
And carbon granules (A) and (B) use the occasion (embodiment 2-6) of the graphite granule that graphitized carbon black forms simultaneously, further improve oxidation resistent susceptibility and corrosion resistance nature than embodiment 2-5.And described carbon granules (A) is for to make the graphite granule that forms after the carbon black greying, this graphite granule contain the graphite (embodiment 2-8) of at least a above element that is selected from metal, boron, silicon.Thus, further improve oxidation resistent susceptibility and corrosion resistance nature.Described carbon granules (A), (B), graphite granule also is to make the graphite granule that forms after the carbon black greying, this graphite granule contains the graphite (embodiment 2-9) of at least a above element that is selected from metal, boron, silicon, thus, obtains best oxidation resistent susceptibility and corrosion resistance nature.
Again, embodiment 2-11 carries out raw materials mixed with the raw material as embodiment 2-2 with identical cooperation ratio, is that carbon granules (A) is scattered in the organic binder bond in advance, then, mixes with other raw materials and obtains raw material.Thus, can improve the dispersiveness of carbon granules (A) in matrix, as a result of, each of thermal shock resistance, oxidation resistent susceptibility and corrosion resistance nature all than the embodiment 2-2 that all cooperates simultaneously, can improve.
Utilizability on the industry
As mentioned above, according to the present invention, can provide a kind of refractory material with excellent thermal shock resistance, oxidation resistent susceptibility and decay resistance, especially can provide phosphorus content few carbon containing refractory. The carbon containing refractory that described phosphorus content is few is separated out few to the carbon in the ingot steel, it is also few to disperse heat from container, is useful refractory material. According to the present invention, can also provide a kind of raw material for refractory be used to making described refractory material again.
Claims (11)
1. raw material for refractory composition, it is characterized in that, described raw material for refractory composition is made up of carbon granules (A), carbon granules (B) and fireproof refractory, described carbon granules (A) is for being selected from carbon black and carbon black being carried out the graphite granule that greying forms, and its DBP absorbed dose (x) is more than 80ml/100g; The graphite granule of described carbon granules (B) for being selected from carbon black and the carbon black greying being formed, its DBP absorbed dose (x) is less than 80ml/100g.
2. raw material for refractory composition as claimed in claim 1, it is characterized in that, for the fireproof refractory of 100 weight parts, the total weight of carbon granules (A) and carbon granules (B) is the 0.1-10 weight part, and the weight ratio (A/B) of carbon granules (A) and carbon granules (B) is 1/99-99/1.
3. raw material for refractory composition as claimed in claim 1 or 2 is characterized in that, the average primary particle diameter of carbon granules (A) is 10-50nm, and the average primary particle diameter of carbon granules (B) is 50-500nm.
4. raw material for refractory composition as claimed in claim 1 or 2 is characterized in that, the ratio (x/y) of the DBP absorbed dose (y) of the DBP absorbed dose (x) of carbon granules (A) and the compression sample of carbon granules (A) is more than 1.15.
5. raw material for refractory composition as claimed in claim 1 or 2 is characterized in that, at least one side of carbon granules (A) and carbon granules (B) is the graphite granule that the carbon black greying is formed.
6. raw material for refractory composition as claimed in claim 1 or 2 is characterized in that, two sides in carbon granules (A) and the carbon granules (B) are all the graphite granule that the carbon black greying is formed.
7. raw material for refractory composition as claimed in claim 1 or 2, it is characterized in that, at least one side of carbon granules (A) and carbon granules (B) is the graphite granule that the carbon black greying is formed, and this graphite granule contains at least a above element that is selected from metal, boron, silicon.
8. raw material for refractory composition as claimed in claim 1 or 2, it is characterized in that, two sides in carbon granules (A) and the carbon granules (B) are all the graphite granule that the carbon black greying is formed, and this graphite granule contains at least a above element that is selected from metal, boron, silicon.
9. raw material for refractory composition as claimed in claim 1 or 2 is characterized in that, fireproof refractory is to be made up of magnesium oxide.
10. raw material for refractory composition as claimed in claim 1 or 2 is characterized in that, carbon granules (A) is scattered in the organic binder bond in advance, then, mixes with other raw materials.
The refractory materials that forms 11. claim 1 or 2 described raw material for refractory compositions are shaped.
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| JP200165369 | 2001-03-08 | ||
| JP2001065369A JP4227734B2 (en) | 2001-03-08 | 2001-03-08 | Refractory raw material, refractory raw material composition, refractory, and method for producing graphite particles usable for them |
| JP2001118216 | 2001-04-17 |
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| CNB028011317A Division CN1262516C (en) | 2001-03-08 | 2002-03-06 | Refractory materials, method for production thereof and refraratory using the material |
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| JP3691836B1 (en) | 2004-08-27 | 2005-09-07 | 東洋炭素株式会社 | Expanded graphite sheet |
| BRPI0608165B8 (en) * | 2005-04-19 | 2021-04-20 | Krosaki Harima Corp | refractory and its production method, materials of the refractory |
| KR100701198B1 (en) * | 2005-12-20 | 2007-03-29 | 주식회사 포스코 | Composition of carbonaceous refractory with fine flake graphite powder |
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