AU657694B2 - High-strength molding of calcium silicate and production thereof - Google Patents
High-strength molding of calcium silicate and production thereof Download PDFInfo
- Publication number
- AU657694B2 AU657694B2 AU83172/91A AU8317291A AU657694B2 AU 657694 B2 AU657694 B2 AU 657694B2 AU 83172/91 A AU83172/91 A AU 83172/91A AU 8317291 A AU8317291 A AU 8317291A AU 657694 B2 AU657694 B2 AU 657694B2
- Authority
- AU
- Australia
- Prior art keywords
- molding
- glass fiber
- calcium silicate
- tobermorite
- pulp
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
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- 238000000465 moulding Methods 0.000 title claims description 67
- 239000000378 calcium silicate Substances 0.000 title claims description 38
- 229910052918 calcium silicate Inorganic materials 0.000 title claims description 38
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 71
- 239000000463 material Substances 0.000 claims description 53
- 239000003365 glass fiber Substances 0.000 claims description 46
- MKTRXTLKNXLULX-UHFFFAOYSA-P pentacalcium;dioxido(oxo)silane;hydron;tetrahydrate Chemical compound [H+].[H+].O.O.O.O.[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O MKTRXTLKNXLULX-UHFFFAOYSA-P 0.000 claims description 31
- 235000012239 silicon dioxide Nutrition 0.000 claims description 30
- 239000010453 quartz Substances 0.000 claims description 17
- 239000013078 crystal Substances 0.000 claims description 13
- 229910002026 crystalline silica Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 238000002441 X-ray diffraction Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 8
- 239000002657 fibrous material Substances 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- 239000012779 reinforcing material Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 description 21
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 9
- 238000005452 bending Methods 0.000 description 8
- 239000000292 calcium oxide Substances 0.000 description 7
- 235000012255 calcium oxide Nutrition 0.000 description 7
- 238000013329 compounding Methods 0.000 description 7
- 238000001879 gelation Methods 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000003014 reinforcing effect Effects 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000000920 calcium hydroxide Substances 0.000 description 5
- 235000011116 calcium hydroxide Nutrition 0.000 description 5
- 239000005909 Kieselgur Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000004566 building material Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- UGGQKDBXXFIWJD-UHFFFAOYSA-N calcium;dihydroxy(oxo)silane;hydrate Chemical compound O.[Ca].O[Si](O)=O UGGQKDBXXFIWJD-UHFFFAOYSA-N 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- C04B28/18—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 mixtures of the silica-lime type
- C04B28/186—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 mixtures of the silica-lime type containing formed Ca-silicates before the final hardening step
- C04B28/188—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 mixtures of the silica-lime type containing formed Ca-silicates before the final hardening step the Ca-silicates being present in the starting mixture
-
- 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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/36—Inorganic materials not provided for in groups C04B14/022 and C04B14/04 - C04B14/34
-
- 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
- C04B28/18—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 mixtures of the silica-lime type
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00189—Compositions or ingredients of the compositions characterised by analysis-spectra, e.g. NMR
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Civil Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Paper (AREA)
Description
OPI DATE 02/03/93 AOJP DATE 13/05/93 PCT NUMBER PCT/JP91/0106 9 t1111hl iili iiJl 11 iili AU9 183 172 (51) WAN;5Ia( 5 (11) R]rt~aI4 WO 93/02986 C04B 28 /18 Al (21) MEWH4 PCT/JP91/01069 C 22)P9 M AR F119914_8YJ9f(09. 08. 91) ,J'~ftt±(ONODA CEMENT CO., LTD. )[IJP/JP) f 756 W0*+f3~4+fB 2 t Yamaguch i, (JP) (72) 9 11.
1P~.m&L(NAKANO, Mas ayuk i)[CJP/JP) (KURA1OTO, Ryozo)[JP/JP) Z,1:11(OTOZAKI, Shigeo)CJP/JP) P(KANEKO, Ka tsu ak i )JP/JP) W*t~(TAIMURA, Noritoshi)CJP/JP) C(74) It:91A 09 j(SUZUYE, Takehiko et at.) ~Sl3Tokyo, (JP) AU, CA, DE(WMHft4),FR C IT (W7)i4N), KR, NL SE (Wll4A SU, US.
(54) Title :HIGH-STRENGTH MOLDING OF CALCIUM SILICATE AND PRODUCTION THEREOF (54) RH®D?# om~m 0- (57) Abstract A high-strength molding or calcium silicate comprising a mixture of tobermorite, C-S-H and quartz and containing glass fibers and pulp. It has a Ti to Qi ratio of 0.1 to 1.0 according to powder X-ray diffractometry and an absolute dry bulk density of 0.3 to 0.7 g/cc, and is non-combustible material similar to natural wood.
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MW 1 1 -f NL 7't 5i 3- NO /nr RU It, 5i*1 SD 3X-y SE L9-~ SK A- jt*Q SN I'L TD V' TG I UA 9' 4'5i -k' us iqms.uhi~ 1
[TRANSLATION]
DESCRIPTION
"MOLDING OF CALCIUM SILICATE HAVING HIGH STRENGTH AND ITS MANUFACTURING METHOD" Technical Field The present invention relates to a molding of calcium silicate having high strength useful for building materials.
Background Art A molding of calcium silicate, which is obtained by hydrothermally synthesizing calcareous material and silicic material, has been widely used as building material having light weight, high strength, high heat resistance, incombustibility property. In r-cent years, such a molding of calcium silicate has been further improved, and there have been made various proposals that the molding of calcium silicate has working properties such as bulk specific gravity, strength, abating, cutting, polishing, screw-nail holding property, and an adhesive property.
However, in the actual state, it is not easy to obtain such a molding having the above-mentioned properties, and the manufacture of the building material, which is similar to the natural timber, has not been realized yet. Conventionally, a matrix of xonotlite, which is reinforced with glass fiber, is typically used as the above-mentioned type material.
2 However, in such a material, since an adhesive strength between glass fiber and xonotlite is low, 5 to 10% by weight of synthetic resin is normally added thereto so as to enhance the adhesive strength. In deed, high adhesive strength to the glass fiber was obtained and its bending strength was satisfied. However, such a material was easily burned since a small amount of synthetic resin existed in the material. Also, heat resistance and incombustibility of such a material were low, and its workability was extremely lowered as compared with the timbers.
Disclosure of the Invention According to the present invention, an object of the present invention is to provide a molding of calcium 15 silicate having high strength wherein glass fiber and pulp o are dispersed and strongly adhered without compounding synthetic resin, thereby obtaining incombustible building material, which is similar to a natural timber.
0 0 More specifically, the present invention provides a molding of calcium silicate having high strength omprising calcium silicate hydrate, quartz, tobermorite and a reinforcing material made of glass fiber and pulp, c cwherein said molding contains 2-10 wt of said glass fiber S' and 2-10 wt of said pulp, a Ti/Qi ratio obtained by powder-X-ray diffraction is 0.1-1.0, wherein Ti represents the intensity of the X-ray diffraction of a (002) face of 1 tobermorite crystal, and Qi represents the intensity of the X-ray diffraction of a (101) face of quartz crystal, and said molding has an absolute bulk density is 0.3-0.7 g/cc.
Moreover, there is provided a method for manufacturing a molding of calcium silicate containing tobermorite and quartz and having high strength, from a calcareous material, a silicic material, and a fiber material, as raw materials, wherein the silicic material is formed of crystalline silica and amorphous silica mixed at a weight ratio of the amorphous silica to the total of the stafflahleerkeep/83172.9.reyp-l 20,12 3 crystalline silica and the amorphous silica, of 0.2-0.8, the fiber material consists of alkali-proof glass fiber and pulp, the calcareous material and the silicic material are added such that the CaO/SiO 2 molar ratio is 0.6-0.9, and the fiber material is added such that the amount of each of the alkali-proof glass fiber and the pulp is 2-10 wt comprising the steps of: mixing all of the calcareous material, and part or all of the non-crystalline silica, of the raw materials with water to form a slurry having a temperature of 50 0
C.;
making said slurry into a gel by heating said slurry at a temperature of 80 0 C. or higher at atmospheric pressure; S" 15 uniformly mixing said gel obtained in the above step with the rest of said raw material; molding a mixture obtained in the above step (c) by dehydration at a pressure of 3-30 3kg/cm 2 to 0 i form a molding; and pressurizing and heating the molding obtained in the above step in an autoclave under a ,o °saturation vapor pressure, at a temperature of S°140 0 -200 0 for 2-18 hours until the Ti/Qi ratio measured by powder-X-ray-diffraction is 0.1-1.0, wherein Ti represelts an intensity of the X-ray diffraction of a (002) face of tobermorite S* crystal, and Qi represents an intensity of the Xray diffraction of a (101) face of quartz crystal, respectively.
0 V stafflahleenkeepl83172.91.retype_1 20.12 4 -4- Brief Description of the Drawings Fig. 1 is an SEM (scanning electronic microscope) photograph showing a crystal structure of a molding of calcium silicate of Example 1 of the present invention; Fig. 2 is a view explaining a method for testing an abating property of the molding of calcium silicate according to the present invention; Fig. 3 is an SEM (Scanning Electron Microscop"-, photograph showing a crystal structure of a molding of calcium silicate of Example 5 of the present invention; Fig. 4 is a powder X-ray diffraction chart of the molding of calcium silicate of Example Figs. 5(B) and Figs. 6(A) and 6(B) are SEM photographs showing a broken surface of glass fiber and that of pulp when the molding of calcium silicate of Example 5 is bent and broken.
Best Mode of Carrying Out the Invention According to a first invention, there is provided a molding of calcium silicate, glass fiber and pulp are dispersed and adhered to calcium silicate in which tobermorite, C S H and quartz are mixed. Each content of glass fiber and pulp mixed therein ranges from 2 to 10%. If the content is below sufficient strength of the material cannot be obtained. Also, even if the content exceeds 10%, the strength of the material is not desirably improved.
/Moreover, when powder X-ray diffraction of calcium 7 E V/ oV i0 5 silicate constituting the mode is performed, a Ti/Qi ratio is 0.1 to 1.0, and an absolute bulk density is 0.3 to 0.7 g/cc wherein Ti and Qi show intensity of the X-ray diffraction of a tobermorite crystal (002) face and that of silica crystal (101) face, respectively.
Therefore, it is required that strength of matrix of calcium silicate itself be high.
For obtaining material, which is similar to a natural timber, by adding reinforcing material to calcium silicate, glass fiber is favorably used as reinforcing material. However, in order to enhance strength of the calcium silicate base material by use of glass fiber, the following points are required. That is, strength of the matrix of calcium silicate itself must be high; adhesion strength of the matrix of calcium silicate to glass fiber must be high; and strength of calcium silicate is not reduced by erosion of glass fiber serving as reinforcing material.
Inventors of the present invention made various experiments and confirmed the following facts.
That is, in a case that the matrix of calcium silicate was formed of C S H and quartz, the strength of the matrix was low, and the adhesion strength of the matrix of calcium silicate to glass fiber was insufficient. As a result, glass fiber was i drawn from the matrix in the case of bending breakage, AI, and a desirable strength was not able to be obtained.
i, 6 Moreover, in a case that most of the matrix was formed of tobermorite crystal, the strength of glass fiber was lowered, and the matrix and glass fiber were simultaneously broken in the case of bending breakage, or glass fiber was broken before the breakage of the matrix. Therefore, reinforcing effect of glass fiber was not shown. In contrast, in a case that tobermorite, C S H, and quartz were mixed into the matrix, and glass fiber was adhered to such the matrix, the strength of the matrix was high, and both adhesion strength of the matrix of calcium silicate to glass fiber and the strength of glass fiber itself were high. Particularly, regarding the strength of the matrix, the Ti/Qi ratio (Ti and Qi are the same as the above) was 0.1 to and the high strength was shown. Then, when the Ti/Qi ratio was out of the range of 0.1 to 1.0, the strength of the glass fiber was lowered.
Moreover, in order to improve working properties of the material such as the cutting of the molding, abating, polishing, screw-nail holding property, 2 to by weight of pulp must be adhered to the matrix. If the value is below no effect is brought about, and if the value is over 10%, incombustibility is considerably lowered.
In addition, if the absolute bulk density is below 0.3, a necessary screw-nail holding property cannot be expected. Moreover, if the absolute bulk density is w
O"
I 7I -7over 0.7, it is difficult to perform nailing or cutting, abating, and the like. Therefore, the absolute bulk density is set to 0.3 to 0.7 g/cc.
According to a second invention, there is provided a method for manufacturing the molding of calcium silicate of the first invention.
First, regarding calcareous material, hydrated lime, quicklime or milk of lime may be used. Regarding silicic material, crystalline silica and amorphous silica and its weight ratio of amorphous silica/ (crystalline silica amorphous silica) ranges from 0.2 to 0.8. If the value is out of the range, the molding of calcium silicate having high strength of the present invention cannot be obtained. Regarding crystalline silica, normal silica powder can be used. Regarding amorphous silica, diatomaceous earth, zeolite, silica flour can be used, but diatomaceous earth is preferably used, and its grain size may be 50.m or less. The compounding ratio of calcareous material to silicic material is set from 0.6 to 0.9 at a CaO/SiO 2 molar ratio. If the value is out of this range, the product based on the object of the invention cannot be obtained.
Moreover, if the value is below 0.6, generation of tobermorite becomes difficult. If the value is over 0.9, glass fiber is eroded, so that a'molding having a desired bending strength cannot be obtained. The compounding ratio of calcareous material to silicic -Ii h" i 8 material is set to preferably 0.7 to 0.85 at the CaO/SiO 2 molar ratio.
Regarding glass fiber, a chopped strand, which is obtained by cutting alkali proof glass fiber to have a suitable length, may be used, and its compounding ratio is 2 to 10% by weight. If the value is below 2% by weight, a desired reinforcing effect cannot be obtained.
If the value is over 10% by weight, it is difficult to perform the molding process, and the reinforcing effect is not desirably increased. Pulp is also used together with glass fiber. The use of pulp improves dispersibility of glass fiber, and largely distributes improvement of processing and working of the molding in addition to reinforcing effect. A normal timber pulp is used after being disaggregated in a wet manner or a dry manner. Regarding the compounding ratio of the pulp, if the ratio is below 2% by weight, the reinforcing effect cannot be obtained. And, if the ratio is over 10% by weight, incombustibility of the molding is considerably reduced, and the reinforcing effect is little improved.
Regarding the compound of these materials, calcareous material and at least a part of amorphous silica are mixed with water, and used as slurry. The residual amorphous silica is added later similar to crystalline silica. Then, the adding ratio of the final amorphous silica preferably ranges from 0.2 to 0.8 at the amorphous silica/(crystalline silica amorphous 9silica) ratio. If the value is low, the strength of the gel after being galled is weak, and the shape maintaining property is insufficient at the time of drawing the molding from a metal molding after the mixed materials are dehydrated and molded, and the handling of the molding becomes difficult. Moreover, if the value is high, pressure rises too much at the time of drawing the molding from the metal molding, and this is unfavorable in view of the manufacturing of the molding.
Regarding the addition of calcareous material to amorphous material, the CaO/SiO 2 molar ratio is preferably 0.8 or more. If the ratio is below 0.8, gelation does not largely advance. In this case, it is of course that all calcareous material may be added thereto. However, addition of alkali proof glass fiber is unfavorable since glass fiber is eroded by free lime.
Regarding a water/solid weight ratio, there is no special limitation, but the value preferably ranges from 3 to 10. At such a water ratio, gelation sufficiently advances, and swelling of gel does not enlarged too much. The important point when the materials are mixed is that the mixture is performed at temperature of 50 0
C
or less. If the mixture is performed at temperature of over 50 0 C, tobermorite, which is generated by the reaction in the autoclave, is considerably delayed, ther is a possibility that the initial product cannot be obtained. The following reason can be considered.
I
a
I
4! I ;I 10 That is, a large amount of C S H, which is difficult to transfer to tobermorite, is generated if calcareous material and amorphous silica are mixed with each other at temperature of over 50°C. It is desirable that 5 gelation be performed at 80 0 C under normal pressure.
Though gel time is influenced by rear-tivity of amorphous silica, gel time is normally 1 to 5 hours. It is preferable that mixing for gel time be intermittently performed.
Then, residual materials are added to the aboveobtained gel, and uniformly mixed. In this case, the above residual materials are materials in which the materials excepting materials, which are added before gelation, from the materials to be used, and alkali proof glass fiber is always included in the above residual materials. Though water is further added there'o, the water/solid weight ratio is not particularly limited. For uniformly mixing fiber material, the above water ratio preferably ranges from 2.0 to 4.0. As a mixer to be used in this case, a diffusion type mixer such as an omni type mixer is preferably used. Then, mixing time within 5 minutes is sufficient for this case. Thereafter, the mixture is introduced into the metal molding, pressurized and dehydrated to be molded. Pressure to'be applied in this case is suitably,3 to 30 kgf/cm 2 If pressure is below 3 kgf/cm 2 the shape maintaining property, which is w- -i-I i ~Llrrnrc I
I
11 after drawing the molding from the metal molding, is not good, and deformation is generated at the time of transferring. If pressure is over 30 kgf/cm 2 layershape cracks are easily generated in the molding after the molding is pressurized and cured. A molding box can be arbitrarily used. However, the m lding box having a thickness of 100 mm or less is preferably used since the uniformity of the reaction may be lost if the thickness is too large. The water/solid weight ratio of the obtained molding normally ranges from 1.0 to In this case, the bulk density of the dried product is about 0.3 to 0.7 g/cc.
Then, the above molding is thermally reacted in the autoclave. The reaction is normally performed at temperature of 140 to 200°C under saturated aqueous vapor. If the temperature is below 1400°C, generation of tobermorite is considerably delayed, and if the temperature is over 200°C, xonotlite is partially generated. Therefore, either condition is unfavorable since the strength of the product is lowered.
In view of economy and stability of the quality of the product, the reaction is preferably performed at temperature of 160 to 195°C, and more preferably 170 to 190°C. The reaction time is set to the condition that Ti/Qi ratio is 0.1 to 1.0 in the case-that powder Xray-diffraction of the reacted molding is performed.
For example, in Examples 1 to 4 of the present
I
12 invention, the reaction time is 3 to 8 hours in the case that the temperature is 180°C, 5 to 18 hours in the case that the temperature is 160 0 C, and 2 to 6 hours in the case that the temperature is 195 0 C. The present invention is, of course, not limited to the above temperature and time. After the cured molding is synthesized, the cured molding is dried, and a final product is obtained.
The following will explain Examples 1 to 4 and comparisons 1 to 3.
2.47 kg of quicklime powder was introduced into 8.
kg of hot water having temperature of 90 0 C, and slacked, so that milk of lime was obtained. The obtained milk of lime was cooled at temperature of 32 0
C.
Thereafter, 0.67 kg of diatomaceous earth fine powder (325 mesh whole-under) was added to the cooled milk of lime, and cold water was added thereto such that the water/solid weight ratio was set to 3.5, and was uniformly mixed. Thereafter, the mixture was heated in a warm bath, and gelled at temperature of 80 to 92 0 C for two hours. After gelation, the gelled substance was cooled to 60 0 C. Then, 2.02 kg of silica powder (Toyane silica powder 250 mesh under), 0.67 kg of diatomaceous earth powder, and 0.37 kg of alkali proof glass fiber, and 0.37 kg of pulp were added theretb, and uniformly mixed for two minutes by the omni type mixer. The compositions of this mixture were as follows: i j 13 CaO/SiO 2 molar ratio 0.83 amorphous silica/(crystalline silica amorphous silica) 0.4 alkali proof glass fiber compounding ratio pulp compounding ratio The mixture was introduced into the metal mold having an inner size of 610 x 1220 mm, and dehydrated at 12.0 kgf/cm 2 to obtain a molding. The thickness of the molding drawn from the metal mold was 18 mm. The molding was put in the autoclave and reacted for a predetermined time at temperature of 180°C under saturated aqueous vapor, taken out of the autoclave, and dried in an absolute dry manner at 105 0 C by a dryer.
The bulk density of the dried product was 0.54 to 0.56 g/cc. However, the size and the thickness of the product were unchanged, that is, 610 x 1220 mm of the size and 18 mm of the thickness.
Fig. 1 shows an SEM photograph of Example 1. In the photograph, the entire surface of quartz is covered with C S H presenting white agglomeration, and it is shown that tobermorite is partially generated.
Table 1 shows the measuring result of the physical properties of the products obtained according to Examples 1 to 4 and comparisons 1 to 3.
In Table 1, the products shown in the comparisons are formed such that the Ti/Qi ratio is set to be out of the range of 0.1 to 1.0. The bending strength shown in 1 -h 1 1
I
14 14 Table 1 were measured in accordance with JIS-A-1408.
The size of the object to be measured was set to 80 mm of the width x 180 mm of the length x 15 mm of the thickness, and the span length is set to 100 mm.
Combustibility was measured in accordance with JIS-A-1321.
Regarding the abating property, the object having the size of 50 mm of length 10 mm of width and mm of thickness is cut from the portion close to substantially the center of the product. By use of a blade whose angle is 280, the object whose depth of cut is 1 mm is abated at a cutting speed of 20 mm/min. In Table 1, a symbol o denotes a good abating property in which abatement is continuous, x denotes a bad abating property in which abatement is discontinuous, and A shows an intermediate abating property.
i i i C 1 ~i -CI~
I
0 M
FICIE
Table 1 Autoclave SEM X-ray Dif- Bulk Bending Ratio Incombus- Abating Constant Observing fraction Density Strength Inten- tibility Property Pressure Result Ti/Qi Peak p o sity Time (hr) Intensity (g/cc) (kgf/cm 2 o/p 2 Ratio
C-S-H
Tobermorite 1st Rate 1 3 Quartz can 0.15 0.54 86 295 of Flame o be Observed Retardance
C-S-H
Tobermorite 1st Rate 2 4 can be 0.42 0.55 118 390 of Flame o Embodi- Observed Retardance ments C-S-H Tobermorite 1st Rate 3 5 can be 0.58 0.54 97 333 of Flame o Observed _____Retardance
C-S-H
Tobermorite 1st Rate 4 8 can be 0.97 0.56 84 268 of Flame o _Observed _____Retardance
C-S-H
Tobermorite 1st Rate 2 can be 0.08 0.56 52 116 of Flame x Observed ___Retardance Most of Compa- Matrix is 1st Rate risons 6 10 Formed of 1.12 0.54 63 216 of Flame A Tobermorite ____Retardance Most of Matrix is 1st Rate 7 15 Formed of 1.45 0.55 46 152 of Flame x Tobermorite Retardance
I
L ii- m a t e r M M -0 1 L crystalline silica and amorphous silica mixed at a weight ratio of the amorphous silica to the total of the statlahleerIkeepl831 7 2 .91.retype) 20.12
'U
16 Example 5 will be explained as follows: The product was obtained by the same method as Example 1 excepting that the reaction time in the autoclave was set to 5 hours 30 minutes. Fig. 3 shows an SEM photograph of the matrix of the molding of calcium silicate obtained in Example It can be understood from Fig. 3 that tobermorite and C S H are mixed with each other. Fig. 4 is a chart of powder X-ray diffraction of the matrix of the molding of calcium silicate obtained in Example 5. As shown in Fig. 4, the peak of tobermorite and that of quartz are shown, and the intensity ratio of Ti/Qi was 0.64 wherein Ti (002) surface of tobermorite (28 7.820) and Qi (101) surface of quartz (28 26.650).
Figs. 5(B) and Figs. 6(A) and 6(B) are SEM photographs showing the broken surfaces of glass fiber and pulp when the molding of Example 5 is bent and broken.
More specifically, Fig. 5(A) shows the state that the surface of glass fiber is covered with a base material of calcium silicate. Fig. 5(B) shows one enlarged glass fiber, which is shown in Fig. "t can be understood from Fig. 5(B) that C S H and tobermorite are strongly adhered to the surface of the glass fiber, thereby the base material and glass fiber are strongly adhered to each other. Fig. 6(A) shows the same type of broken surface as Fig. Specifically, i S n I l J n r 17 Fig. 6(A) shows the state that the surface of pulp is covered with a base material of calcium silicate.
Fig. 6(B) shows an enlarged pulp, which is shown in Fig. It can be understood from Fig. 6(B) that C S H and part of tobermorite are strongly adhered to the surface of the pulp, thereby the base material and pulp are strongly adhered to each other.
The following will explain Examples 6 to 8 and comparisons 4 to 6.
In Examples 6 to 8 and comparisons 4 to-6, the product was obtained by the same method as Example 4 excepting that the ratio of amorphous silica and the adding method were changed. The results are shown in Table 2.
I
w Table 2 Amorphous Silica/ Method of Adding Bulk Bending Ratio (Crystalline Amorphous Silica Density p Strength Strenth Note Silica (g/cc) o o/p Amorphous Before After (kgf/cm 2 Silica) Gelation Gelation 6 0.2 0.2 0 0.54 79.6 273 Embodiment 7 0.6 0.2 0.4 0.55 94.4 312 8 0.8 0.2 0.6 0.55 81.1 268 Shape Maintaining Property in Weak After 4 0.1 0.1 0 Drawing Molding, Handling of Molding cannot be Performal Comparisons 5 0.9 0.5 0.4 0.55 45.1 149 A large Number of Layer-shape Cracks are Formed in Product 6 0.9 0.2 0.7 0.54 49.4 171 19 Industrial Applicability According to the present invention, the molding of calcium silicate having bulk density of 0.3 to 0.7 g/cc is light, and the strength ratio (bending strength)/ (bulk density) 2 is 260 or more. Also, working processes such as cutting, abating, polishing can be easily performed, no dust is generated, and holding force of bisscrew is large. Furthermore, since a crack, swelling, a pore are not generated on the surface and the inside of the product, and the molding of the present invention has good incombustibility, heat resistance, and stability of size, the molding of the present invention can be widely used in a wall material, a partition material, a floor material, and a heat insulating material.
I
Claims (2)
1. A molding of calcium silicate having high strength comprising calcium silicate hydrate, quartz, tobermorite and a reinforcing material made of glass fiber and pulp, wherein said molding contains 2-10 wt of said glass fiber and 2-10 wt of said pulp, a Ti/Qi ratio obtained by powder-X-ray diffraction is 0.1-1.0, wherein Ti represents the intensity of the X-ray diffraction of a (002) face of tobermorite crystal, and Qi represents the intensity of the X-ray diffraction of a (101) face of quartz crystal, and said molding has an absolute bulk density is 0.3-0.7 g/cc.
2. A method of manufacturing a molding of calcium silicate containing tobermorite and quartz and having high 15 strength, from a calcareous material, a silicic material, and a fiber material, as raw materials, wherein the silicic material is formed of crystalline silica and amorphous silica mixed at a weight ratio of the amorphous silica to 0" the total of the crystalline silica and the amorphous silica, of 0.2-0.8, the fiber material consists of alkali- proof glass fiber and pulp, the calcareous material and the Ssilicic material are added such that the CaO/SiO molar 00 ratio is 0.6-0.9, and the fiber material is added such that e* the amount of each of the alkali-proof glass fiber and the S0 25 pulp is 2-10 wt comprising the steps of: o mixing all of the calcareous material, and part S' or all of the non-crystalline silica, of the raw materials with water to form a slurry having a temperature of 50 0 C.; making said slurry into a gel by heating said slurry at a temperature of 80 0 C. or higher at atmospheric pressure; uniformly mixing said gel obtained in the above step with the rest of said raw material; molding a mixture obtained in the above step (c) by dehydration at a pressure of 3-30 kg/cm 2 to staff/ahleenfkeep/83172.91.retype 1 20.12 4 I I 'i- 21 form a molding; and pressurizing and heating the molding obtained in the above step in an autoclave under a saturation vapor pressure, at a temperature of 140 0 -200 0 for 2-18 hours until the Ti/Qi ratio measured by powder-X-ray-diffraction is 0.1-1.0, wherein Ti represents an intensity of the X-ray diffraction of a (002) face of tobermorite crystal, and Qi represents an intensity of the X- ray diffraction of a (101) face of quartz crystal, respectively. DATED THIS 20TH DAY OF DECEMBER 1994 ONODA CEMENT CO., LTD By its Patent Attorneys: GRIFFITH HACK CO Fellows Institute of Patent Attorneys of Australia 1r 0 o PS C 0 4 0e a: 00 *1 00 0e 0 0 w O 0 0 staff/ahlee/keep/83172.9.retypej_ 20.12 L_ i_:i 22 ABSTRACT A molding of calcium silicate having high strength, which is similar to a natural timber, wherein tobermorite, C S H and quartz are mixed, and glass fiber and pulp are contained, respectively, and a Ti/Qi peak ratio of which is powder X-ray diffracted is 0.1 to 1.0, and an absolute bulk density of the molding is 0.3 to 0.7 g/cc. i VU 1 A U I4 f' N
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2030597A JP2514734B2 (en) | 1990-02-09 | 1990-02-09 | High-strength calcium silicate compact and method for producing the same |
PCT/JP1991/001069 WO1993002986A1 (en) | 1990-02-09 | 1991-08-09 | High-strength molding of calcium silicate and production thereof |
Publications (2)
Publication Number | Publication Date |
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AU8317291A AU8317291A (en) | 1993-03-02 |
AU657694B2 true AU657694B2 (en) | 1995-03-23 |
Family
ID=34835708
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
AU83172/91A Ceased AU657694B2 (en) | 1990-02-09 | 1991-08-09 | High-strength molding of calcium silicate and production thereof |
Country Status (4)
Country | Link |
---|---|
KR (1) | KR960006229B1 (en) |
AU (1) | AU657694B2 (en) |
DE (1) | DE69116700T2 (en) |
TW (1) | TW197999B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN114772984B (en) * | 2022-04-14 | 2023-08-04 | 广东新元素板业有限公司 | Preparation method of high-toughness fiber reinforced silicate board |
-
1991
- 1991-08-08 TW TW080106267A patent/TW197999B/zh active
- 1991-08-09 KR KR1019930701084A patent/KR960006229B1/en not_active IP Right Cessation
- 1991-08-09 DE DE69116700T patent/DE69116700T2/en not_active Expired - Fee Related
- 1991-08-09 AU AU83172/91A patent/AU657694B2/en not_active Ceased
Also Published As
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DE69116700T2 (en) | 1996-09-19 |
DE69116700D1 (en) | 1996-03-07 |
TW197999B (en) | 1993-01-11 |
KR960006229B1 (en) | 1996-05-11 |
AU8317291A (en) | 1993-03-02 |
KR930702245A (en) | 1993-09-08 |
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