WO2011108700A2 - 耐火成形体、耐火成形体の製造方法および金属鋳造用部材 - Google Patents
耐火成形体、耐火成形体の製造方法および金属鋳造用部材 Download PDFInfo
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- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Definitions
- the present invention relates to a fireproof molded body, a method for manufacturing a fireproof molded body, and a member for metal casting.
- a ladle When casting molten aluminum or magnesium using die casting technology, a ladle is used as a container for transporting a predetermined amount of molten metal from the holding furnace to the casting machine and pouring it into the mold of the casting machine.
- a ladle In a casting apparatus for mass production, a ladle is automatically controlled by being mounted on a robot arm or the like, and programmed to scoop up a predetermined amount of molten metal from a holding furnace and carry it to a casting machine for injection. Further, in a casting apparatus intended for small-volume production, the ladle is manually controlled while being fixed to a manual lift handle or the like.
- Patent Document 1 Japanese Patent Laid-Open No. 2005-118878
- a slurry-like ceramic material is sequentially pasted onto a molded body.
- a ceramic ladle reinforced with an E-glass cloth has been proposed.
- Patent Document 2 Japanese Patent Laid-Open No. 2009-234812. No.
- Patent Document 1 Although a ceramic ladle reinforced with an E-glass cloth having low thermal conductivity and impact resistance is obtained, one cloth wetted with a slurry ceramic material is obtained. Since the ladle is produced by sticking to the mold by hand, there is a technical problem that the manufacturing efficiency is low and it is difficult to improve the productivity. In addition to the ladle, metal casting members that come into contact with molten metal such as firewood, molten metal holding furnace, ladle, float, spout, hot top ring header, etc. have low thermal conductivity and excellent thermal shock resistance.
- molten metal such as firewood, molten metal holding furnace, ladle, float, spout, hot top ring header, etc.
- the present invention provides a novel fire-resistant molded article having low thermal conductivity, high durability against physical shock and thermal shock, and high homogeneity, and is capable of reducing the productivity of the fire-resistant molded article. It is an object of the present invention to provide a simple and easy manufacturing method and a metal casting member.
- the inorganic short fibers are usually in a state of an inorganic short fiber aggregate in which a plurality of short fibers are bound or twisted with a sizing agent.
- the fiber aggregate is defibrated and dispersed into individual inorganic short fibers at the time of kneading, so that the fluidity of the kneaded product is remarkably reduced, and voids such as soot and voids are formed in the molded product, causing defective molding. It was found that only a very small amount of inorganic short fibers could be added. Since the thickness of the thinnest portion of the ladle is about 1 cm, when the gap is generated, the homogeneity is lowered and sufficient toughness cannot be imparted.
- the present inventors have further studied, and comprise inorganic particles and bundle-like inorganic fiber aggregates, in which the bundle-like inorganic fiber aggregates are dispersed between the inorganic particles.
- the present inventors have found that the above technical problem can be solved by a fireproof molded body having a structure, and have completed the present invention based on this finding.
- the present invention (1) A fireproof molded article comprising an inorganic particle and a bundle-like inorganic fiber aggregate, and having an internal structure in which the bundle-like inorganic fiber aggregate is dispersed between the inorganic particles; (2) It has a binder, inorganic particles, and bundled inorganic fiber aggregates, and has an internal structure in which the bundled inorganic fiber aggregates are dispersed between the inorganic particles bound by the binder.
- fireproof molded body 1 The fireproof molded body according to the above (1) (hereinafter appropriately referred to as fireproof molded body 1), (3) The refractory molded article according to (2), comprising 1 to 50% by mass of the binder, 30 to 95% by mass of the inorganic particles, and 1 to 30% by mass of the bundle-like inorganic fiber aggregates, (4) The fireproof molded article according to (2) or (3), wherein the bundle-like inorganic fiber aggregate has a diameter of 0.01 to 5 mm and a length of 3 to 30 mm. (5) It contains calcium silicate particles as the inorganic particles and a bundle of inorganic fiber aggregates, and has an internal structure in which the bundle of inorganic fiber aggregates is dispersed between the calcium silicate particles.
- the fireproof molded body according to the above (1) (hereinafter appropriately referred to as fireproof molded body 2), (6)
- the refractory molded article according to (5) comprising 65 to 99% by mass of the inorganic particles and 1 to 30 parts by mass of the bundle-like inorganic fiber aggregate, (7)
- Method 1 for producing a fire-resistant molded article A method for producing a fire-resistant molded article (hereinafter referred to as “Method 1 for producing a fire-resistant molded article”), (10) A kneaded product obtained by kneading a fire-resistant molded body-forming material containing a binder, inorganic particles, and a bundle-like inorganic fiber aggregate formed by coating a resin with a glass transition temperature of 40 ° C. or less on the surface.
- the material for forming a refractory molded body has a solid content of 1 to 50% by mass of the binder, 30 to 95% by mass of the inorganic particles, and a resin having a glass transition temperature of 40 ° C. or less on the surface.
- the method for producing a fireproof molded article according to the above (10), comprising 1 to 30% by mass of a bundle-like inorganic fiber aggregate comprising: (12) The method for producing a refractory molded body according to (10) or (11) above, wherein a tap flow value of the kneaded product when measured according to JIS R 5201 is 150 mm or more, (13) A slurry for forming a refractory molded body containing a bundle of inorganic fiber aggregates containing a raw material of calcium silicate particles and having a surface coated with a resin having a glass transition temperature of 40 ° C.
- Refractory Molded Process 2 A method for producing a refractory molded article, which is subjected to a hydrothermal treatment and then a drying treatment (hereinafter referred to as Refractory Molded Process 2 as appropriate), (14) The method for producing a refractory molded body according to (13), wherein the raw material of the calcium silicate particles is a lime raw material powder and a silicate raw material powder, (15) The method for producing a refractory molded body according to (14), wherein the hydrothermal treatment is performed under a water vapor pressure of 7 kg / cm 2 or more, (16) The bundle of inorganic fibers formed by coating the surface with a resin having a glass transition temperature of 40 ° C.
- a bundle-like inorganic fiber aggregate formed by coating the surface with a resin having a glass transition temperature of 40 ° C. or less is a resin having a glass transition temperature of 40 ° C. or less with respect to 100 parts by mass of the bundle-like inorganic fiber aggregate.
- the fire-resistant molded body such as the fire-resistant molded body 1 or the fire-resistant molded body 2 according to the present invention is composed of an inorganic material such as inorganic particles so that the thermal conductivity is reduced and the homogeneity is high.
- an inorganic material such as inorganic particles so that the thermal conductivity is reduced and the homogeneity is high.
- the manufacturing method 1 of the fireproof molded object of this invention when manufacturing a fireproof molded object, as an inorganic fiber material, the bundle-shaped inorganic fiber aggregate
- calcium silicate is used as a raw material for inorganic particles in the coexistence of a bundle-like inorganic fiber aggregate whose surface is coated with a resin having a glass transition temperature of 40 ° C. or less.
- a slurry for forming a refractory molded body containing the raw material of particles can be dehydrated and then hydrothermally treated to synthesize inorganic particles in a state where bundled inorganic fiber aggregates are dispersed and simultaneously form a refractory molded body.
- the fireproof molded article of the present invention comprises inorganic particles and bundle-like inorganic fiber aggregates, and has an internal structure in which the bundle-like inorganic fiber aggregates are dispersed between the inorganic particles. To do.
- the fireproof molded body of the present invention include fireproof molded body 1 and fireproof molded body 2.
- the refractory molded body 1 includes a binder, inorganic particles, and bundle-like inorganic fiber aggregates, and the bundle-like inorganic fiber aggregates are dispersed between the inorganic particles bonded by the binder.
- the refractory molded body 2 has a structure and includes calcium silicate particles as inorganic particles and a bundle of inorganic fiber aggregates, and the bundle of inorganic fiber aggregates between the calcium silicate particles. It has an internal structure in which the body is dispersed.
- the refractory molded body 1 and the refractory molded body 2 are different in that the refractory molded body 1 must contain a binder and the refractory molded body 2 must contain calcium silicate particles as inorganic particles.
- the following description will be made by appropriately comparing the two.
- the inorganic particles are refractory particles that function as a matrix component of the refractory molded article (the main component constituting the skeleton of the refractory molded article), and any refractory inorganic particles can be used.
- the refractory molded body of the present invention is the refractory molded body 1
- examples of the inorganic particles include silica particles, alumina particles, mullite particles, silicon carbide particles, silicon nitride particles, silicon aluminum oxynitride particles, zircon particles, magnesia.
- the fireproof molded body of the present invention is the fireproof molded body 2
- the inorganic particles include calcium silicate particles, and specific examples of the calcium silicate particles include zonotolite particles, tobermorite particles, and wollastonite particles. it can.
- the average particle diameter of the inorganic particles is preferably 0.1 to 6000 ⁇ m, more preferably 0.1 to 5000 ⁇ m, and further preferably 0.1 to 4500 ⁇ m.
- the average particle diameter of the inorganic particles is less than 0.1 ⁇ m, the surface area increases, and it tends to stick to the dispersion medium during the production of the refractory molded body, and the fluidity tends to decrease. It becomes difficult to be demonstrated.
- the average particle diameter means a value measured by a laser diffraction / scattering method, and can be measured using, for example, “SALD-2200” manufactured by Shimadzu Corporation.
- the refractory molded article of the present invention preferably contains 30 to 99% by mass of inorganic particles.
- the refractory molded article of the present invention is the refractory molded article 1
- it preferably contains 30 to 95% by mass of inorganic particles, more preferably contains 40 to 90% by mass, and contains 45 to 80% by mass. Is more preferred.
- the fireproof molded body of the present invention is the fireproof molded body 2
- it preferably contains 65 to 99% by mass of inorganic particles, more preferably contains 75 to 96% by mass, and 80 to 95% by mass. More preferably it comprises.
- the content of the inorganic particles can be calculated from the amount of raw material used at the time of manufacturing the refractory molded body.
- the inorganic fibers constituting the bundle-like inorganic fiber aggregate are not particularly limited as long as they have a predetermined heat resistance (fire resistance) according to the use of the fire-resistant molded article,
- a glass fiber, an alumina fiber, a mullite fiber, a silica alumina fiber, a rock wool fiber, etc. can be mentioned.
- the fire-resistant molded article of the present invention is formed by a method involving hydrothermal treatment such as the method 2 for producing a fire-resistant molded article described later. Alkali resistant glass fibers are preferred.
- the bundle-like inorganic fiber aggregate includes a chopped strand obtained by cutting a strand in which a plurality of filaments (also referred to as single fibers or continuous fibers) are bundled to a predetermined length, or a plurality of filaments.
- a strand of several dozen strands also referred to as single fibers or continuous fibers combined, wound into a cylindrical shape and cut into a predetermined length, a yarn obtained by twisting a plurality of strands (spun yarn) ) are cut into a predetermined length, and short fibers such as bulk fibers are collected in parallel in the fiber length direction to form a continuous bundle.
- chopped strands that are easily available, or roving or twisted yarns cut to a predetermined length are preferred, and twisted yarns cut to a predetermined length Is more preferred.
- twisted yarns cut to a predetermined length unevenness due to twisting is likely to occur on the surface, and the anchor effect is easily exhibited in the fireproof molded body, so that the toughness of the fireproof molded body is easily improved.
- the bundle-like inorganic fiber aggregate is preferably an aggregate of 20 to 10,000 inorganic fibers, more preferably an aggregate of 100 to 8000, 200 It is more preferable that 6000 pieces are assembled.
- the bundle-like inorganic fiber aggregate varies depending on the specific gravity of the inorganic fiber, but the fineness is preferably 10 to 5000 tex, more preferably 50 to 4000 tex, and more preferably 100 to More preferably, it is 3000 tex.
- the fineness of 1 tex means that the weight per 1000 m of bundle-like inorganic fiber aggregates is 1 g.
- the bundle-like inorganic fiber aggregate preferably has a diameter of 0.01 to 5 mm, more preferably 0.05 to 4 mm, and more preferably 0.1 to 3 mm. Is more preferable.
- the bundle-like inorganic fiber aggregate is preferably 3 to 200 mm in length.
- the bundle-like inorganic fiber aggregate is preferably 3 to 30 mm in length, and the bundle-like inorganic fiber aggregate is preferably 5 to 25 mm. More preferably, the thickness is 10 to 20 mm.
- the bundle-like inorganic fiber aggregate is preferably 3 to 200 mm in length, preferably 10 to 120 mm, and preferably 20 to 80 mm. More preferably.
- the diameter and length of a bundle-like inorganic fiber aggregate mean the arithmetic mean value when the diameter and length of 100 bundle-form inorganic fiber aggregates are measured.
- the fireproof molded article easily contains a large amount of the inorganic fiber aggregate, and the inorganic fiber aggregate is contained in the fireproof molded article. It becomes difficult to come off, and it becomes easy to impart high toughness to the fireproof molded body.
- the bundle of inorganic fiber aggregates preferably has a density of 0.5 to 4 g / cm 3 , more preferably 1 to 3 g / cm 3 , and more preferably 1.5 to 4 g / cm 3. More preferred is 3 g / cm 3 .
- the fire-resistant molded product of the present invention preferably contains 1 to 30% by mass of a bundle of inorganic fiber aggregates.
- the refractory molded article of the present invention is the refractory molded article 1
- it preferably contains 1 to 30% by mass of bundle-like inorganic fiber aggregates, more preferably contains 5 to 30% by mass. What comprises 30 mass% is further more preferable.
- the refractory molded body of the present invention is the refractory molded body 2
- it preferably contains 1 to 30% by mass of bundle-like inorganic fiber aggregates, more preferably 2 to 20% by mass. What comprises 13 mass% is further more preferable.
- the fireproof molded body of the present invention comprises 1 to 30 masses of bundle-like inorganic fiber aggregates, sufficient toughness can be imparted to the fireproof molded body.
- the content of the bundle-like inorganic fiber aggregate is less than 1% by mass, it becomes difficult to impart sufficient toughness to the fire-resistant molded product, and when it exceeds 30% by mass, the fluidity of the molding material decreases during molding. It becomes difficult to mold.
- the content of the bundle-like inorganic fiber aggregate can be calculated from the amount of raw material used at the time of manufacturing the refractory molded body.
- the refractory molded article of the present invention is the refractory molded article 1
- the refractory molded article 1 further contains a binder as an essential component together with the inorganic particles and bundled inorganic fiber aggregates.
- an inorganic binder is preferable, and examples of the inorganic binder include cement, aluminum phosphate, sodium silicate, colloidal silica, and the like. Among these, cement is preferable.
- the cement is not particularly limited as long as it functions as an inorganic binder, and examples thereof include at least one selected from hydraulic cements such as pordrant cement, white cement, fly ash cement, silica cement, and alumina cement. Can do.
- alumina cement having high heat resistance is suitable.
- the alumina cement means a cement containing CaO.Al 2 O 3 as a main component, and for example, an Al 2 O 3 content ratio of 70% by mass or more is preferable.
- the refractory molded body of the present invention is the refractory molded body 1
- the refractory molded body 1 preferably contains 1 to 50% by mass of a binder, more preferably 5 to 40% by mass. What contains 40 mass% is further more preferable.
- the content of the binder is less than 1% by mass, it becomes difficult to sufficiently bind inorganic particles and the like, and when it exceeds 50% by mass, the content of other components such as inorganic particles is reduced, which is sufficient for a fireproof molded body. It becomes difficult to give a sufficient strength.
- the refractory molded body of the present invention is the refractory molded body 2, it is preferable not to include a binder, but a binder may be included.
- a binder examples include the same ones as described above.
- the refractory molded body 2 can include, for example, less than 1% by mass of a binder.
- the fireproof molded body of the present invention is the fireproof molded body 2
- carbon fiber, pulp, rayon, polyester fiber, alkali resistant glass fiber, or the like may be included as a fiber component.
- the content ratio of the fiber component in the refractory molded body 2 is preferably 5% by mass or less in terms of solid content.
- a fiber component is distinguished from the said bundle-like inorganic fiber aggregate, and shall mean the short fiber added in order to ensure a moldability.
- the fireproof molded body of the present invention has an internal structure in which bundle-like inorganic fiber aggregates are dispersed between inorganic particles, and the internal structure in which bundle-like inorganic fiber aggregates are uniformly dispersed throughout the fireproof molded article It is suitable to have.
- the fireproof molded article of the present invention can exhibit high toughness by having an internal structure in which bundle-like inorganic fiber aggregates are dispersed.
- the fireproof molded article of the present invention preferably has a Charpy impact value of 0.5 to 10 mJ / mm 2 as measured according to JIS R 1662. When the Charpy impact value is within the above range, sufficient toughness can be imparted to the fireproof molded body.
- the fire-resistant molded article of the present invention preferably has a bending strength of 1 to 20 MPa when measured according to JIS A 1408. When the bending strength is within the above range, sufficient strength can be imparted to the fireproof molded body.
- Specific examples of the refractory molded body according to the present invention include a metal casting member.
- the metal casting member include a molten metal holding member for metal casting, a component for forming a metal casting apparatus, and a component for these.
- the molten metal holding member for metal casting include a ladle, a slag, a molten metal holding furnace, a ladle, and the like
- specific examples of the metal casting apparatus component include a float, a spout, and a hot top.
- a ring header etc. can be mentioned.
- the fireproof molded article of the present invention can be suitably produced by the method for producing a fireproof molded article of the present invention.
- the fireproof molded body 1 of the present invention can be suitably produced by the manufacturing method 1 of the fireproof molded body of the present invention described later, and the fireproof molded body 2 of the present invention is fireproof molded of the present invention described later. It can be suitably produced by the production method 2 of the body.
- the refractory molded article of the present invention can also be produced by a method other than the method for producing the refractory molded article of the present invention.
- the glass transition temperature on the surface instead of a bundle-like inorganic fiber aggregate formed by coating a resin of 40 ° C. or lower, a yarn obtained by twisting a plurality of strands with a predetermined strength and having no resin coating on the surface is cut into a predetermined length The method using what was done can also be mentioned.
- the inorganic fiber aggregates are allowed to exist in the fireproof molded body while maintaining the bundle shape without defibrating the inorganic fiber aggregate even when kneading the fireproof molded body forming material. be able to.
- the fire-resistant molded article of the present invention is composed of an inorganic material such as inorganic particles, and has an internal structure in which bundle-like inorganic fiber aggregates are dispersed between inorganic particles, thereby reducing thermal conductivity.
- durability against physical shock and thermal shock can be improved.
- the refractory molded body of the present invention is the refractory molded body 2
- the composition may contain only a small amount of binder or no binder, and in this case, the thermal conductivity can be more effectively reduced. Can do.
- the method for producing a refractory molded body of the present invention comprises a method 1 for producing a refractory molded body and a method 2 for producing a refractory molded body.
- Method 1 for producing a refractory molded body will be described, and then Method 2 for producing a refractory molded body will be described.
- the manufacturing method 1 of the refractory molded body of the present invention comprises kneading a refractory molded body forming material containing inorganic particles and a bundle-like inorganic fiber aggregate formed by coating a resin with a glass transition temperature of 40 ° C. or lower on the surface.
- the obtained kneaded product is molded.
- the production method 1 of the refractory molded article of the present invention can be particularly preferably applied when producing the refractory molded article 1 of the present invention.
- examples of the inorganic particles include the same particles as those mentioned in the description of the refractory molded body 1 of the present invention.
- the refractory molded body forming material preferably contains 30 to 95% by mass of inorganic particles in solid content (when converted to solid content), and preferably 40 to 90% by mass.
- the content is more preferably 45 to 80% by mass.
- the refractory molded body forming material includes a bundle-like inorganic fiber aggregate formed by coating the surface with a resin having a glass transition temperature of 40 ° C. or lower.
- Examples of the bundle-like inorganic fiber aggregate can include the same ones as described above.
- the resin coated on the surface of the bundle-like inorganic fiber aggregate is not particularly limited as long as it has a glass transition temperature of 40 ° C. or less.
- acrylonitrile-butadiene copolymer latex styrene-butadiene copolymer latex And acrylic acid ester copolymer latex.
- cover resin with a glass transition temperature more than 40 degreeC with the resin of glass transition temperature 40 degrees C or less on the bundle-like inorganic fiber aggregate surface.
- the resin having a glass transition temperature exceeding 40 ° C. include polystyrene, polyethylene terephthalate, and polycarbonate.
- the resin having a glass transition temperature of 40 ° C. or lower occupies 50 to 99% by mass of the entire resin to be coated.
- the resin having a glass transition temperature of more than 40 ° C. is preferably 1 to 50% by mass.
- the amount of resin coated on the surface of the bundle-like inorganic fiber aggregate is preferably 1 to 30 parts by mass and more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the bundle-like inorganic fiber aggregate. It is preferably 3 to 15 parts by mass, more preferably 5 to 15 parts by mass.
- the amount of the resin coated on the surface of the bundle-like inorganic fiber aggregate is less than 1 part by mass with respect to 100 parts by mass of the bundle-like inorganic fiber aggregate, it is difficult to hold the inorganic fiber aggregate in a bundle state during the kneading process.
- the amount exceeds 30 parts by mass, voids are generated around the inorganic fiber aggregate after firing, and the inorganic fiber aggregate is easily removed, and the toughness of the resulting fireproof molded article is likely to be lowered.
- the resin coating on the bundle-like inorganic fiber aggregate can be performed, for example, by impregnation or spraying.
- the refractory molded body forming material contains 1 to 30% by mass of a bundle-like inorganic fiber aggregate formed by coating the surface with a resin having a glass transition temperature of 40 ° C. or lower.
- the content is preferably 5 to 30% by mass, more preferably 10 to 30% by mass.
- a fireproof molded object formation material contains the binder mentioned later, it is preferable that the content rate of a bundle-like inorganic fiber polymer exists in the said range.
- the material for forming the fire-resistant molded article contains 1 to 30% by mass of a bundle of inorganic fiber aggregates, thereby imparting sufficient toughness to the resulting fire-resistant molded article. Can do.
- the fireproof molded body forming material preferably contains a binder.
- the binder include the same ones as described above.
- the solid content preferably contains 1 to 50% by mass of the binder, preferably 5 to 40% by mass. More preferably, the content is more preferably 10 to 40% by mass.
- the content of the binder in the solid content is less than 1% by mass, it becomes difficult to bind inorganic particles and the like, and when the content exceeds 50% by mass, the content of other components such as inorganic particles is decreased, resulting in It becomes difficult to give sufficient strength and heat resistance to the fire-resistant molded article.
- the fireproof molded body forming material contains a solvent such as water, a monovalent alcohol such as ethanol or propanol, or a polar organic solvent such as a divalent alcohol such as ethylene glycol.
- a solvent such as water, a monovalent alcohol such as ethanol or propanol, or a polar organic solvent such as a divalent alcohol such as ethylene glycol.
- the refractory molded body forming material contains a solvent, the solid content can be dispersed and easily poured into a mold. The amount of the solvent added can be appropriately set according to the desired bulk density and use of the fire-resistant molded body material.
- the method for producing the fire-resistant molded body forming material is not particularly limited, and is a bundle of inorganic fibers formed by coating inorganic particles or a resin having a glass transition temperature of 40 ° C. or lower on the surface. It can be produced by a method in which a solid content such as an aggregate is added to a solvent, or a method in which the solid content and the solvent are introduced into a kneader and stirred to some extent before kneading.
- the kneading can be performed using a known kneading apparatus such as a universal stirrer or various kneaders, and is preferably performed using a dispersion kneading machine such as an ultrasonic processing apparatus, a cutter mixer, or a three roll.
- a kneader is used as the kneading apparatus, the rotational speed and kneading time of the kneader can be appropriately set according to the desired bulk density and use of the fireproof molded body material.
- a tap flow value measured by JIS R 5201 is preferably 150 mm or more.
- the upper limit of the tap flow value is not particularly limited, but it is appropriate that the tap flow value is usually 300 mm or less.
- the tap flow value of the kneaded product can be controlled to 150 mm or more.
- the product maintains suitable fluidity, and a fire-resistant molded body with high homogeneity can be produced without forming voids such as soot and voids.
- the kneaded material obtained by kneading the fireproof molded object formation material is shape
- the molding is preferably performed by filling a molding die with a refractory molded body forming material.
- the filling of the kneaded material into the mold is preferably performed by pouring while deaeration using, for example, a flexible vibrator.
- molding die a wooden mold, a metal mold
- a synthetic resin mold is preferable from the viewpoint of dimensional accuracy and dimensional stability.
- molding can also be performed by apply
- the kneaded product is filled in a mold and then dried and fired as necessary.
- the kneaded product is left in the mold or coated in the shape of the target product, and after curing (leaving) at room temperature for approximately one day, the mold is removed when molded in the mold. Then, it is preferable to perform the heating treatment at a temperature of about 110 ° C. for about 24 hours. In the above molding, if the ambient temperature (room temperature) is below freezing point, it may not be possible to remove the mold in one day. Therefore, after pouring into the mold, the temperature is about 15 to 30 ° C. It is desirable to cure.
- the baking treatment of the dried product obtained by the drying treatment at a temperature of 300 to 1300 ° C. for about 0.5 to 4 hours. Crystallized water in the dried product can be removed by the firing treatment.
- Examples of the fire-resistant molded article obtained by the manufacturing method 1 of the fire-resistant molded article of the present invention include the same as those described in the description of the fire-resistant molded article of the present invention.
- the manufacturing method 1 of the fireproof molded object of this invention when the fireproof molded object formation material contains a binder, the fireproof molded object 1 of this invention can be produced suitably.
- the manufacturing method 2 of the fire-resistant molded body of the present invention is for forming a fire-resistant molded body including a bundle-like inorganic fiber aggregate formed by covering the surface with a resin having a glass transition temperature of 40 ° C. or less, including a raw material of calcium silicate particles. The slurry is dehydrated and then hydrothermally treated and then dried.
- the manufacturing method 2 of the refractory molded body of the present invention can be preferably applied when producing the refractory molded body 2 of the present invention.
- examples of the calcium silicate particles include the same as those mentioned in the description of the refractory molded body 2 of the present invention.
- examples of the raw material for the calcium silicate particles include lime raw material powder and silicate raw material powder.
- lime raw material powder examples include one or more powders selected from slaked lime, quick lime, carbide soot and the like
- silicate raw material powder examples include one or more powders selected from diatomaceous earth, silica stone, ferrosilicon dust, and the like. Can be mentioned.
- the raw material of the calcium silicate particles comprises a lime raw material powder and a silicate raw material powder
- the lime raw material powder is converted to CaO
- the silicate raw material powder is converted to SiO 2
- the mixing ratio of the lime raw material powder to the silicic acid raw material powder is preferably 0.6 to 1.3, and 0.8 to 1.2 in terms of molar ratio. Is more preferably 0.9 to 1.1.
- the lime raw material powder and the silicate raw material powder are slurried and subjected to a hydrothermal treatment and a drying treatment to produce calcium silicate particles such as zonotolite particles and tobermorite particles in the refractory molded body.
- the refractory molded body forming slurry is in solid content (in terms of solid content). Occasionally) 20 to 99% by mass of lime raw material powder and silicic acid raw material powder are preferably contained, more preferably 25 to 80% by mass, and 35 to 55% by mass. More preferably.
- a fire-resistant molded article obtained while uniformly dispersing a bundle-like inorganic fiber aggregate formed by coating the surface with a resin having a glass transition temperature of 40 ° C. or lower It is easy to impart sufficient strength to the refractory, and it is easy to maintain the shape of the obtained fireproof molded body in a desired shape.
- the refractory molded body forming slurry may contain calcium silicate particles as well as a raw material of calcium silicate particles as a raw material of inorganic particles.
- the calcium silicate particles that can be included in the slurry for forming a refractory molded body include calcium silicate hydrate particles, specifically, zonotrite particles and tobermorite particles, and zonotrite particles are preferable.
- the calcium silicate hydrate particles can be prepared by a known method using the lime raw material powder and the silicate raw material powder, and will be described later by using the calcium silicate hydrate particles together with the inorganic particle raw material. Handling properties after the dehydration molding process can be improved.
- a slurry for forming a refractory molded body Preferably contains 3 to 95 parts by mass of calcium silicate hydrate particles, in terms of solid content, when the total content of the lime raw material powder and the silicate raw material powder is 100 parts by mass, More preferably, the content is 5 to 30 parts by mass.
- the content ratio of the calcium silicate hydrate particles is within the above range, the handling property after the dehydration molding process described later can be effectively improved.
- the slurry for fireproof molded object formation may contain a wollastonite particle as a calcium-silicate particle.
- Wollastonite is an inorganic substance with an acicular crystal structure having an infinite silicon-oxygen chain (SiO 3 ) structure linked by calcium cations, expressed as CaSiO 3 (CaO ⁇ SiO 2 ). Although it is macroscopically, it is powdery. Wollastonite produced as a natural mineral is produced in the limestone area as wollastonite, and may contain trace amounts (for example, less than 0.5% by weight) of Al 2 O 3 and Fe 2 O 3 as impurities.
- wollastonite particles include NYARD-G manufactured by US Interpace Corporation.
- machinability can be improved and the dimensional stability of the fireproof molded object obtained can be improved.
- the refractory molded body slurry when using calcium silicate particles containing lime raw material powder and silicate raw material powder, and further using wollastonite particles, the refractory molded body slurry is When converted to solid content, when the total content of the lime raw material powder and the silicic acid raw material powder is 100 parts by mass, the wollastonite particles are preferably contained in an amount of 7 to 120 parts by mass. More preferably, 90 parts by mass is contained. When the content ratio of the wollastonite particles is within the above range, the machinability can be effectively improved, and the dimensional stability of the obtained fireproof molded article can be improved.
- the molded body forming slurry contains 5 to 170 parts by mass of calcium silicate hydrate particles in terms of solid content, when the total content of the lime raw material powder and the silicate raw material powder is 100 parts by mass. It is preferable that the content is 11 to 50 parts by mass.
- the slurry for forming a refractory molded body contains 10 to 150 parts by mass of wollastonite particles when the total content of the lime raw material powder and the silicic acid raw material powder is 100 parts by mass in terms of solid content. It is preferable to contain 16 to 111 parts by mass.
- the content ratio of the calcium silicate hydrate particles is within the above range, the handling property after the dehydration molding process described later can be effectively improved, and the content ratio of the wollastonite particles is within the above range. By being, it can improve machinability effectively and can improve the dimensional stability of the fireproof molded object obtained.
- the slurry for fireproof molded object formation may also contain inorganic particles other than a calcium silicate particle.
- inorganic particles other than the calcium silicate particles include silica particles, alumina particles, mullite particles, silicon carbide particles, silicon nitride particles, silicon aluminum oxynitride particles, zircon particles, magnesia particles, zirconia particles, graphite particles, Boron nitride (BN) particles, aluminum nitride (AlN) particles, titanium diboride (TiB 2 ) particles, fly ash balloon particles, perlite particles, vermiculite particles, calcium fluoride particles, magnesium fluoride particles, calcium oxide particles, oxidation
- magnesium particles, barium oxide particles, barium sulfate particles, and the like can be given.
- the slurry for refractory molded body formation preferably contains the inorganic particles together with the wollastonite particles or together with the wollastonite particles.
- wollastonite It is preferable to add so that the total amount of the particles and the inorganic particles is within the content range of the wollastonite particles described above.
- the proportion of wollastonite particles in the total amount of wollastonite particles and the above inorganic particles is large, and it is more preferable that only wollastonite particles are included. .
- the slurry for forming a refractory molded body includes a raw material of calcium silicate particles and calcium silicate particles
- the raw material of calcium silicate particles and the calcium silicate particles are both In the obtained refractory molded article, it will be contained as calcium silicate particles.
- the slurry for forming a refractory molded body includes a bundle of inorganic fiber aggregates whose surfaces are coated with a resin having a glass transition temperature of 40 ° C. or lower.
- the bundle-like inorganic fiber aggregate examples include the same ones as described above.
- the production method 2 of the refractory molded article of the present invention can be applied particularly preferably when producing the refractory molded article 2 of the present invention.
- the bundle-like inorganic fiber aggregate is preferably 3 to 200 mm in length, more preferably 10 to 120 mm, and still more preferably 20 to 80 mm.
- the bundle-like inorganic fiber aggregate can be suitably dispersed in the obtained fireproof molded article 2 and the bundle-like inorganic fiber aggregate can be dispersed.
- the slurry for forming a refractory molded body used in the manufacturing method 2 of the refractory molded body of the present invention is generally higher in fluidity than the material for forming a refractory molded body used in the manufacturing method 1 of the refractory molded body of the present invention.
- the inorganic fiber aggregates those having a relatively long length can be used.
- the resin coated on the surface of the bundle-like inorganic fiber aggregate is not particularly limited as long as it has a glass transition temperature of 40 ° C. or less.
- acrylonitrile-butadiene copolymer latex styrene-butadiene copolymer latex And one or more selected from acrylic ester copolymer latex, polystyrene, polyethylene terephthalate, polycarbonate and the like.
- the amount of resin coated on the surface of the bundle-like inorganic fiber aggregate is preferably 1 to 30 parts by mass and more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the bundle-like inorganic fiber aggregate. It is preferably 3 to 15 parts by mass, more preferably 5 to 15 parts by mass.
- the amount of the resin to be coated on the surface of the bundle-like inorganic fiber aggregate is less than 1 part by mass with respect to 100 parts by mass of the bundle-like inorganic fiber aggregate, the slurry for forming a fire-resistant molded article described later or dehydration It is difficult to maintain the bundle state of the inorganic fiber aggregate during molding, and when it exceeds 30 parts by mass, voids are generated around the inorganic fiber aggregate by the drying treatment or baking treatment described later, and the inorganic fiber aggregate is easily removed. The toughness of the resulting refractory molded body tends to decrease.
- the resin coating on the bundle-like inorganic fiber aggregate can be performed, for example, by impregnation or spraying.
- the slurry for refractory molded body formation has a glass transition temperature of 40 on the surface with respect to 100 parts by mass of the raw material of the inorganic particles in solid content (when converted to solid content). It is preferable to contain 1 to 30 parts by mass, preferably 2 to 20 parts by mass, and more preferably 2 to 13 parts by mass of a bundle-like inorganic fiber aggregate formed by coating a resin having a temperature of 0 ° C. or lower.
- the material for forming the fireproof molded body contains a bundle-like inorganic fiber aggregate formed by coating a resin having a glass transition temperature of 40 ° C. or less on the surface in the above ratio. Sufficient toughness can be imparted to the resulting fireproof molded article.
- the slurry for fire-resistant molded article may further contain carbon fiber, pulp, rayon, polyester fiber, alkali-resistant glass fiber and the like as a fiber component. It is preferable that the content ratio of the fiber component in the slurry for forming a refractory molded body is 5% by mass or less in terms of solid content.
- the fiber component is distinguished from the bundle-like inorganic fiber aggregate, and means a short fiber added to ensure moldability, and the fireproof molding of the present invention.
- the slurry for fire-resistant molded object formation contains a fiber component, the moldability at the time of the dehydration molding mentioned later can be improved.
- the slurry for fireproof molded object formation may contain a binder further.
- the binder include the same ones as described above.
- the content ratio of the fiber component in the slurry for forming a refractory molded body is preferably less than 1% by mass in terms of solid content, and preferably contains no binder as much as possible.
- the slurry for forming a refractory molded body contains a binder, inorganic particles and the like are sufficiently bonded, and it is easy to impart sufficient strength to the obtained refractory molded body. Even if it does not contain a binder, sufficient strength can be imparted to the resulting fireproof molded article, and when no binder is contained, the thermal conductivity of the resulting fireproof molded article can be effectively reduced.
- examples of the solvent constituting the slurry for forming a refractory molded body include water or water containing water as a main component and a slight amount of a hydrophilic organic solvent, which is water. It is preferable.
- the method for preparing the slurry for forming the refractory molded body is not particularly limited.
- a lime raw material powder and a silicic acid raw material powder, a zonotlite slurry (sonotolite particle-containing slurry), a wollastonite particle, and a resin having a glass transition temperature of 40 ° C. or less on the surface so as to have a desired concentration with respect to an aqueous solvent It can be prepared by adding a bundle of inorganic fiber aggregates to be coated, adding a fiber component as desired, and stirring sufficiently.
- the said slurry for fireproof molded object formation is spin-molded.
- the slurry may contain a medium other than water as the liquid medium.
- the removal of the liquid medium other than water is also referred to as dehydration molding. .
- the dehydration molding is performed by, for example, a suction dehydration molding method, a pressure dehydration molding method, or a suction pressure dehydration method in which the slurry is poured into a molding die having a net installed at the bottom and the liquid medium such as water is sucked. be able to.
- a pump or the like when the slurry is transported to a molding die or the like, a pump or the like may be used, or the molding die is disposed under the tank containing the slurry, and the slurry It may be conveyed by its own weight.
- a dehydrated molded product having a shape similar to the fire-resistant molded product to be obtained is suitable, and examples thereof include a cylindrical shape, a bottomed cylindrical shape, a board shape, and a block shape.
- the bulk density of the fireproof molded body after the drying treatment described later is preferably 0.2 to 2.0 g / cm 3 , more preferably 0.5 to 1.5 g / cm 3 , and still more preferably 0.00. It is appropriate to adjust the pressure so that the pressure is 6 to 1.0 g / cm 3 .
- the dehydrated product obtained by dehydrating the slurry is subjected to hydrothermal treatment.
- the hydrothermal treatment is preferably performed in a water vapor atmosphere after the dehydrated product is transferred into an autoclave.
- the hydrothermal treatment condition is preferably performed under the condition that target calcium silicate particles are obtained from the raw material of calcium silicate particles, preferably under a water vapor pressure of 7 kg / cm 2 or more, and 14 kg / cm 2 or more. It is more preferable to carry out under a water vapor pressure, and it is more preferable to carry out under a water vapor pressure of 17 kg / cm 2 or more.
- the hydrothermal treatment time is not particularly limited, and can be appropriately selected according to the type of calcium silicate particles to be obtained and the water vapor pressure during hydrothermal treatment.
- the hydrothermal treatment time is suitably 5 to 48 hours.
- the hydrothermal treatment temperature is not particularly limited, and can be appropriately selected according to the type of calcium silicate particles to be obtained, the water vapor pressure during hydrothermal treatment, the hydrothermal treatment time, and the like.
- the lime raw material powder that is the raw material and the silicic acid raw material powder can be reacted to generate zonotlite particles that are calcium silicate particles.
- the hydrated product subjected to the hydration treatment is subjected to a drying treatment.
- the drying treatment temperature is preferably 50 to 300 ° C., more preferably 100 to 200 ° C.
- the drying treatment time is preferably 1 to 24 hours.
- the drying treatment atmosphere is preferably an air atmosphere.
- the production method 2 of the refractory molded body of the present invention is suitable as a method for producing the refractory molded body 2 of the present invention.
- the slurry for forming a refractory molded body containing the bundle-shaped inorganic fiber aggregates obtained is dehydrated and then hydrothermally treated and then dried to obtain the inorganic fiber aggregates while suppressing defibration.
- the inventors have found that a large amount of an inorganic fiber aggregate can be contained in a fireproof molded body, and have completed the present invention.
- fire-resistant molding containing a raw material of calcium silicate particles in the coexistence of a bundle-like inorganic fiber aggregate whose surface is coated with a resin having a glass transition temperature of 40 ° C. or less. Since the body-forming slurry is dehydrated and then hydrothermally treated, it is possible to form a refractory molded body while simultaneously synthesizing calcium silicate particles in a state where bundled inorganic fiber aggregates are dispersed. It is possible to suppress defibration and dispersion to individual inorganic fibers during the formation of the body, and even when a large amount of inorganic fiber aggregates are used, a fire-resistant molded body can be easily produced under high productivity.
- the fireproof molded article of the present invention can be suitably produced by the method for producing a fireproof molded article of the present invention.
- the refractory molded body 1 of the present invention can be suitably produced by the manufacturing method 1 of the refractory molded body of the present invention
- the refractory molded body 2 of the present invention is preferably manufactured by the manufacturing method 2 of the refractory molded body of the present invention. Can be produced.
- the fireproof molded article of the present invention contains inorganic particles and bundle-like inorganic fiber aggregates and does not contain a binder
- the production method 1 of the fireproof molded article of the present invention It can be produced by preparing a fire-resistant molded material that does not contain a binder and then molding it by a slip casting method.
- the mud casting (slip casting) method has a desired thickness by pouring a fire-resistant molding material that has been adjusted to an appropriate viscosity using a solvent into a mold made of a porous material and absorbing the solvent into the mold. According to this method, a high-density fire-resistant molded body is formed even when the fire-resistant molded body is densely filled in a mold and the fire-resistant molded body does not contain a binder. Can be produced.
- the member for metal casting of the present invention includes inorganic particles and bundle-like inorganic fiber aggregates, and has a fireproof molded article having an internal structure in which the bundle-like inorganic fiber aggregates are dispersed between the inorganic particles. Thus, at least the surface thereof is formed.
- the metal casting member of the present invention is a member used at a location where the metal casting apparatus comes into contact with the molten metal, and specifically includes a metal casting molten metal holding member and a metal casting apparatus constituent member.
- the molten metal holding member for metal casting include ladle, bowl, molten metal holding furnace, ladle and the like
- the metal casting apparatus constituent member include float, spout, hot top ring header and the like.
- the metal casting member of the present invention is the same as the refractory molded body of the present invention except that the shape thereof is limited to that formed for the metal casting member application, and constitutes the metal casting member.
- the method for producing a metal casting member of the present invention is also a method 1 for producing a fireproof molded body or a method for producing a fireproof molded body of the present invention, except that the shape of the product is limited to the shape of the metal casting member.
- 2 is filled with the above-mentioned fire-resistant molded body forming material in a mold having a desired molding surface shape, or the above-mentioned slurry for fire-resistant molded body is dehydrated and hydrothermally treated and then dried. Can be produced.
- the metal casting member of the present invention may be formed by forming a fireproof lining material made of the fireproof molded body of the present invention on the surface of a metal casing.
- the refractory lining material is formed on the surface of a metal casing, for example, it is formed by sticking a lining material made of a thin plate-shaped refractory molded body formed on a predetermined size to the surface of the metal casing. can do.
- the lining material to be attached to the surface of the metal casing is the same as the manufacturing method 1 of the fireproof molded body or the manufacturing method 2 of the fireproof molded body of the present invention, except that the shape is specified as a thin plate shape or the like. Can be produced.
- the metal casting member of the present invention can be produced by attaching the lining material to the surface of the metal casing as appropriate using mortar or the like.
- a kneaded product of the refractory molded body forming material is prepared by the same method as the manufacturing method 1 of the refractory molded body of the present invention.
- the kneaded material for forming the lining material is coated on the surface of the metal casing so as to have a desired shape, and then appropriately dried and fired under the same conditions as in Production Method 1 of the refractory molded article of the present invention.
- the metal casting member of the invention can also be produced.
- the shape of the metal casing can be any shape corresponding to the shape of the metal casting member such as the metal casting molten metal holding member to be obtained.
- the metal casting member to be obtained is a ladle.
- the metal casting member is a ladle
- an open container having an inlet and a spout together with a bottom and a side wall and an opening at the top can be mentioned.
- the whole open container is formed of the fireproof molded body of the present invention, and the inner surface of the open container is partially or entirely provided with the lining material formed of the fireproof molded body of the present invention. Can do.
- the metal casting member is a ladle
- a bottomed cylindrical pan body having a molten metal inlet and a pouring port, and an opening and closing which can seal the molten metal inlet. It has a free upper lid and an openable / closable pouring lid capable of sealing the molten metal pouring port, and is entirely formed of the fireproof molded body of the present invention in the pan body, the pouring port and the pouring port.
- the thing which has the lining material formed by the fireproof molded object of this invention can be mentioned to all or a part of the inner surface.
- the metal casting member of the present invention is a molten metal holding member for metal casting
- the metal casting member may have a support metal fitting as necessary.
- another casting apparatus configuration such as a robot arm is provided. Attachment to a member can be performed easily.
- the support metal fitting is integrated with the main body portion in advance at a desired position. can do. Further, it is possible to attach the support fitting by exposing the support fitting portion while forming the support fitting integrally with the metal casing in advance and providing a lining material on the surface of the metallic casing to cover the surface. .
- Example 1 As shown in Table 1, 30.0 parts by mass of high alumina cement is included as a binder, 40.0 parts by mass of silica and 30.0 parts by mass of wollastonite particles are included as inorganic particles, and a glass transition temperature is formed on the surface.
- the surface of a bundle of glass fibers having a thickness of 10 mm is coated with 10 parts by mass of an acrylonitrile / butadiene copolymer latex resin having a glass transition temperature of ⁇ 31 ° C. with respect to 100 parts by mass of the bundle of glass fibers.
- the solid content of the refractory molded body forming material was weighed out so as to contain 2.2 parts by mass and filled into a kneader.
- 15 parts by mass of water is added to 100 parts by mass of the solid content of the refractory molded body forming material (a bundle of inorganic fiber aggregates coated with cement, inorganic particles and resin) in the kneader.
- a kneaded product was prepared by kneading for 10 minutes.
- the kneaded material is applied to a thickness of 50 mm on a metal casing 5 having a shape corresponding to the shape of the ladle (shown in black in the drawing), and 105 ° C. Was dried for 24 hours, and further fired at 700 ° C. for 3 hours to form a refractory lining material 6 (shown by diagonal lines in the figure), and a ladle 4 was produced.
- voids such as soot and voids were not observed.
- the kneaded product is filled into a box-shaped mold, dried at 105 ° C. for 24 hours, and further fired at 700 ° C. for 3 hours to obtain a quadrangular prism-shaped molded product.
- the Charpy impact value measured by JIS R 1662 was measured. The bulk density was 1.6 g / cm 3 and the Charpy impact value was 1.1 mJ / mm 2 . Further, when the fracture surface of this molded product was visually observed, a bundle of inorganic fiber aggregates b (in the aggregate made of inorganic particles a) between the inorganic particles a bonded with cement as shown in FIG. was confirmed to be uniformly dispersed.
- Example 2 to Example 7 Except for changing the blending ratio of the cement-like, inorganic particles, and the bundle-like inorganic fiber aggregate obtained by coating the surface with a resin having a glass transition temperature of 40 ° C. or lower, as shown in Table 1, the same manner as in Example 1 was performed. A ladle with a support member was produced. No voids such as soot and voids were observed in each obtained ladle. Table 2 shows the composition of the fireproof molded body constituting the obtained ladle. Moreover, the tap flow value was measured like Example 1 using the kneaded material obtained in each Example. The results are shown in Table 1.
- Example 2 a square columnar molded product was produced using the kneaded product in the same manner as in Example 1, and the bulk density and Charpy impact value of each molded product were measured in the same manner as in Example 1. The results are shown in Table 2. As a result of visual observation of the fracture surface of each molded product, it was confirmed that the bundle-like inorganic fiber aggregates were uniformly dispersed between the inorganic particles bonded with cement.
- Example 1 As shown in Table 3, instead of acrylonitrile-butadiene copolymer latex-coated glass fiber chopped strands, glass fiber chopped strands not coated with resin (diameter 1 mm, length obtained by chopping aligned glass continuous fibers) A ladle with a supporting member was produced in the same manner as in Example 1 except that a 10 mm bundle of glass fiber aggregates) was used. It was confirmed that voids having a diameter of 2 cm or more were generated in the obtained ladle. Table 4 shows the composition of the fireproof molded body constituting the obtained ladle. Further, the tap flow value was measured in the same manner as in Example 1 using the kneaded material used for the production of the ladle.
- Comparative Example 2 (Comparative Example 2 to Comparative Example 4) Although it tried to produce a ladle with a supporting member in the same manner as in Comparative Example 1 except that the blending ratio of cement, inorganic particles, and glass fiber chopped strands not coated with resin was changed as shown in Table 3, The fluidity of the kneaded product was low, and none of them could be molded.
- Example 8 As shown in Table 5, as a bundle-like inorganic fiber aggregate formed by coating the surface with a resin having a glass transition temperature of 40 ° C. or lower, instead of acrylonitrile / butadiene copolymer latex coated glass fiber chopped strand, acrylonitrile / butadiene is used.
- Copolymer latex-coated silica fiber chopped strand (on the surface of a bundle of silica fibers having a diameter of 1 mm and a length of 10 mm obtained by chopping together aligned silica continuous fibers, 100 mass of the bundle of silica fibers And 10 parts by weight of an acrylonitrile / butadiene copolymer latex having a glass transition temperature of ⁇ 31 ° C.) and a cement, inorganic particles, and a resin having a glass transition temperature of 40 ° C. or less on the surface.
- Table 5 To produce a ladle equipped with the support member in the same manner as in Example 1. No voids such as soot and voids were observed in each obtained ladle.
- Table 6 shows the composition of the fireproof molded body constituting the obtained ladle.
- Example 2 the tap flow value was measured in the same manner as in Example 1 using the kneaded material obtained in each Example. The results are shown in Table 5. Further, a square columnar molded product was produced using the kneaded product in the same manner as in Example 1, and the bulk density and Charpy impact value of each molded product were measured in the same manner as in Example 1. The results are shown in Table 6. When the cross sections of the respective molded products were visually observed, it was confirmed that the bundle-like inorganic fiber aggregates were uniformly dispersed between the inorganic particles bonded with cement.
- Example 10 to Example 11 As a bundle-like inorganic fiber aggregate formed by coating a resin having a glass transition temperature of 40 ° C. or less on the surface, instead of acrylonitrile / butadiene copolymer latex coated glass fiber chopped strand, acrylonitrile / butadiene copolymer latex coated alumina fiber is used.
- Example 2 the tap flow value was measured in the same manner as in Example 1 using the kneaded material obtained in each Example. The results are shown in Table 5. Further, a square columnar molded product was produced using the kneaded product in the same manner as in Example 1, and the bulk density and Charpy impact value of each molded product were measured in the same manner as in Example 1. The results are shown in Table 6. As a result of visual observation of the fracture surface of each molded product, it was confirmed that the bundle-like inorganic fiber aggregates were uniformly dispersed between the inorganic particles bonded with cement.
- Example 12 As a bundle-like inorganic fiber aggregate formed by coating a resin having a glass transition temperature of 40 ° C. or less on the surface, a mixed resin-coated glass fiber of acrylonitrile / butadiene copolymer latex and polystyrene instead of an acrylic resin-coated glass fiber chopped strand Chopped strand (on the surface of a bundle of glass fibers having a diameter of 1 mm and a length of 10 mm obtained by chopping together aligned glass continuous fibers, the glass transition temperature with respect to 100 parts by mass of the bundle of glass fibers. Using a mixed resin of acrylonitrile / butadiene copolymer latex and polystyrene at 31 ° C.
- Example 7 the tap flow value was measured in the same manner as in Example 1 using the kneaded material obtained in the above production example. The results are shown in Table 7. Further, using the kneaded product, a quadrangular columnar molded product was produced in the same manner as in Example 1, and the bulk density and Charpy impact value of the molded product were measured in the same manner as in Example 1. The results are shown in Table 8. When the fracture surface of the molded product was visually observed, it was confirmed that the bundle-like inorganic fiber aggregates were uniformly dispersed between the inorganic particles bonded with cement.
- Example 13 to Example 18 As the binder, aluminum phosphate having a solid concentration of 95% by mass is used instead of high alumina cement, and the aluminum phosphate, inorganic particles, and a resin having a glass transition temperature of 40 ° C. or less are coated on the surface.
- a ladle with a supporting member was produced in the same manner as in Example 1 except that the blending ratio of the bundle-like inorganic fiber aggregate was changed as shown in Table 9. No voids such as soot and voids were observed in each obtained ladle.
- Table 10 shows the composition of the fireproof molded body constituting the obtained ladle.
- Example 10 when the tap flow value was measured in the same manner as in Example 1 using the kneaded material obtained in each Example, it was 150 or more in all cases. Further, a square columnar molded product was produced using the kneaded product in the same manner as in Example 1, and the bulk density and Charpy impact value of each molded product were measured in the same manner as in Example 1. The results are shown in Table 10. When the fracture surface of each molded product was visually observed, it was confirmed that the bundle-like inorganic fiber aggregates were uniformly dispersed between the inorganic particles bonded with the binder.
- the ladle and ladle obtained in Examples 1 to 18 have high homogeneity because no scum or voids are formed in the refractory molded body. It can also be seen that the bundle-like inorganic fibrous aggregates are uniformly dispersed in a large amount in the inside thereof, the thermal conductivity is low, and the toughness is high.
- Example 1 to 18 since the bundle-like inorganic fiber aggregate whose surface is coated with a resin having a glass transition temperature of 40 ° C. or less is used as the inorganic fiber material, the bundle-like shape at the time of kneading is used. It can be seen that defibration of the inorganic fiber aggregate can be suppressed, and a fireproof molded article containing a large amount of inorganic fiber aggregate can be easily produced under high productivity.
- the ladle obtained in Comparative Example 1 uses a bundle-like inorganic fiber aggregate whose surface is not coated with a resin as the inorganic fiber material. It turns out that only the thing with low homogeneity in which the space
- Example 19 As shown in Table 11, with respect to 800 parts by mass of water, as raw materials for calcium silicate particles as inorganic particles, 25 parts by mass of quicklime powder, 25 parts by mass of silica powder, and calcium silicate particles were synthesized in advance by a stirring autoclave. 10 parts by mass of the zonotlite slurry in terms of solid content, 40 parts by mass of wollastonite particles (NYARD-G manufactured by Interpace, USA), and a bundle of inorganic fibers obtained by coating the surface with a resin having a glass transition temperature of 40 ° C.
- a bundle of acrylonitrile-butadiene copolymer latex-coated glass fiber chopped strand E glass fiber roving (fineness 270 tex) chopped (cut), having a fineness of 270 tex, a diameter of 0.5 mm, and a length of 50 mm
- the bundle of glass fiber aggregate 100 3 parts by weight of 3 parts by weight of an acrylonitrile / butadiene copolymer latex resin having a glass transition temperature of ⁇ 31 ° C. and 3 parts by weight of an alkali-resistant glass fiber (manufactured by Nippon Electric Glass Co., Ltd.)
- the slurry was sufficiently mixed to prepare a slurry for forming a refractory molded body.
- the slurry for forming a fire-resistant molded body was dehydrated and press-molded into a flat plate shape, and then cured in an autoclave in a pressurized steam atmosphere of 205 ° C. and 17 kg / cm 2 for 48 hours, followed by hydrothermal treatment, and then at 125 ° C.
- the plate was dried for 15 hours to obtain a plate-like refractory molded body (dried body) having a length of 200 mm, a width of 200 mm, a thickness of 30 mm and a bulk density of 0.85 g / cm 3 .
- Table 12 shows the composition of the obtained fireproof molded article. No voids such as soot and voids were observed in the refractory molded body.
- the obtained refractory molded body was subjected to X-ray diffraction analysis.
- the refractory molded body contained calcium silicate particles obtained by reacting quicklime and silica as inorganic particles, and the calcium silicate particles were substantially zonotrite particles. It was confirmed that. It was 8.0 MPa when the bending strength of the obtained refractory molded article was measured in accordance with JIS A 1408. Moreover, it was 1.5 mJ / mm ⁇ 2 > when the Charpy impact value of the obtained fireproof molded object was measured according to prescription
- the obtained fired body had a bulk density of 0.85 g / cm 3 , a bending strength measured according to JIS A 1408, and 8.0 MPa.
- the Charpy impact value measured according to the rules of R 1662 was 1.2 mJ / mm 2 . The results are shown in Table 12.
- Example 20 to Example 22 A flat fire-resistant molded body (as in Example 19) except that the amount of the bundle-like inorganic fiber aggregate formed by coating a resin with a glass transition temperature of 40 ° C. or less on the surface was changed as shown in Table 11. Dried body). No voids such as soot and voids were observed in the obtained refractory molded bodies. Moreover, when the fracture surface of each said molded object was visually observed, it has confirmed that the bundle-like inorganic fiber aggregate has disperse
- Example 19 Further, the bending strength and Charpy impact value of each obtained refractory molded body were measured in the same manner as in Example 19. The results are shown in Table 12. Further, the bulk density, bending strength, and Charpy impact value of the fired body obtained by firing the above fire-resistant molded bodies at 500 ° C. for 12 hours were measured in the same manner as in Example 19. The results are shown in Table 12.
- Example 14 Further, the bending strength and Charpy impact value of each obtained refractory molded body were measured in the same manner as in Example 19. The results are shown in Table 14. Furthermore, the bending strength and Charpy impact value of the fired body obtained by firing the fireproof molded body at 500 ° C. for 12 hours were measured in the same manner as in Example 19. The results are shown in Table 14.
- Comparative Example 7 when the fracture surface of the obtained fireproof molded article was visually observed, it was confirmed that the bundle-like inorganic fiber aggregate was opened.
- Comparative Examples 8 to 10 the bundle-like inorganic fiber aggregates are opened to increase the viscosity of the slurry for forming a refractory molded body and the moldability is deteriorated. As a result, voids such as soot and voids are formed in the molded body. As a result, no uniform molded body could be obtained.
- Table 14 shows the composition and bulk density of the obtained refractory molded article. Moreover, the bending strength and Charpy impact value of each refractory molded body obtained in Comparative Example 7 were measured in the same manner as in Example 19.
- Example 23 to Example 24 As shown in Table 15, the lengths of the bundle-like inorganic fiber aggregates obtained by coating the surface with a resin having a glass transition temperature of 40 ° C. or less were changed to 10 mm (Example 23) and 120 mm (Example 24), respectively.
- a flat fireproof molded body (dried body) was produced in the same manner as in Example 20 except that. No voids such as soot and voids were observed in the obtained refractory molded bodies. Moreover, when the fracture surface of each said molded object was visually observed, it has confirmed that the bundle-like inorganic fiber aggregate has disperse
- Example 25 As shown in Table 17, in Example 25, as a bundle-like inorganic fiber aggregate covering the surface with a resin having a glass transition temperature of 40 ° C. or less, an alkali-resistant continuous glass fiber (alkali-resistant glass fiber roving (Nippon Electric Glass ( In Example 26, a bundle of inorganic fiber aggregates having a fineness of 270 tex and a length of 50 mm obtained by chopping (fineness 270 tex) manufactured by Co., Ltd. was used.
- alkali-resistant continuous glass fiber alkali-resistant glass fiber roving (Nippon Electric Glass
- Example 26 a bundle of inorganic fiber aggregates having a fineness of 270 tex and a length of 50 mm obtained by chopping (fineness 270 tex) manufactured by Co., Ltd. was used.
- Example 27 A bundle of 270 tex, 0.5 mm in diameter and 50 mm in length, obtained by chopping (twisting two yarns) and chopping (with a fineness of 270 tex and a twist number of 4.4 per 25 mm)
- an alkali-resistant glass fiber composite yarn (twisting 135 tex of alkali-resistant glass fiber composite yarn, twisted together)
- Example 20 except that a bundle-like inorganic fiber assembly having a fineness of 270 tex and a length of 50 mm obtained by chopping (cutting) a 270 tex and a twist number of 4.4 per 25 mm) was used.
- the fire-resistant molded bodies (dried bodies and fired bodies) obtained in Examples 19 to 27 have no homogeneity due to the absence of soot and voids.
- the bundle-like inorganic fiber aggregates are uniformly dispersed in a large amount in the inside, the thermal conductivity is low, and it has high bending strength and impact resistance. I understand.
- Examples 19 to 27 as the inorganic fiber material, a bundle-like inorganic fiber aggregate whose surface is coated with a resin having a glass transition temperature of 40 ° C. or lower is used. It can be seen that defibration of the shaped inorganic fiber aggregate can be suppressed, and a fire-resistant molded article containing a large amount of inorganic fiber aggregate can be easily produced under high productivity.
- the refractory molded body obtained in Comparative Example 6 was replaced with a bundle of inorganic fiber aggregates whose surface was coated with a resin having a glass transition temperature of 40 ° C. or lower, and the surface was glass transition temperature. Since the bundle of carbon fiber chopped strands not coated with a resin of 40 ° C. or lower is used, not only the bundle of carbon fibers is opened at the time of forming the fireproof molded body, It can be seen that the carbon fibers are burned out and the impact resistance is reduced. Further, since the fire-resistant molded articles obtained in Comparative Examples 7 to 10 are formed using bundle-like inorganic fiber aggregates whose surfaces are not covered with a resin having a glass transition temperature of 40 ° C.
- Inorganic fiber aggregates are opened at the time of forming the fire-resistant molded product, and only those having low impact resistance can be obtained (Comparative Example 7). It can be seen that a uniform molded product cannot be obtained (Comparative Examples 8 to 10).
- a novel fire-resistant molded article having low thermal conductivity, high homogeneity, and high durability against physical impact and thermal shock is provided, and the fire-resistant molded article is highly productive. It is possible to provide a method for simply producing the molten metal holding member for metal casting below.
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Abstract
Description
大量生産を目的とした鋳造装置において、ラドルはロボットアーム等に搭載され自動制御されており、所定量の金属溶湯を保持溶炉からすくい上げて鋳造機まで運んで注入するようにプログラムされている。また、少量生産を目的とした鋳造装置において、ラドルは手動リフトハンドル等に固定された状態で手動で制御されている。
しかしながら、鋳鉄は熱伝導性が高いことから、鋳鉄製のラドルを用いた場合、保持溶炉や運搬される金属溶湯の温度を低下させてしまう。このため、保持溶炉や金属溶湯の温度低下を考慮して保持溶炉の温度を鋳造温度よりも相当に高い温度に維持しなければならず、エネルギー損失が大きくなるという技術課題が存在している。
また、ラドル以外にも、例えば樋、溶湯保持炉、取鍋、フロート、スパウト、ホットトップリングヘッダー等の溶湯と接触する金属鋳造用部材においても、熱伝導性が低く、優れた耐熱衝撃性を有するものが求められるようになっているが、例えば金属鋳造用部材として、特許文献2に記載の炭素繊維を混入したケイ酸カルシウム製の部材を用いた場合、金属溶湯の温度が炭素繊維の耐熱温度よりも高いことから、使用に伴って炭素繊維が次第に焼失して、亀裂を生じ易くなる。
従って、本発明は、熱伝導性が低いとともに、物理的な衝撃や熱衝撃に対する耐久性が高く、均質性の高い新規な耐火成形体を提供するとともに、該耐火成形体を高い生産性の下で簡便に製造する方法および金属鋳造用部材を提供することを目的とするものである。
しかしながら、本発明者等が検討したところ、無機短繊維は、通常、複数の短繊維がサイジング剤で結着されるか加撚された無機短繊維集合体の状態にあるが、これらの無機短繊維集合体は、混練時に個々の無機短繊維に解繊し分散して、混練物の流動性を著しく低下させてしまい、成形物にスやボイド等の空隙を生じて成形不良を引き起こすことから、極少量の無機短繊維しか添加できないことが判明した。ラドルは最薄部の肉厚が1cm程度であることから、上記空隙を生じた場合には、均質性が低下し、十分な靱性を付与することができなくなってしまう。
(1)無機粒子と、束状の無機繊維集合体とを含んでなり、前記無機粒子間に前記束状の無機繊維集合体が分散された内部構造を有することを特徴とする耐火成形体、
(2)バインダーと、無機粒子と、束状の無機繊維集合体とを含んでなり、前記バインダーで結合された前記無機粒子間に前記束状の無機繊維集合体が分散された内部構造を有する上記(1)に記載の耐火成形体(以下、適宜、耐火成形体1と称する)、
(3)前記バインダーを1~50質量%、前記無機粒子を30~95質量%、前記束状の無機繊維集合体を1~30質量%含んでなる上記(2)に記載の耐火成形体、
(4)前記束状の無機繊維集合体の直径が0.01~5mmであり、長さが3~30mmである上記(2)または(3)に記載の耐火成形体、
(5)前記無機粒子としてケイ酸カルシウム粒子を含むとともに、束状の無機繊維集合体を含んでなり、前記ケイ酸カルシウム粒子間に前記束状の無機繊維集合体が分散された内部構造を有する上記(1)に記載の耐火成形体(以下、適宜、耐火成形体2と称する)、
(6)前記無機粒子を65~99質量%、前記束状の無機繊維集合体を1~30質量部含んでなる上記(5)に記載の耐火成形体、
(7)前記束状の無機繊維集合体の直径が0.01~5mmであり、長さが3~200mmである上記(5)または(6)に記載の耐火成形体、
(8)JIS R 1662により測定したときのシャルピー衝撃値が0.5~10mJ/mm2である上記(1)~(7)のいずれか1項に記載の耐火成形体、
(9)無機粒子と、表面にガラス転移温度40℃以下の樹脂を被覆してなる束状の無機繊維集合体とを含む耐火成形体形成材料を混練した後、得られた混練物を成形することを特徴とする耐火成形体の製造方法(以下、適宜、耐火成形体の製法1と称する)、
(10)バインダーと、無機粒子と、表面にガラス転移温度40℃以下の樹脂を被覆してなる束状の無機繊維集合体とを含む耐火成形体形成材料を混練した後、得られた混練物を成形する上記(9)に記載の耐火成形体の製造方法、
(11)前記耐火成形体形成材料が、固形分中に、前記バインダーを1~50質量%、前記無機粒子を30~95質量%、前記表面にガラス転移温度40℃以下の樹脂を被覆してなる束状の無機繊維集合体を1~30質量%含む上記(10)に記載の耐火成形体の製造方法、
(12)JIS R 5201により測定したときの前記混練物のタップフロー値が150mm以上である上記(10)または(11)に記載の耐火成形体の製造方法、
(13)ケイ酸カルシウム粒子の原料を含むとともに、表面にガラス転移温度40℃以下の樹脂を被覆してなる束状の無機繊維集合体を含む耐火成形体形成用スラリーを、脱水成形し、次いで水熱処理した後、乾燥処理することを特徴とする耐火成形体の製造方法(以下、適宜、耐火成形体の製法2と称する)、
(14)前記ケイ酸カルシウム粒子の原料が石灰原料粉末およびケイ酸原料粉末である上記(13)に記載の耐火成形体の製造方法、
(15)前記水熱処理を7kg/cm2以上の水蒸気圧下で行う上記(14)に記載の耐火成形体の製造方法、
(16)前記耐火成形体形成用スラリーが、固形分中に、前記無機粒子の原料100質量部に対し、前記表面にガラス転移温度40℃以下の樹脂を被覆してなる束状の無機繊維集合体を1~30質量部含む上記(13)~(15)のいずれかに記載の耐火成形体の製造方法、
(17)前記表面にガラス転移温度40℃以下の樹脂を被覆してなる束状の無機繊維集合体が、束状の無機繊維集合体100質量部に対してガラス転移温度40℃以下の樹脂を1~30質量部被覆してなるものである上記(9)~(16)のいずれか1項に記載の耐火成形体の製造方法、
(18)無機粒子と、束状の無機繊維集合体とを含んでなり、前記無機粒子間に前記束状の無機繊維集合体が分散された内部構造を有する耐火成形体により、少なくともその表面が形成されてなることを特徴とする金属鋳造用部材、
を提供するものである。
本発明の耐火成形体は、無機粒子と、束状の無機繊維集合体とを含んでなり、前記無機粒子間に前記束状の無機繊維集合体が分散された内部構造を有することを特徴とするものである。
耐火成形体1は、バインダーと、無機粒子と、束状の無機繊維集合体とを含んでなり、前記バインダーで結合された前記無機粒子間に前記束状の無機繊維集合体が分散された内部構造を有するものであり、耐火成形体2は、無機粒子としてケイ酸カルシウム粒子を含むとともに、束状の無機繊維集合体を含んでなり、前記ケイ酸カルシウム粒子間に前記束状の無機繊維集合体が分散された内部構造を有するものである。
耐火成形体1と耐火成形体2は、耐火成形体1がバインダーを含むことを必須とし、耐火成形体2が無機粒子としてケイ酸カルシウム粒子を含むことを必須とするものである点において相違するものの、その他の点においては共通する技術事項を含むものであるので、以下、適宜両者を対比しつつ説明するものとする。
本発明の耐火成形体が耐火成形体1である場合、無機粒子としては、例えば、シリカ粒子、アルミナ粒子、ムライト粒子、炭化ケイ素粒子、窒化ケイ素粒子、シリコンアルミニウムオキシニトリド粒子、ジルコン粒子、マグネシア粒子、ジルコニア粒子、グラファイト粒子、ワラストナイト粒子等のケイ酸カルシウム粒子、窒化硼素(BN)粒子、窒化アルミニウム(AlN)粒子、二硼化チタン(TiB2)粒子、フライアッシュバルーン粒子、パーライト粒子、バーミキュライト粒子、フッ化カルシウム粒子、フッ化マグネシウム粒子、酸化カルシウム粒子、酸化マグネシウム粒子、酸化バリウム粒子及び硫酸バリウム粒子等から選ばれる一種以上を挙げることができる。
本発明の耐火成形体が耐火成形体2である場合、無機粒子としてケイ酸カルシウム粒子を含み、ケイ酸カルシウム粒子として、具体的にはゾノトライト粒子、トバモライト粒子、ワラストナイト粒子等を挙げることができる。
本発明の耐火成形体が耐火成形体1である場合、無機粒子を30~95質量%含んでなるものが好ましく、40~90質量%含んでなるものがより好ましく、45~80質量%含んでなるものがさらに好ましい。
また、本発明の耐火成形体が耐火成形体2である場合、無機粒子を65~99質量%含んでなるものが好ましく、75~96質量%含んでなるものがより好ましく、80~95質量%含んでなるものがさらに好ましい。
無機粒子の含有量が上記範囲内にあることにより、耐火成形体に十分な強度を付与し易くなるとともに、耐火成形体の形状を所望形状に維持し易くなる。
上記無機粒子の含有量は、耐火成形体製造時に用いた原料量から算出することができる。
なお、本出願書類において、上記繊度が1texであるとは、束状の無機繊維集合体1000mあたりの重量が1gであることを意味する。
本発明の耐火成形体が耐火成形体1である場合、束状の無機繊維集合体は、束状の無機繊維集合体は、長さが3~30mmであることが好ましく、5~25mmであることがより好ましく、10~20mmであることがさらに好ましい。
また、本発明の耐火成形体が耐火成形体2である場合、束状の無機繊維集合体は、長さが3~200mmであることが好ましく、10~120mmであることが好ましく、20~80mmであることがさらに好ましい。
本発明の耐火成形体が耐火成形体1である場合、束状の無機繊維集合体を1~30質量%含んでなるものが好ましく、5~30質量%含んでなるものがより好ましく、10~30質量%含んでなるものがさらに好ましい。
本発明の耐火成形体が耐火成形体2である場合、束状の無機繊維集合体を1~30質量%含んでなるものが好ましく、2~20質量%含んでなるものがより好ましく、2~13質量%含んでなるものがさらに好ましい。
本発明の耐火成形体が、束状の無機繊維集合体を1~30質量含んでなるものであることにより、耐火成形体に十分な靱性を付与することができる。束状の無機繊維集合体の含有量が1質量%未満であると、耐火成形体に十分な靱性を付与し難くなり、30質量%を超えると、成形時に成形材料の流動性が低下して成形し難くなる。
上記束状の無機繊維集合体の含有量は、耐火成形体製造時に用いた原料量から算出することができる。
セメントとしては、無機バインダーとして機能するものであれば特に制限されないが、例えば、ポルドラントセメント、白色セメント、フライアッシュセメント、シリカセメント、アルミナセメント等の水硬性セメント等から選ばれる一種以上を挙げることができる。上記セメントとしては、耐熱性の高いアルミナセメントが好適である。ここで、アルミナセメントとは、CaO・Al2O3を主成分とするセメントを意味し、例えば、Al2O3含有割合が70質量%以上であるものが好適である。
耐火成形体2中の繊維成分の含有割合は、固形分換算で5質量%以下であることが好ましい。
なお、本出願書類において、繊維成分とは、上記束状の無機繊維集合体とは区別されるものであり、成形性を確保するために添加される短繊維を意味するものとする。
上記金属鋳造用溶湯保持部材として、具体的には、ラドル、樋、溶湯保持炉、取鍋等を挙げることができ、上記金属鋳造装置構成部材として、具体的には、フロート、スパウト、ホットトップリングヘッダー等を挙げることができる。
本発明の耐火成形体は、本発明の耐火成形体の製造方法により好適に作製することができる。具体的には、本発明の耐火成形体1は、後述する本発明の耐火成形体の製法1により好適に作製することができ、本発明の耐火成形体2は、後述する本発明の耐火成形体の製法2により好適に作製することができる。
本発明の耐火成形体の製造方法は、耐火成形体の製法1と耐火成形体の製法2からなるが、先ず耐火成形体の製法1について説明した後、耐火成形体の製法2について説明するものとする。
本発明の耐火成形体の製法1は、無機粒子と、表面にガラス転移温度40℃以下の樹脂を被覆してなる束状の無機繊維集合体とを含む耐火成形体形成材料を混練した後、得られた混練物を成形することを特徴とするものである。
本発明の耐火成形体の製法1は、本発明の耐火成形体1を作製する場合に特に好ましく適用することができる。
無機粒子の含有量が上記範囲内にあることにより、得られる耐火成形体に十分な強度を付与し易くなるとともに、得られる耐火成形体の形状を所望形状に維持し易くなる。
束状の無機繊維集合体の表面にガラス転移温度40℃以下の樹脂を被覆することにより、無機繊維集合体に一定の柔軟性を付与し得るため、耐火成形体形成材料の混練時においても、無機繊維集合体を解繊することなく、束形状を保持したまま耐火成形体中に存在させることが可能になると考えられる。
また、耐火成形体形成材料が後述するバインダーを含む場合も、束状の無機繊維重合体の含有割合は、上記範囲内にあることが好ましい。
本発明の耐火成形体の製法1において、耐火成形体の形成材料が、束状の無機繊維集合体を1~30質量%含有することにより、得られる耐火成形体に十分な靱性を付与することができる。
上記成形は、耐火成形体形成材料を成形型に充填することにより行うことが好ましい。
混練物の成形型への充填は、例えばフレキシブルバイブレータなどを用いて脱気しながら流し込んで行うことが好ましい。また、成形型としては、木型、金型、合成樹脂型などを使用することができる。これ等の成形型のうち、合成樹脂型が、寸法精度や寸法安定性などの点から好適である。
上記成形時において、成形型への溶媒の吸収を促進するために、加圧ないしは真空引きを補助的に行ってもよい。
また、上記成形は、所望粘度を有するように粘度調整して得られた混練物を、所望箇所(例えばケーシング表面)に塗工することによっても行うことができる。
なお、上記成形時において、雰囲気温度(室温)が氷点下になるような場合は1日で脱型できない場合があるので、成形型に流し込んだ後は、ほぼ15~30℃程度の温度雰囲気下で養生することが望ましい。
本発明の耐火成形体の製法2は、ケイ酸カルシウム粒子の原料を含むとともに、表面にガラス転移温度40℃以下の樹脂を被覆してなる束状の無機繊維集合体を含む耐火成形体形成用スラリーを、脱水成形し、次いで水熱処理した後、乾燥処理することを特徴とするものである。
本発明の耐火成形体の製法2は、本発明の耐火成形体2を作製する場合に好ましく適用することができる。
無機粒子の原料の含有量が上記範囲内にあることにより、表面にガラス転移温度40℃以下の樹脂を被覆してなる束状の無機繊維集合体を均一に分散させつつ、得られる耐火成形体に十分な強度を付与し易くなるとともに、得られる耐火成形体の形状を所望形状に維持し易くなる。
耐火成形体形成用スラリー中に含み得るケイ酸カルシウム粒子としてはケイ酸カルシウム水和物粒子を挙げることができ、具体的にはゾノトライト粒子やトバモライト粒子を挙げることができ、ゾノトライト粒子が好ましい。
ケイ酸カルシウム水和物粒子は、上記石灰原料粉末およびケイ酸原料粉末を用いて公知の方法により調製することができ、無機粒子の原料とともにケイ酸カルシウム水和物粒子を用いることにより、後述する脱水成形処理後のハンドリング性を向上することができる。
ケイ酸カルシウム水和物粒子の含有割合が上記範囲内にあることにより、後述する脱水成形処理後のハンドリング性を効果的に向上させることができる。
ワラストナイト(Wollastonite)は、CaSiO3(CaO・SiO2)で表記される、カルシウムカチオンで繋がれた無限の珪素-酸素鎖(SiO3)構造を有する、結晶構造が針状の無機物質であるが、巨視的には粉末状のものである。天然鉱物として産出されるワラストナイトは、珪灰石として石灰岩地帯に産出し、不純物として微量(例えば、0.5重量%未満)のAl2O3やFe2O3を含有することもある。ワラストナイト粒子として、具体的には、米国インターペース社製NYARD-G等を挙げることができる。
本発明の耐火成形体の製法2において、耐火成形体形成用スラリーがワラストナイト粒子を含むことにより、機械加工性を向上させ、得られる耐火成形体の寸法安定性を向上させることができる。
ワラストナイト粒子の含有割合が上記範囲内にあることにより、機械加工性を効果的に向上させ、得られる耐火成形体の寸法安定性を向上させることができる。
ケイ酸カルシウム水和物粒子の含有割合が上記範囲内にあることにより、後述する脱水成形処理後のハンドリング性を効果的に向上させることができ、ワラストナイト粒子の含有割合が上記範囲内にあることにより、機械加工性を効果的に向上させ、得られる耐火成形体の寸法安定性を向上させることができる。
上記ケイ酸カルシウム粒子以外の無機粒子としては、例えば、シリカ粒子、アルミナ粒子、ムライト粒子、炭化ケイ素粒子、窒化ケイ素粒子、シリコンアルミニウムオキシニトリド粒子、ジルコン粒子、マグネシア粒子、ジルコニア粒子、グラファイト粒子、窒化硼素(BN)粒子、窒化アルミニウム(AlN)粒子、二硼化チタン(TiB2)粒子、フライアッシュバルーン粒子、パーライト粒子、バーミキュライト粒子、フッ化カルシウム粒子、フッ化マグネシウム粒子、酸化カルシウム粒子、酸化マグネシウム粒子、酸化バリウム粒子及び硫酸バリウム粒子等から選ばれる一種以上を挙げることができる。
本発明の耐火成形体の製法2において、耐火成形体形成用スラリーは、上記無機粒子を、上述したワラストナイト粒子に代えてまたはワラストナイト粒子とともに含むことが好ましく、この場合、ワラストナイト粒子および上記無機粒子の合計量が上述したワラストナイト粒子の含有量範囲内になるように添加することが好ましい。機械加工性や寸法安定性を考慮した場合には、ワラストナイト粒子および上記無機粒子の合計量に占めるワラストナイト粒子の割合が多いことが好ましく、ワラストナイト粒子のみからなることがより好ましい。
束状の無機繊維集合体の長さが上記範囲内にあることにより、得られる耐火成形体2において、束状の無機繊維集合体を好適に分散することができるとともに、束状の無機繊維集合体が抜け難くなって靭性を向上し易くなる。
本発明の耐火成形体の製法2で用いる耐火成形体形成用スラリーは、本発明の耐火成形体の製法1で用いる耐火成形体形成材料に比べて一般に流動性が高いものであるために、束状の無機繊維集合体として、比較的長さの長いものを使用することができる。
本発明の耐火成形体の製法2において、耐火成形体の形成材料が、表面にガラス転移温度40℃以下の樹脂を被覆してなる束状の無機繊維集合体を上記の割合で含有することにより、得られる耐火成形体に十分な靱性を付与することができる。
耐火成形体形成用スラリー中の繊維成分の含有割合は、固形分換算で5質量%以下であることが好ましい。
本出願書類において、繊維成分とは、上記束状の無機繊維集合体とは区別されるものであり、成形性を確保するために添加される短繊維を意味するものとし、本発明の耐火成形体の製法2において、耐火成形体形成用スラリーが繊維成分を含むことにより、後述する脱水成形時における成形性を向上させることができる。
耐火成形体形成用スラリーがバインダーを含むことにより、無機粒子等を十分に結合させ、得られる耐火成形体に十分な強度を付与し易くなるが、本発明の耐火成形体の製法2においては、バインダーを含まなくても得られる耐火成形体に十分な強度を付与することができ、バインダーを含まない場合には得られる耐火成形体の熱伝導性を効果的に低減することができる。
本発明の耐火成形体の製造方法において、スラリーは液体媒体として水以外の媒体を含む場合もあるが、本出願書類においては、水以外の液体媒体を除去する場合も脱水成形と称することとする。
脱水成形物は、得ようとする耐火成形体に相似する形状を有するものが適当であり、例えば、円筒状、有底筒状、ボード状、ブロック状のものを挙げることができる。
また、水熱処理時間も特に制限されず、得ようとするケイ酸カルシウム粒子の種類や水熱処理時の水蒸気圧に応じて適宜選択することができる。例えば、石灰原料粉末とケイ酸原料粉末とを14kg/cm2以上の水蒸気圧下で水熱処理してゾノトライト粒子を得ようとする場合、水熱処理時間は5~48時間であることが適当である。
水熱処理温度も特に制限されず、得ようとするケイ酸カルシウム粒子の種類、水熱処理時の水蒸気圧、水熱処理時間等に応じて適宜選択することができる。
乾燥処理温度は、50~300℃であることが好ましく、100~200℃であることがより好ましい。
また、乾燥処理時間は1~24時間であることが好ましい。乾燥処理雰囲気は、大気雰囲気であることが好ましい。
具体的には、本発明の耐火成形体の製法1により本発明の耐火成形体1を好適に作製することができ、本発明の耐火成形体の製法2により本発明の耐火成形体2を好適に作製することができる。
また、本発明の耐火成形体が、無機粒子と、束状の無機繊維集合体とを含んでなり、バインダーを含まないものである場合には、例えば、本発明の耐火成形体の製法1において、バインダーを含まない耐火成形体形成材料を調製した上で、泥しょう鋳込み(スリップキャスト)法により成形することにより作製することができる。
泥しょう鋳込み(スリップキャスト)法は、溶媒を用いて適度な粘度に調整した耐火成形体形成材料を多孔質材からなる成形型に流し込み、溶媒を成形型に吸収させることによって所望厚みを有する目的物に成形する方法であり、本法によれば、耐火成形体形成材料を成形型に緻密に充填して、耐火成形体形成材料がバインダーを含まない場合であっても高密度な耐火成形体を作製することができる。
次に、本発明の金属鋳造用部材について説明する。
本発明の金属鋳造用部材は、無機粒子と、束状の無機繊維集合体とを含んでなり、前記無機粒子間に前記束状の無機繊維集合体が分散された内部構造を有する耐火成形体により、少なくともその表面が形成されてなることを特徴とするものである。
本発明の金属鋳造用部材は、その形状が金属鋳造用部材用途に成形されてなるものに限定される点を除けば、本発明の耐火成形体と同様であり、金属鋳造用部材を構成する無機粒子や束状の無機繊維集合体等の具体例や好適な含有割合、得られる物性等も本発明の耐火成形体と同様である。
また、本発明の金属鋳造用部材を製造する方法も、製造物の形状が金属鋳造用部材の形状に限定される点を除けば、本発明の耐火成形体の製法1または耐火成形体の製法2と同様であり、上述した耐火成形体形成材料を所望の成形面形状を有する成形型に充填したり、上述した耐火成形体形成用スラリーを、脱水成形し、水熱処理した後、乾燥処理することにより作製することができる。
金属製ケーシング表面に貼り付ける内張材は、その形状が薄板状等の形状に特定されることを除けば、本発明の耐火成形体の製法1または耐火成形体の製法2と同様の方法で作製することができる。
上記内張材を、適宜モルタル等を用いて金属製ケーシング表面に貼り付けることにより、本発明の金属鋳造用部材を作製することができる。
表1に示すように、バインダーとして、ハイアルミナセメントを30.0質量部含み、無機粒子として、シリカを40.0質量部、ワラストナイト粒子を30.0質量部含み、表面にガラス転移温度40℃以下の樹脂を被覆してなる束状の無機繊維集合体としてアクリロニトリル・ブタジエン共重合体ラテックスコーティングガラス繊維チョップドストランド(ひき揃えたガラス連続繊維をチョップド(切断)して得た直径1mm、長さ10mmの束状のガラス繊維集合体の表面に、該束状のガラス繊維集合体100質量部に対しガラス転移温度-31℃のアクリロニトリル・ブタジエン共重合体ラテックス樹脂10質量部を被覆したもの)を2.2質量部含むように、耐火成形体形成材料の固形分を秤り取り、ニーダー中に充填した。次いで、上記ニーダー中に、上記耐火成形体形成材料の固形分(セメント、無機粒子および樹脂を被覆してなる束状の無機繊維集合体)100質量部に対して15質量部の水を添加して、10分間混練することにより混練物を作製した。
上記混練物を、ラドル形状に対応した型枠形状を有し、支持部材を配置してなる成形型中に流し込み、105℃で24時間乾燥した後、さらに700℃で3時間焼成することにより、図1に示すような、内容量が6Lで最薄部の厚みが1cmである支持部材付のラドル1を作製した。得られたラドル1は、ラドル本体部2と支持部材3とを有してなるものであり、スやボイド等の空隙は観察されなかった。得られたラドルを構成する耐火成形体の組成を表2に示す。
また、図2に示すように、(図中に黒塗りで示す)取鍋形状に対応した形状を有する金属ケーシング5上に、上記混練物を厚さ50mmになるように塗工し、105℃で24時間乾燥した後、さらに700℃で3時間焼成することにより、(図中に斜線で示す)耐火性内張材6を形成して、取鍋4を作製した。得られた取鍋には、スやボイド等の空隙は観察されなかった。
セメントと、無機粒子と、表面にガラス転移温度40℃以下の樹脂を被覆してなる束状の無機繊維集合体の配合割合を表1に示すとおり変更した以外は、実施例1と同様にして支持部材付のラドルを作製した。得られた各ラドルには、スやボイド等の空隙は観察されなかった。得られたラドルを構成する耐火成形体の組成を表2に示す。
また、各実施例で得られた混練物を用いて、実施例1と同様にしてタップフロー値を測定した。結果を表1に示す。さらに、上記混練物を用いて実施例1と同様にして四角柱状の成形物を作製し、実施例1と同様にして各成形物の嵩密度と、シャルピー衝撃値とを測定した。結果を表2に示す。上記各成形物の破断面を目視観察したところ、いずれもセメントで結合された無機粒子間に束状の無機繊維集合体が均一に分散していることを確認できた。
表3に示すように、アクリロニトリル・ブタジエン共重合体ラテックスコーティングガラス繊維チョップドストランドに代えて、樹脂コーティングしていないガラス繊維チョップドストランド(ひき揃えたガラス連続繊維をチョップドして得た直径1mm、長さ10mmの束状のガラス繊維集合体)を用いた以外は、実施例1と同様にして支持部材付のラドルを作製した。得られたラドルには、直径2cm以上の空隙が生成していることを確認することができた。得られたラドルを構成する耐火成形体の組成を表4に示す。
また、上記ラドルの作製に使用した混練物を用いて、実施例1と同様にしてタップフロー値を測定した。結果を表3に示す。さらに、上記混練物を用いて実施例1と同様にして四角柱状の成形物を作製し、実施例1と同様にして成形物の嵩密度を測定した。結果を表4に示す。上記成形物の破断面を目視観察したところ、束状のガラス繊維集合体が解繊して、個々のガラス繊維が無機粒子間に分散していることを確認できた。
セメントと、無機粒子と、樹脂コーティングしていないガラス繊維チョップドストランドの配合割合を表3に示すとおり変更した以外は、比較例1と同様にして支持部材付のラドルを作製しようとしたが、原料混練物の流動性が低く、いずれも成形することができなかった。
表5に示すように、表面にガラス転移温度40℃以下の樹脂を被覆してなる束状の無機繊維集合体として、アクリロニトリル・ブタジエン共重合体ラテックスコーティングガラス繊維チョップドストランドに代えて、アクリロニトリル・ブタジエン共重合体ラテックスコーティングシリカ繊維チョップドストランド(ひき揃えたシリカ連続繊維をチョップドして得た直径1mm、長さ10mmの束状のシリカ繊維集合体の表面に、該束状のシリカ繊維集合体100質量部に対しガラス転移温度-31℃のアクリロニトリル・ブタジエン共重合体ラテックス10質量部を被覆したもの)を用い、セメントと、無機粒子と、表面にガラス転移温度40℃以下の樹脂を被覆してなる束状の無機繊維集合体の配合割合を表5に示すとおり変更した以外は、実施例1と同様にして支持部材付のラドルを作製した。得られた各ラドルには、スやボイド等の空隙は観察されなかった。得られたラドルを構成する耐火成形体の組成を表6に示す。
表面にガラス転移温度40℃以下の樹脂を被覆してなる束状の無機繊維集合体として、アクリロニトリル・ブタジエン共重合体ラテックスコーティングガラス繊維チョップドストランドに代えて、アクリロニトリル・ブタジエン共重合体ラテックスコーティングアルミナ繊維チョップドストランド(ひき揃えたアルミナ連続繊維をチョップドして得た直径1mm、長さ10mmの束状のアルミナ繊維集合体の表面に、該束状のアルミナ繊維集合体100質量部に対しガラス転移温度-31℃のアクリロニトリル・ブタジエン共重合体ラテックス10質量部を被覆したもの)を用い、セメントと、無機粒子と、表面にガラス転移温度40℃以下の樹脂を被覆してなる束状の無機繊維集合体の配合割合を表5に示すとおり変更した以外は、実施例1と同様にして支持部材付のラドルを作製した。得られた各ラドルには、スやボイド等の空隙は観察されなかった。得られたラドルを構成する耐火成形体の組成を表6に示す。
表面にガラス転移温度40℃以下の樹脂を被覆してなる束状の無機繊維集合体として、アクリル樹脂コーティングガラス繊維チョップドストランドに代えて、アクリロニトリル・ブタジエン共重合体ラテックスとポリスチレンの混合樹脂コーティングガラス繊維チョップドストランド(ひき揃えたガラス連続繊維をチョップドして得た直径1mm、長さ10mmの束状のガラス繊維集合体の表面に、該束状のガラス繊維集合体100質量部に対しガラス転移温度-31℃のアクリロニトリル・ブタジエン共重合体ラテックスとポリスチレンの混合樹脂(質量比でアクリロニトリル・ブタジエン共重合体ラテックス量:ポリスチレン樹脂量=7:3の混合樹脂)10質量部を被覆したもの)を用い、セメントと、無機粒子と、表面にガラス転移温度40℃以下の樹脂を被覆してなる束状の無機繊維集合体の配合割合を表7に示すとおり変更した以外は、実施例1と同様にして支持部材付のラドルを作製した。得られたラドルには、スやボイド等の空隙は観察されなかった。得られたラドルを構成する耐火成形体の組成を表8に示す。
アクリロニトリル・ブタジエン共重合体ラテックスコーティングガラス繊維チョップドストランドに代えて、ポリスチレンコーティングガラス繊維チョップドストランド(ひき揃えたガラス連続繊維をチョップドして得た直径1mm、長さ10mmの束状のガラス繊維集合体100質量部に対し、ガラス転移温度70℃のポリエステル樹脂を10質量部被覆したもの)を用い、セメントと、無機粒子と、ポリスチレンコーティングガラス繊維チョップドストランドの配合割合を表7に示すとおり変更した以外は、実施例1と同様にして支持部材付のラドルを作製しようとしたが、原料混練物の流動性が低く、成形することができなかった。
バインダーとして、ハイアルミナセメントに代えて、固形分濃度が95質量%であるリン酸アルミニウムを用い、該リン酸アルミニウムと、無機粒子と、表面にガラス転移温度40℃以下の樹脂を被覆してなる束状の無機繊維集合体の配合割合を表9に示すとおり変更した以外は、実施例1と同様にして支持部材付のラドルを作製した。得られた各ラドルには、スやボイド等の空隙は観察されなかった。得られたラドルを構成する耐火成形体の組成を表10に示す。
表11に示すように、水800質量部に対し、無機粒子であるケイ酸カルシウム粒子の原料として、生石灰粉末25質量部および珪石粉末25質量部、ケイ酸カルシウム粒子として、予め攪拌式オートクレーブで合成したゾノトライトスラリーを固形分換算で10質量部とワラストナイト粒子(米国インターペース社製NYARD-G)40質量部、表面にガラス転移温度40℃以下の樹脂を被覆してなる束状の無機繊維集合体として、アクリロニトリル・ブタジエン共重合体ラテックスコーティングガラス繊維チョップドストランド(Eガラス繊維ロービング(繊度270tex)をチョップド(切断)して得た、繊度270tex、直径0.5mm、長さ50mmの束状のガラス繊維集合体の表面に、該束状のガラス繊維集合体100質量部に対しガラス転移温度-31℃のアクリロニトリル・ブタジエン共重合体ラテックス樹脂10質量部を被覆したもの)3質量部を混合し、さらに、耐アルカリ性ガラス繊維(日本電気硝子(株)製)3質量部を充分に混合して耐火成形体形成用スラリーを作製した。
得られた耐火成形体の曲げ強度をJIS A 1408の規定に従って測定したところ、8.0MPaであった。また、得られた耐火成形体のシャルピー衝撃値をJIS R 1662の規定に従って測定したところ、1.5mJ/mm2であった。結果を表12に示す。
表面にガラス転移温度40℃以下の樹脂を被覆してなる束状の無機繊維集合体の配合量を表11に示すとおり変更した以外は、実施例19と同様にして平板状の耐火成形体(乾燥体)を作製した。得られた各耐火成形体には、スやボイド等の空隙は観察されなかった。また、上記各成形物の破断面を目視観察したところ、いずれもケイ酸カルシウム粒子間に束状の無機繊維集合体が均一に分散していることを確認できた。
得られた耐火成形体の組成および嵩密度を表12に示す。また、得られた各耐火成形体の曲げ強度およびシャルピー衝撃値を実施例19と同様に測定した。結果を表12に示す。
さらに、上記各耐火成形体を500℃で12時間焼成して得られた焼成体の嵩密度、曲げ強度およびシャルピー衝撃値を実施例19と同様に測定した。結果を表12に示す。
表13に示すように、表面にガラス転移温度40℃以下の樹脂を被覆してなる束状の無機繊維集合体3重量部に代えて、表面に樹脂を被覆していない束状の炭素繊維チョップドストランド(東邦テナックス(株)製、長さ6mm)3質量部を用いた以外は、実施例19と同様にして平板状の耐火成形体(乾燥体)を作製した。得られた耐火成形体の組成および嵩密度を表14に示す。得られた耐火成形体の破断面を目視観察したところ、束状の炭素繊維が開繊していることを確認できた。また、得られた各耐火成形体の曲げ強度およびシャルピー衝撃値を実施例19と同様に測定した。結果を表14に示す。
さらに、上記耐火成形体を500℃で12時間焼成して得られた焼成体の曲げ強度およびシャルピー衝撃値を実施例19と同様に測定した。結果を表14に示す。
表面にガラス転移温度40℃以下の樹脂を被覆してなる束状の無機繊維集合体に代えて、表面に樹脂被覆していない束状の無機繊維集合体(Eガラス連続繊維(135texの合糸2本を撚り合わせてなる、繊度が270texで、25mm当たりの撚り数が4.4であるもの)を引き揃えた状態でチョップド(切断)して得た、繊度270tex、直径0.5mm、長さ50mmの束状のガラス繊維集合体)を用い、該束状の無機繊維集合体の配合量を表13に示すとおりとした以外は、実施例19と同様にして平板状の耐火成形体(乾燥体)を作製した。
比較例7において、得られた耐火成形体の破断面を目視観察したところ、束状の無機繊維集合体が開繊していることを確認できた。比較例8~比較例10においては、束状の無機繊維集合体が開繊して耐火成形体形成用スラリーの粘度が上昇し成形性が悪化してしまい、成形体にスやボイド等の空隙を生じて、いずれも均一な成形体を得ることができなかった。
得られた耐火成形体の組成および嵩密度を表14示す。また、比較例7で得られた各耐火成形体の曲げ強度およびシャルピー衝撃値を実施例19と同様に測定した。結果を表14に示す。さらに、比較例7で得られた耐火成形体を500℃で12時間焼成して得られた焼成体の嵩密度、曲げ強度およびシャルピー衝撃値を実施例19と同様に測定した。結果を表14に示す。
表15に示すように、表面にガラス転移温度40℃以下の樹脂を被覆してなる束状の無機繊維集合体の長さを、それぞれ10mm(実施例23)および120mm(実施例24)に変更した以外は、実施例20と同様にして平板状の耐火成形体(乾燥体)を作製した。得られた各耐火成形体には、スやボイド等の空隙は観察されなかった。また、上記各成形物の破断面を目視観察したところ、いずれもケイ酸カルシウム粒子間に束状の無機繊維集合体が均一に分散していることを確認できた。
得られた耐火成形体の組成および嵩密度を表16に示す。また、得られた各耐火成形体のシャルピー衝撃値を実施例19と同様に測定した。結果を表16に示す。
さらに、上記各耐火成形体を500℃で12時間焼成して得られた焼成体の嵩密度およびシャルピー衝撃値を実施例19と同様に測定した。結果を表16に示す。
表17に示すように、表面にガラス転移温度40℃以下の樹脂を被覆する束状の無機繊維集合体として、実施例25では、耐アルカリガラス連続繊維(耐アルカリガラス繊維ロービング(日本電気硝子(株)製、繊度270tex)をチョップド(切断)して得た、繊度270tex、長さ50mmの束状の無機繊維集合体を用い、実施例26では、ガラス繊維合撚糸(135texのEガラス繊維合糸2本を撚り合わせてなる、繊度が270texで、25mm当たりの撚り数が4.4であるもの)をチョップド(切断)して得た、繊度270tex、直径0.5mm、長さ50mmの束状の無機繊維集合体を用い、実施例27では、耐アルカリガラス繊維合撚糸(135texの耐アルカリガラス繊維合糸2本を撚り合わせてなる、繊度が270texで、25mm当たりの撚り数が4.4であるもの)をチョップド(切断)して得た、繊度270tex、長さ50mmの束状の無機繊維集合体を用いた以外は、実施例20と同様にして平板状の耐火成形体(乾燥体)を作製した。得られた各耐火成形体には、スやボイド等の空隙は観察されなかった。また、上記各成形物の破断面を目視観察したところ、いずれもケイ酸カルシウム粒子間に束状の無機繊維集合体が均一に分散していることを確認できた。
得られた耐火成形体の組成および嵩密度を表18に示す。また、得られた各耐火成形体のシャルピー衝撃値を実施例19と同様に測定した。結果を表18に示す。
さらに、上記各耐火成形体を500℃で12時間焼成して得られた焼成体の嵩密度およびシャルピー衝撃値を実施例19と同様に測定した。結果を表18に示す。
2 ラドル本体部
3 支持部材
4 取鍋
5 金属製ケーシング
6 耐火性内張材
Claims (18)
- 無機粒子と、束状の無機繊維集合体とを含んでなり、前記無機粒子間に前記束状の無機繊維集合体が分散された内部構造を有することを特徴とする耐火成形体。
- バインダーと、無機粒子と、束状の無機繊維集合体とを含んでなり、前記バインダーで結合された前記無機粒子間に前記束状の無機繊維集合体が分散された内部構造を有する請求項1に記載の耐火成形体。
- 前記バインダーを1~50質量%、前記無機粒子を30~95質量%、前記束状の無機繊維集合体を1~30質量%含んでなる請求項2に記載の耐火成形体。
- 前記束状の無機繊維集合体の直径が0.01~5mmであり、長さが3~30mmである請求項2または請求項3に記載の耐火成形体。
- 前記無機粒子としてケイ酸カルシウム粒子を含むとともに、束状の無機繊維集合体を含んでなり、前記ケイ酸カルシウム粒子間に前記束状の無機繊維集合体が分散された内部構造を有する請求項1に記載の耐火成形体。
- 前記無機粒子を65~99質量%、前記束状の無機繊維集合体を1~30質量部含んでなる請求項5に記載の耐火成形体。
- 前記束状の無機繊維集合体の直径が0.01~5mmであり、長さが3~200mmである請求項5または請求項6に記載の耐火成形体。
- JIS R 1662により測定したときのシャルピー衝撃値が0.5~10mJ/mm2である請求項1~請求項7のいずれか1項に記載の耐火成形体。
- 無機粒子と、表面にガラス転移温度40℃以下の樹脂を被覆してなる束状の無機繊維集合体とを含む耐火成形体形成材料を混練した後、得られた混練物を成形することを特徴とする耐火成形体の製造方法。
- バインダーと、無機粒子と、表面にガラス転移温度40℃以下の樹脂を被覆してなる束状の無機繊維集合体とを含む耐火成形体形成材料を混練した後、得られた混練物を成形する請求項9に記載の耐火成形体の製造方法。
- 前記耐火成形体形成材料が、固形分中に、前記バインダーを1~50質量%、前記無機粒子を30~95質量%、前記表面にガラス転移温度40℃以下の樹脂を被覆してなる束状の無機繊維集合体を1~30質量%含む請求項10に記載の耐火成形体の製造方法。
- JIS R 5201により測定したときの前記混練物のタップフロー値が150mm以上である請求項10または請求項11に記載の耐火成形体の製造方法。
- ケイ酸カルシウム粒子の原料を含むとともに、表面にガラス転移温度40℃以下の樹脂を被覆してなる束状の無機繊維集合体を含む耐火成形体形成用スラリーを、脱水成形し、次いで水熱処理した後、乾燥処理することを特徴とする耐火成形体の製造方法。
- 前記ケイ酸カルシウム粒子の原料が石灰原料粉末およびケイ酸原料粉末である請求項13に記載の耐火成形体の製造方法。
- 前記水熱処理を7kg/cm2以上の水蒸気圧下で行う請求項14に記載の耐火成形体の製造方法。
- 前記耐火成形体形成用スラリーが、固形分中に、前記無機粒子の原料100質量部に対し、前記表面にガラス転移温度40℃以下の樹脂を被覆してなる束状の無機繊維集合体を1~30質量部含む請求項13~請求項15のいずれかに記載の耐火成形体の製造方法。
- 前記表面にガラス転移温度40℃以下の樹脂を被覆してなる束状の無機繊維集合体が、束状の無機繊維集合体100質量部に対してガラス転移温度40℃以下の樹脂を1~30質量部被覆してなるものである請求項9~請求項16のいずれか1項に記載の耐火成形体の製造方法。
- 無機粒子と、束状の無機繊維集合体とを含んでなり、前記無機粒子間に前記束状の無機繊維集合体が分散された内部構造を有する耐火成形体により、少なくともその表面が形成されてなることを特徴とする金属鋳造用部材。
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