WO2003076358A1 - Composite inorganique et procede de production associe - Google Patents

Composite inorganique et procede de production associe Download PDF

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Publication number
WO2003076358A1
WO2003076358A1 PCT/JP2003/002591 JP0302591W WO03076358A1 WO 2003076358 A1 WO2003076358 A1 WO 2003076358A1 JP 0302591 W JP0302591 W JP 0302591W WO 03076358 A1 WO03076358 A1 WO 03076358A1
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Prior art keywords
inorganic
inorganic composite
slurry
water
producing
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PCT/JP2003/002591
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English (en)
Japanese (ja)
Inventor
Naoyuki Tsuda
Naoaki Fujita
Masaki Tsujino
Kyon Hun Min
Atsuyoshi Takenaka
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Asahi Glass Company, Limited
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Priority claimed from JP2002065930A external-priority patent/JP2002338329A/ja
Application filed by Asahi Glass Company, Limited filed Critical Asahi Glass Company, Limited
Priority to AU2003211707A priority Critical patent/AU2003211707A1/en
Publication of WO2003076358A1 publication Critical patent/WO2003076358A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/34—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders

Definitions

  • the present invention relates to an inorganic composite suitable for wall materials and the like and a method for producing the same.
  • Ceramic-based siding is widely used as a design material for exterior materials of houses. In recent years, ceramic-based siding with higher design properties has been demanded, and the design of ceramic siding has been improved by making the ceramic siding surface uneven.
  • a material obtained by forming and firing a slurry composed of aluminum dihydrogen phosphate, alumina, acrylamide and water has been proposed. See Table 1 in Japanese Patent Application Laid-Open No. 2002-1773357.
  • An object of the present invention is to provide an inorganic composite that can solve such a problem. Disclosure of the invention
  • the present invention provides a method for producing an inorganic composite by heating an inorganic slurry obtained by adding reinforcing fibers to a water-containing slurry containing a metal hydrogenphosphate, a curing agent, a curing retarder and water.
  • a method for producing an inorganic composite wherein the content of the curing retarder in the slurry in terms of percentage by mass is 0.05 to 30%.
  • 1 and 2 are graphs showing the behavior of the elastic modulus of a sample when the temperature of the sample of the inorganic slurry in Example or Comparative Example of the present invention was raised from room temperature to 37 Ot :.
  • Curve a in FIG. 1 is Experimental Example 1 (sample using 10.0 g of sodium ultrapolyphosphate), curve b is Experimental Example 2 (sample using 1.0 g of sodium ultrapolyphosphate), and curve c is an experimental example 3 (sample using 25.0 g of sodium ultrapolyphosphate).
  • Curve d in Fig. 2 is experimental example 6 (sample using 9.53 g of sodium metaphosphate), curve e is experimental example 7 (sample using 0.18 g of sodium metaphosphate), and curve f is an experimental example. 8 (sample using 51.05 g of sodium metaphosphate), and curve g is Experimental Example 16 (sample not using sodium metaphosphate).
  • B) in Fig. 3 is a photograph of the same thing as (a) seen from obliquely above.
  • the inorganic composite is a composite containing a matrix mainly composed of an inorganic substance and reinforcing fibers.
  • the reinforcing fibers are usually dispersed in the matrix.
  • the water-containing slurry contains water, a metal hydrogen phosphate, a curing agent thereof, and a curing retarder. Further, other components such as a filler may be contained as necessary.
  • the inorganic slurry comprises a water-containing slurry and reinforcing fibers. In the following, dry In some cases, the water content is simply reduced due to the above or the like, or the green sheet (uncured) described later is also referred to as an inorganic slurry.
  • the green sheet is dried so that the inorganic slurry is kept at a temperature of 100 or less to reduce the water content to 3 to 15%, more typically 6 to 15%.
  • the green sheet is heated and hardened, and is formed into a desired shape as needed during the hardening to form an inorganic composite.
  • a reinforcing fiber is added to the water-containing slurry to prepare an inorganic slurry having a water content of more than 15% and 50% or less, and the inorganic slurry is heated at a temperature of 100 T or less.
  • the inorganic slurry is heated at a temperature of 100 T or less.
  • the temperature at which the green sheet is heated is more preferably from 160 to 250.
  • the green sheet during the curing while heating the green sheet to 150 to 250 V.
  • the temperature at which the green sheet is heated is from 160 to 250.
  • First step Aqueous metal hydrogen phosphate solution, its curing agent and curing retarder are mixed and kneaded to obtain a water-containing slurry. Water and various additives may be added to the water-containing slurry as needed.
  • Second step An inorganic slurry is obtained by combining the water-containing slurry with the reinforcing fibers. It is preferable that the inorganic slurry contains water-containing slurry at 100 parts by mass and reinforcing fibers at a ratio of 5 to 40 parts by mass. Further, it is preferable to determine the reinforcing fiber content in the inorganic slurry so that the reinforcing fiber content in the inorganic composite is 3 to 40% by volume.
  • a water-containing slurry is used instead of the resin in the hand lay-up method or the spray-up method used when manufacturing glass fiber reinforced plastic.
  • An example of the method of impregnation is shown below.
  • the method of combining the 7j-containing slurry with the reinforcing fibers is limited to these. However, it can be appropriately selected depending on the molding method, the use of the inorganic composite, and the like.
  • the sheet it is preferable to process the sheet into a shape suitable for molding.
  • the inorganic slurry is dried, for example, at 100 or less to reduce the water content to 3 to
  • the water content is calculated by assuming the difference between one mass of the inorganic slurry before drying and the mass of the inorganic slurry after drying as the amount of vaporized water. Since the amount of water of crystallization mixed from the metal salt of hydrogen phosphate or the like is very small, the above calculation is performed on the assumption that the amount of water of crystallization in the inorganic slurry is zero.
  • a preferred range of the water content is 6 to 10%.
  • Drying is preferably performed, for example, at 30 to 60 for 10 to 50 hours.
  • the elastic modulus at its 2 5 dries such that 1 0 8 ⁇ 1 0 1 G P a inorganic slurry in the second step It can be provided when it is formed in a sheet shape on the upper surface of a carrier material, but is not essential.
  • This step is preferably provided when it is desired to reduce the amount of water vaporized from) and prevent expansion of the uncured material due to rapid vaporization of water inside the uncured material.
  • the inorganic slurry or the dried inorganic slurry (green sheet) is heated from room temperature to 250 and gradually softened by heating. As the temperature increases, the inorganic slurry softens gradually and its modulus decreases and reaches a minimum, after which the modulus increases as curing progresses.
  • the flexibility of the uncured body in a softened state due to such heating is represented by a bending characteristic R measured as follows. If the uncured material in the softened state is bent without causing cracks, a semicircle is formed in the bent portion. When bending the uncured body, it should be rounded into a cylinder, or when the uncured body is flexible, it should be folded.
  • R is preferably 1 to 5, more preferably 1 to 3.
  • Fig. 3 (a) is a photograph of the side surface of the uncured body that has been bent, and Fig. 3 (b) is a photograph of the oblique upper part.
  • the t of the uncured material shown in Fig. 3 is about 2 mm.
  • the inorganic slurry in the method of the present invention preferably has a water content of 6 to 15%, the R of the uncured product is preferably 1 to 5, and the minimum elasticity of the uncured product. rate is preferably 1 0 5 ⁇ 1 0 8 P a .
  • the curing of the inorganic slurry is delayed by adding a curing retarder to the water-containing slurry, and as described above, a decrease in the elastic modulus or an increase in flexibility of the uncured material during heating can be obtained.
  • the uncured body By increasing the flexibility of the uncured body, the workability is increased, and the uncured body can be formed into a complex shape or a shape with deep irregularities in the next molding process, and it has excellent design An inorganic composite can be obtained.
  • the length exceeds 5
  • the flexibility becomes small, and the uncured body may be damaged by the pressure applied during the molding process, or the uncured body may harden before it can be molded into a desired shape.
  • the inorganic slurry (uncured body) softened as described above is formed into a desired shape such as a plate shape, a corrugated plate shape, or an irregular shape according to the use of the inorganic composite.
  • the inorganic slurry softened (uncured material) are those that modulus of 1 0 5 ⁇ 1 0 8 P a or before SL minimum modulus are preferred.
  • the shaping is performed, for example, at a temperature of 160 to 250 at a pressure of 3.0 to 5.0 MPa for several minutes.
  • Step 6 When the temperature is further increased by heating from the temperature at which the inorganic slurry (green sheet) was softened in the fourth step, the elastic modulus of the inorganic slurry gradually increases, and the hardening of the inorganic slurry proceeds.
  • the heating temperature is preferably from 160 to 250.
  • Examples of the forming apparatus include a mold press, a flat plate press, a belt press, and a roll press.
  • steps 4 to 6 can be performed successively in the same molding apparatus.
  • the phosphate group and its hardener may remain in the formed inorganic slurry (phosphate-based inorganic formed body) after the completion of the sixth step, the remaining phosphate group is determined.
  • the inorganic slurry may be taken out of the molding apparatus and heated again. This heating is preferably carried out at 160-250 for about 1-20 hours.
  • the flexural fracture strength is 25 MPa or more and the elastic modulus (flexural modulus) is 15 GPa or more, and building materials such as building exterior materials and the like which require high strength are used.
  • An inorganic composite (phosphate-based inorganic molded article) suitable for industrial members and the like can be produced.
  • the metal hydrogen phosphate is a component that improves the fluidity of the inorganic slurry during molding and processing, and also densifies the structure of the obtained molded body (inorganic composite), and is essential. Its content is preferably 15 to 35%, more preferably 20 to 30%.
  • the metal hydrogen phosphate is preferably used as an aqueous solution or aqueous dispersion when preparing a water-containing slurry.
  • Metal hydrogen phosphate is a metal phosphate having at least one hydroxyl group bonded to a phosphorus atom, that is, metal dihydrogen phosphate (metal primary phosphate), metal sesquiphosphate and monophosphate.
  • metal dihydrogen phosphate metal primary phosphate
  • metal sesquiphosphate metal sesquiphosphate
  • monophosphate A generic term for hydrogen metal salts (secondary metal phosphate salts).
  • the metal hydrogen phosphate is preferably a metal dihydrogen phosphate.
  • the metal constituting the metal hydrogen phosphate is preferably a trivalent metal such as aluminum and a divalent metal such as magnesium, calcium and zinc, and particularly preferably aluminum.
  • Hydrogen phosphate metal salt is aluminum dihydrogen phosphate (aluminum primary phosphate: A 1 (H 2 P0 4 ) 3), monohydrogen phosphate aluminum (second aluminum phosphate: A 1 2 (HP0 4) 3 ), magnesium dihydrogen phosphate (magnesium primary phosphate: Mg (H 2 P0 4) 2), and dihydrogen phosphate: zinc group consisting (first zinc phosphate Zn (H 2 P ⁇ 4) 2) It is preferably at least one metal hydrogen phosphate selected from the group consisting of: Among them, aluminum dihydrogen phosphate, which has excellent solubility in water, easy handling of an aqueous solution, and economical efficiency, is particularly preferable.
  • Some hydrogen phosphate metal salts are commercially available not only in aqueous solution but also in solid form. If a combination of aqueous solution and solid form is used, as described in the description of the third step, It is easy to adjust the water content before the temperature rise (softening) of the inorganic slurry.
  • examples of the metal sesquiphosphate include aluminum sesquiphosphate
  • examples of the metal monohydrogen phosphate include aluminum monohydrogen phosphate and iron monohydrogen phosphate. Since metal sesquiphosphate and metal monohydrogen phosphate both have poor solubility in water unlike metal dihydrogen phosphate, metal sesquiphosphate or metal monohydrogen phosphate is dispersed in water. It is preferable to use it as an aqueous dispersion.
  • the curing agent is a curing agent for the metal hydrogen phosphate, that is, a material which is mixed with the metal hydrogen phosphate and heated to react with the metal hydrogen phosphate and harden it.
  • the content of the curing agent is preferably 25 to 45%. If it is less than 25%, the 7-containing slurry, that is, the inorganic slurry containing the slurry is molded, heated, and cured, and the phosphoric acid-based inorganic molded article (inorganic composite) obtained has metal hydrogen hydrogen phosphate remaining therein. There is a possibility that the strength of the molded article becomes insufficient or its water resistance is reduced. It is more preferably at least 30%. If it exceeds 45%, the ratio of the metal salt of hydrogen phosphate to the curing agent becomes too small, and the matrix of the molded product may become coarse and its strength may be insufficient. It is more preferably at most 40%. Examples of the curing agent include metal hydroxides, metal oxides and silicates, and one or a combination of two or more of these can be used.
  • the curing agent is selected from the group consisting of one or more metal hydroxides selected from the group consisting of aluminum hydroxide, calcium hydroxide and magnesium hydroxide, aluminum oxide, magnesium oxide, zinc oxide and calcium oxide.
  • the above metal oxide or wollastonite (calcium silicate) is preferable.
  • the curing retarder is used for retarding the curing of the inorganic slurry, and is essential.
  • the content of the curing retarder is preferably 0.05 to 30%. If it is less than 0.05%, the above-mentioned R may become too large. More preferably, it is 1% or more. If it exceeds 30%, the viscosity of the water-containing slurry becomes too large, and it may be difficult to prepare an inorganic slurry. It is more preferably at most 25%.
  • the curing retarder is preferably a metal phosphate.
  • the metal phosphate is sodium phosphate excellent in water solubility. Further, in order to make the heat softening property of the inorganic slurry appropriate and to increase the strength of the molded body (inorganic composite), the molar ratio (P / Na) of sodium to phosphorus of the sodium phosphate is required. It is preferably one or more.
  • water is an essential component of the water-containing slurry, it may be contained in the form of an aqueous solution or aqueous dispersion of metal hydrogen phosphate or the like, as described above, or may be contained in the form of water alone. Is also good.
  • the 7K-containing slurry may contain components (additives) other than the above components in a range that does not impair the object of the present invention.
  • additives include lightweight aggregates or fillers for reducing the weight and cost of phosphoric acid-based inorganic molded products (inorganic composites), pigments for improving the design of molded products, and the like.
  • Shirasu balloons, glass balloons, pearlite, etc. are used as lightweight aggregates, silica sand, silica fume, glass powder, clay, etc. mainly containing acidic oxides are used as fillers, and titanium oxide, zinc oxide, phthalocyanine are used as pigments , Red stalks, mapico, and the like, respectively.
  • the inorganic slurry is obtained by adding reinforcing fibers to the water-containing slurry, and the addition ratio is 5 to 40 parts by mass, as described above, with the water-containing slurry being 100 parts by mass. preferable. If the amount is less than 5 parts by mass, the shape retention and strength of the inorganic slurry during softening may be insufficient. It is more preferably at least 10 parts by mass. If the amount exceeds 40 parts by mass, the matrix of the molded article (inorganic composite) may be coarse and the strength thereof may be insufficient.
  • reinforcing fibers those similar to the reinforcing materials used in conventional inorganic composite materials can be used.
  • short fibers or long fibers such as glass fibers, ceramic fibers, carbon fibers, and discs may be used.
  • Reinforcing fibers may be added using a product obtained by processing these short fibers or long fibers into mat, cloth, or the like.
  • the material and form of the reinforcing fibers are appropriately selected, and if necessary, one type may be used alone, or two or more types may be used in combination.
  • Examples of the glass composition of the glass fiber include A glass, E glass, ECR glass, S glass, and AR glass.
  • the ceramic fiber examples include an alumina fiber, a silicon-alumina fiber, and a silicon nitride fiber.
  • the reinforcing fiber it is preferable to use a glass fiber of E glass composition which is inexpensive and widely used.
  • the glass fibers of glass composition include those processed into short fibers such as milled fibers and chopped strands, continuous fibers (long fibers) such as yarns and rovings, mats, woven fabrics, and nonwoven fabrics. Can be used.
  • Alumina fibers, silicon-alumina fibers, whiskers, etc. can react with the metal hydrogen phosphate contained in the water-containing slurry, and have a wettability with the matrix or Adhesion is relatively good. Therefore, their surface treatment is not always necessary.
  • glass fibers and carbon fibers have relatively low reactivity with metal hydrogen phosphate, it is preferable to perform a surface treatment for applying a surface treatment agent containing an epoxy resin.
  • reinforcing fibers are dispersed in the inorganic matrix for the purpose of improving the strength of the composite.
  • the inorganic composite of the present invention is produced, for example, as follows using the method of the present invention.
  • a water-containing slurry to be fired to become an inorganic matrix is prepared.
  • a layer of an inorganic slurry in which the water-containing slurry is impregnated with a reinforcing fiber by a hand lay-up method or the like is formed in a sheet shape on a carrier such as a polyethylene terephthalate (PET) film.
  • PET polyethylene terephthalate
  • the sheet-like inorganic slurry was held at 60, for example, for 16 hours to form a sheet, and then the sheet was peeled off from the carrier, and further held, for example, at 60 for 8 hours, and dried to form a green sheet. I do.
  • the water content of the green sheet is typically 9 to 13%.
  • the green sheet is peeled off from the carrier, and if necessary, molding such as a hot press is performed at a temperature at or near a temperature at which the elastic modulus of the green sheet is minimized, and thereafter, typically, 150 to 250 ° C. And fired to form an inorganic composite.
  • Typical firing times are 15 to 20 hours at 150, 3 to 5 hours at 220, or 2 hours at 250. If firing is performed for more than 5 hours at 220 and for more than 2 hours at 250, the glass fiber may be deteriorated when glass fiber is used as the reinforcing fiber.
  • the above-described molding such as a heat press is performed. That is, heating is performed by applying a pressure of 20 to 5 OMPa to the green sheet preferably at 160 to 25 O :, more preferably at 160 to 20 O: for 2 to 30 minutes. Press and then Bake like a stick.
  • the inorganic matrix contains Na, Al, P, O.
  • N a and P, N a and P are all, (Alpha 1 Ro_ ⁇ 4) as in the form of (N a 2 0) x ( A 1 P0 4) ⁇ (Na 2 0) It is expressed by the x content and x.
  • X When X is less than 0.08, it becomes difficult to form deep irregularities on the surface, or the strength decreases. Preferably it is 0.09 or more. If it exceeds 0.38, the strength will decrease. Preferably it is 0.33 or less, more preferably 0.19 or less.
  • the content of the inorganic matrix in (A 1 P0 4) ⁇ ( Na 2 ⁇ ) x is preferably 30 to 70%. If it is less than 30%, it may be difficult to form deep irregularities on the surface, or the strength may be reduced. It is more preferably at least 35%, particularly preferably at least 40%. If it exceeds 70%, the strength may decrease. It is more preferably at most 60%, particularly preferably at most 55%.
  • a 1 Content of A 1 is represented by the content of both the A 1 is present in (A 1 P_ ⁇ 4) ⁇ (Na 2 ⁇ ) x and A 1 2 0 3 Neu Zureka form of.
  • the content of A 1 2 ⁇ 3 in this sense should not be 0. In the present invention with a and this this, that the inorganic matrix containing A 1 2 ⁇ 3.
  • the content of the A 1 2 ⁇ 3 is preferably 20 to 60%. If it is less than 20%, the firing time may be too long. It is more preferably at least 30%. If it exceeds 60%, it may be difficult to form deep irregularities on the surface, or the strength may be reduced. It is more preferably at most 50%.
  • the inorganic matrix preferably contains Ca and Si, though not essential.
  • C a O ⁇ S i 0 content of 2 0. 1 all either one of C a and S i is determined as in the form of C a 0 ⁇ S i 0 2 Preferably it is 10%. If it is less than 0.1%, the effect of improving releasability is small. It is preferably at least 1%. If it exceeds 10%, the strength may be reduced. It is preferably at most 6%, more preferably at most 4%.
  • Ca 2 O 3 SiO 2 crystals (wollastonite) exist in the inorganic matrix.
  • the inorganic matrix in the present invention consists essentially of the above components, but may contain other components as long as the purpose of the present invention is not impaired.
  • a metal element other than the above may be contained for the purpose of coloring or the like.
  • the total content be 10% or less, since the content ratio of these elements is represented by the content calculated assuming that each element forms an oxide with the lowest valence. Examples of the oxide, C r 2 ⁇ 3, M n O, F e 0, C O_ ⁇ , N i 0, C u O , Z n O, N b 2 ⁇ 5, W0 2, and the like.
  • an organic substance such as acrylamide may be contained, but the total content of the organic substance is preferably less than 5%.
  • the reinforcing fiber should be appropriately selected according to the use of the inorganic composite of the present invention, etc., and typically, glass fiber, steel fiber, carbon fiber and poly-P— One or more fibers selected from the group consisting of phenylene terephthalamide fibers. It is preferable to use glass fiber when the application is a wall material, etc.
  • the inorganic composite of the present invention essentially consists of 60 to 97% by volume of an inorganic matrix and 3 to 40% by volume of reinforcing fibers. Is preferred. If the reinforcing fiber content is less than 3% by volume, the strength of the inorganic composite may decrease.
  • the content is more than 40% by volume, the strength may be rather reduced, the fuzz on the surface of the inorganic composite material may be remarkable, and the design property may be reduced.
  • the inorganic matrix is 80-94% by volume and the reinforcing fibers are 6-20% by volume.
  • the flexural strength ⁇ of the inorganic composite of the present invention measured in accordance with the provisions of JIS K 7555, is preferably at least 38 3a.
  • the flexural modulus E measured according to the same rule is 6 GPa or more.
  • the measurement of ⁇ and ⁇ is performed under the following conditions.
  • Test method 3-point bending test.
  • This water-containing slurry was impregnated with 12.5 parts by mass of glass fiber (G5E, manufactured by Asahi Fiberglass Co., Ltd.) with 100 parts by mass of the slurry to form an inorganic slurry.
  • the glass fibers are chopped strand short fibers having a length of 30 mm.
  • the obtained inorganic slurry was applied to the upper surface of a PET film as a carrier material by a hand lapping method to form a sheet of about 20 OmmX 20 OmmX 2 mm.
  • the sheet was kept at 60 for about 24 hours and dried.
  • the water content of the dried sheet was 8%.
  • the PET film was peeled off from the dried sheet (green sheet), and the green sheet was cut into a size of 15 mm ⁇ 5 Omm ⁇ 2 mm to obtain a sample for elastic modulus measurement.
  • the sample bending module (Seiko Denshi Kogyo Co., Ltd.: D MS 110) modulus of from room temperature at a measuring frequency 1 H z at up to 370 i.e. actual elastic modulus E 5 (Unit: Pa) were measured.
  • the results are shown in FIG. 1 (curve a).
  • the figure The vertical axis of FIG. 2 to 1 and later a 1 og scale, for example, "1. 0 0 E + 0 6" is the meaning of 1 0 6.
  • Table 1 also shows the water content of the green sheet, the R and the minimum elastic modulus.
  • the temperature change of the elastic modulus is shown as curve b in FIG. Table 1 also shows the water content of the green sheet, the R and the minimum elastic modulus.
  • the temperature change of the elastic modulus is shown as a curve c in FIG. Table 1 also shows the water content of the green sheet, the R and the minimum elastic modulus.
  • Experimental Example 1 except that Ultra Sodium Polyphosphate was used, Experimental Example 4 was sodium metaphosphate (Kanto Kagaku Co., Ltd .: deer first grade), and Experimental Example 5 was disodium dihydrogen diphosphate (Kishida Chemical Co., Ltd.). (See Table 1).
  • Table 1 also shows the content after drying, that is, the water content of the green sheet, the R, and the minimum elastic modulus.
  • a water-containing slurry was obtained in the same manner as in Experimental Example 1, except that the composition shown in Table 2 was used and the kneading conditions were changed to about 500 rpm for about 10 minutes using a stirring blade having a diameter of 7 cm.
  • the sheet was kept at 60 for 2 days and dried.
  • the water content of the dried sheet was 10%.
  • the PET film was peeled off from the dried sheet (green sheet), and the daline sheet was cut into a size of 15 mm ⁇ 5 Omm ⁇ 2.5 mm to obtain a sample for elastic modulus measurement.
  • the elastic modulus from room temperature to 370 was measured in the same manner as in Experimental Example 1. The results are shown in FIG. 2 (curve d).
  • the elastic modulus of this sample was about 10 9 Pa at room temperature, but was 10 6 to 10 7 at 70 to 170. reduced to about a.
  • the minimum elastic modulus was 3 ⁇ 10 6 Pa, and when it exceeded 150, it began to increase and hardening started.
  • a sample (uncured body) was taken out at the stage of heating up to 170, and the bending characteristic R was examined. In other words, this sample could be bent with a radius of 2.5 mm so that it could be folded without any gaps.
  • Experimental Example 10 was disodium dihydrogen diphosphate (manufactured by Kishida Chemical), Experimental Example 11 was sodium tripolyphosphate (Kanto Chemical Co., Ltd .: deer grade 1), and Experimental Example 12 was methaline.
  • Experimental example 13 was aluminum metaphosphate (manufactured by Lhasa Industries), potassium metaphosphate (manufactured by Kanto Chemical Co., Ltd .: deer grade 1), and drying was performed at 60 for about 20 hours. (See Table 3). Table 3 also shows the water content of the green sheet, the R and the minimum elastic modulus.
  • Experimental Example 14 was performed in the same manner as in Experimental Example 1 except that the water content of the green sheet was 4%, except that the amount of glass fiber was 45% (see Table 4). .
  • Table 4 shows the water content of the green sheet, the R and the minimum elastic modulus together, and the bending properties of Experimental Examples 14 and 15 were insufficient compared to, for example, Experimental Example 1.
  • R could not be measured.
  • Example 16 The experiment was performed in the same manner as in Experimental Example 6 except that sodium metaphosphate was not added (see Table 4).
  • the temperature change of the elastic modulus is shown as a curve g in FIG. Table 4 also shows the water content of the green sheet, the R and the minimum elastic modulus.
  • Experimental example 16 hardly softened compared to experimental examples 6 to 8 (curves d, e, f). Also, even if a sample was taken out at 70 to 17 O: and bent to measure R, it could not be bent without generating cracks, that is, the bending characteristics were, for example, experimental examples 6 to 8 Was insufficient compared to
  • the experiment was performed in the same manner as in Experimental Example 6 except that the amount of glass fiber was set to 42% and the drying was performed at 60 for about 20 hours (see Table 4).
  • Table 4 also shows the water content of the green sheet, the above and the minimum elastic modulus.
  • Example 1 4 Example 1 5 Example 1 6 Example 1 7 Example 1 8 Alumina) 36.0 36.0 72.0 72.0 72.0
  • raw materials having the mass indicated in g were mixed in columns from alumina to a 50% aqueous solution of monobasic aluminum phosphate to prepare a water-containing slurry. That is, the raw materials (powder raw materials) other than the 50% aqueous solution of monobasic aluminum phosphate are put into a 300 ml 1-desk cup and mixed, and then the 50% aqueous solution of monobasic aluminum phosphate is added, and a cross stirrer blade of 7 cm in length is added. And stirred at 500 rpm for 10 minutes to produce a water-containing slurry.
  • Alumina Showa Denko A-43-L, sodium metaphosphate: Industrial products manufactured by Yoneyama Chemical Co., Ltd. Disodium dihydrogen diphosphate: manufactured by Kishida Chemical Co., Ltd. Sodium tripolyphosphate: manufactured by Kanto Chemical Co., Ltd., wollastonite: Kinsei Matech Corporation FPW-400, Stearic acid: Kanto Kagaku deer grade 1.
  • a sheet-like inorganic slurry layer (200 mmX20 OmmX2.5 mm) impregnated with the water-containing slurry by a hand lay-up method with a glass fiber having a mass shown in g in the column of glass fiber in the table was added to P. Formed on ET film.
  • E5 glass fiber G5E (specific gravity: 2.54) manufactured by Asahi Fiber One Dallas, which is a chopped strand type short fiber having a length of 3 Omm, was used.
  • the sheet After holding at 60 to 16 hours, the sheet was peeled off from the PET film, and this sheet was further dried at 60 at 8 hours to obtain a green sheet.
  • the water content of the green sheet (excluding crystallization water) was 12%.
  • compositions of the inorganic composites of P1 to P13 thus obtained are shown in Table 5 to '7 (A 1 P04 4 ) ⁇ Shown in the column from (Na 2 0) x to glass fiber content.
  • the unit is X: dimensionless, the content of the inorganic matrix and the content of the glass fiber are all volume%, and the others are mass percentages.
  • an inorganic composite having deep irregularities on the surface was prepared as follows. In other words, the carving depth (depth of unevenness
  • the mass per lm 2 of the inorganic composite was 4.5 kg.
  • the noncombustibility of this inorganic composite was determined based on the provisions of Article 2, Item 9 of the Building Standards Law (Revised on June 2, 2012). Was to do.
  • the inorganic slurry (green sheet) has sufficient flexibility at the time of heat molding, so that the inorganic slurry (green sheet) does not break during molding and has various shapes. Body) is obtained.
  • inorganic composites for building materials and industrial structural materials or members that require complex shapes and deep irregularities.
  • it can be used as an exterior material, an interior material, and the like used for renovating buildings such as houses.

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  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

L'invention concerne un procédé de production d'un composite inorganique consistant à utiliser une bouillie à base aqueuse renfermant un hydrogène-phosphate métallique, un durcisseur, un retardeur de durcissement et de l'eau, à ajouter des fibres de renforcement et à chauffer la bouille inorganique obtenue. Ce procédé est caractérisé en ce que la teneur, en termes de pourcentage en masse, de retardeur de durcissement dans la bouille à base aqueuse est comprise entre 0,05 et 30 %. L'invention concerne également un composite inorganique renfermant une matrice inorganique et des fibres de renforcement, caractérisé en ce que la matrice inorganique renferme (AlPO4) .(Na2O)x (x = entre 0,08 et 0,38) et Al2O3.
PCT/JP2003/002591 2002-03-11 2003-03-05 Composite inorganique et procede de production associe WO2003076358A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003211707A AU2003211707A1 (en) 2002-03-11 2003-03-05 Inorganic composite and process for producing the same

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2002065930A JP2002338329A (ja) 2001-03-09 2002-03-11 リン酸系水性スラリー、無機成形体用材料、リン酸系無機成形体およびその製造方法
JP2002-65930 2002-03-11
JP2002-261368 2002-09-06
JP2002261368 2002-09-06

Publications (1)

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WO2003076358A1 true WO2003076358A1 (fr) 2003-09-18

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AU (1) AU2003211707A1 (fr)
WO (1) WO2003076358A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116535136A (zh) * 2023-03-21 2023-08-04 湖北省交通规划设计院股份有限公司 一种厂拌热再生环氧沥青混合料及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01239049A (ja) * 1988-03-17 1989-09-25 Nissan Chem Ind Ltd 結合剤
EP1044942A1 (fr) * 1999-03-31 2000-10-18 Asahi Fiber Glass Co., Ltd. Procédé de preparation d'un corps inorganique moulé

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01239049A (ja) * 1988-03-17 1989-09-25 Nissan Chem Ind Ltd 結合剤
EP1044942A1 (fr) * 1999-03-31 2000-10-18 Asahi Fiber Glass Co., Ltd. Procédé de preparation d'un corps inorganique moulé

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116535136A (zh) * 2023-03-21 2023-08-04 湖北省交通规划设计院股份有限公司 一种厂拌热再生环氧沥青混合料及其制备方法
CN116535136B (zh) * 2023-03-21 2024-04-26 湖北省交通规划设计院股份有限公司 一种厂拌热再生环氧沥青混合料及其制备方法

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