JPS6158436B2 - - Google Patents
Info
- Publication number
- JPS6158436B2 JPS6158436B2 JP4408576A JP4408576A JPS6158436B2 JP S6158436 B2 JPS6158436 B2 JP S6158436B2 JP 4408576 A JP4408576 A JP 4408576A JP 4408576 A JP4408576 A JP 4408576A JP S6158436 B2 JPS6158436 B2 JP S6158436B2
- Authority
- JP
- Japan
- Prior art keywords
- amorphous silica
- crystals
- secondary particles
- crystal
- particles
- 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.)
- Expired
Links
- 239000013078 crystal Substances 0.000 claims description 114
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 104
- 239000011163 secondary particle Substances 0.000 claims description 76
- 239000011164 primary particle Substances 0.000 claims description 66
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 50
- 239000000378 calcium silicate Substances 0.000 claims description 49
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 49
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 80
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 54
- 229910000019 calcium carbonate Inorganic materials 0.000 description 50
- 235000012241 calcium silicate Nutrition 0.000 description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 47
- 239000002002 slurry Substances 0.000 description 36
- 239000002994 raw material Substances 0.000 description 33
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 28
- 239000001569 carbon dioxide Substances 0.000 description 27
- 229910002092 carbon dioxide Inorganic materials 0.000 description 27
- 239000007789 gas Substances 0.000 description 26
- 239000002131 composite material Substances 0.000 description 25
- 238000002441 X-ray diffraction Methods 0.000 description 21
- 239000007858 starting material Substances 0.000 description 21
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 17
- 239000001110 calcium chloride Substances 0.000 description 17
- 229910001628 calcium chloride Inorganic materials 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- 238000010306 acid treatment Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 16
- 229910004298 SiO 2 Inorganic materials 0.000 description 15
- 239000000292 calcium oxide Substances 0.000 description 14
- 235000012255 calcium oxide Nutrition 0.000 description 14
- 238000000635 electron micrograph Methods 0.000 description 12
- 235000012239 silicon dioxide Nutrition 0.000 description 12
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 11
- 235000011941 Tilia x europaea Nutrition 0.000 description 11
- 239000004571 lime Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 238000000465 moulding Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 239000000835 fiber Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000005452 bending Methods 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 239000011246 composite particle Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 159000000007 calcium salts Chemical class 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000004626 scanning electron microscopy Methods 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 239000010456 wollastonite Substances 0.000 description 5
- 229910052882 wollastonite Inorganic materials 0.000 description 5
- 239000004927 clay Substances 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 239000012744 reinforcing agent Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000010425 asbestos Substances 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011490 mineral wool Substances 0.000 description 3
- 229910052895 riebeckite Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- -1 zonotrite Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229920002978 Vinylon Polymers 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- SHFGJEQAOUMGJM-UHFFFAOYSA-N dialuminum dipotassium disodium dioxosilane iron(3+) oxocalcium oxomagnesium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Na+].[Na+].[Al+3].[Al+3].[K+].[K+].[Fe+3].[Fe+3].O=[Mg].O=[Ca].O=[Si]=O SHFGJEQAOUMGJM-UHFFFAOYSA-N 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000008279 sol Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Porous Artificial Stone Or Porous Ceramic Products (AREA)
- Silicon Compounds (AREA)
Description
【発明の詳細な説明】 技術分野 本発明は新規な非晶質シリカ成形体に関する。[Detailed description of the invention] Technical field The present invention relates to a novel amorphous silica molded article.
背景技術
従来非晶質シリカとしては代表的なものとして
シリカゲルが知られている。これは主に珪酸ナト
リウム水溶液を塩酸、硫酸等の酸で中和し、沈澱
を析出させ、水洗乾燥して製造され、更に必要が
あれば減圧下に加熱して活性化される。該シリカ
ゲルは製造法により不定形又は球状で収得される
が、それ自体成形能を有さず、従つてこれを成形
するに当つては結合剤等の利用を必須とする。し
かるにかかる方法により得られるシリカゲル成形
体は、重質でありしかも強度が弱く、保温材、断
熱材等の用途には到底実用できない。また上記シ
リカゲルは水と接すると急激に水分を吸収し崩壊
する性質を有し、水と直接接する系での使用は不
可能又は困難である。更にこれは耐熱ガラス等の
耐火耐熱材用原料としての用途には不適当であ
る。BACKGROUND ART Silica gel is conventionally known as a typical amorphous silica. This is mainly produced by neutralizing an aqueous sodium silicate solution with an acid such as hydrochloric acid or sulfuric acid, precipitating a precipitate, washing with water and drying, and if necessary, activating it by heating under reduced pressure. The silica gel can be obtained in an amorphous or spherical shape depending on the manufacturing method, but it does not have moldability per se, so it is essential to use a binder or the like to mold it. However, the silica gel molded body obtained by such a method is heavy and has low strength, and cannot be put to practical use as a heat retaining material, a heat insulating material, or the like. Furthermore, the silica gel has the property of rapidly absorbing water and disintegrating when it comes into contact with water, making it impossible or difficult to use it in systems where it comes into direct contact with water. Furthermore, it is unsuitable for use as a raw material for fire-resistant and heat-resistant materials such as heat-resistant glass.
発明の目的
本発明は上記従来公知のシリカゲルとは異な
り、非晶質シリカから実質的に構成され、しかも
軽量にして且つ優れた機械的強度を備えた新しい
非晶質シリカの成形体を提供するものである。Purpose of the Invention The present invention provides a new amorphous silica molded product that is substantially composed of amorphous silica and is lightweight and has excellent mechanical strength, unlike the conventionally known silica gel. It is something.
発明の構成
即ち本発明は起源結晶とする珪酸カルシウム結
晶の晶癖を保有し約１〜500μｍの長さ、約50Å
〜約１μｍの厚さおよび約100Å〜50μｍの巾を
有し且つ、長さが厚さの少なくとも10倍である外
観結晶様非晶質シリカ一次粒子が多数不規則に三
次元的に結合して形成された約10〜150μｍの直
径を有し実質的に球殻状を呈する二次粒子から主
として構成され、該二次粒子が少なくとも一方向
に圧縮され、且つ相互に絡合されていることを特
徴とする非晶質シリカ成形体に係る。Structure of the Invention That is, the present invention possesses the crystal habit of a calcium silicate crystal as a source crystal, has a length of about 1 to 500 μm, and has a crystal habit of about 50 Å.
A large number of crystal-like amorphous silica primary particles having a thickness of ~1 μm, a width of about 100 Å ~ 50 μm, and a length at least 10 times the thickness are irregularly bonded in a three-dimensional manner. It is mainly composed of secondary particles having a diameter of about 10 to 150 μm and having a substantially spherical shell shape, and the secondary particles are compressed in at least one direction and entangled with each other. The present invention relates to a characteristic amorphous silica molded body.
本発明の非晶質シリカ成形体は、通常次式で表
わされる空隙率が少なくとも50％、好ましくは60
〜97％であり、軽量にして優れた機械的強度を有
している。 The amorphous silica molded body of the present invention usually has a porosity expressed by the following formula of at least 50%, preferably 60%.
~97%, and is lightweight and has excellent mechanical strength.
空隙率（％）＝（１−成形体の見掛比重／成形体の真比
重）×100
殊に本発明成形体は何れも0.1〜0.4g/cm3程度の
低嵩密度で３〜30Kg/cm2程度の大きな曲げ強度を
備えている。また上記嵩密度はより大きくするこ
とも可能であり、この嵩密度に比例して本発明成
形体はより大きな機械的強度を有する。たとえば
0.4g/cm3〜1.0g/cm3の嵩密度の成形体では20〜100
Kg/cm2程度の大きな曲げ強度を有する。本発明成
形体がこの様に軽量で優れた機械的強度を備えて
いるのは、主としてこれを構成している二次粒子
の形状及び性質に起因する。即ち該二次粒子は、
上記の通り特定の形状及び大きさを有する非晶質
シリカ一次粒子が多数不規則に三次元的に絡合し
て形成されており且つ内部が中空もしくは粗にな
つており、直径的10〜150μｍの範囲の実質的に
球殻状の形態を有し、空隙率が少なくとも75％、
好ましくは約80〜98％であることに基づいて、そ
の水性スラリーを成形する時には、成形時の圧力
により二次粒子が少なくともその圧力方向に圧縮
され且つ該圧縮された粒子が相互に強固に絡合
し、これを乾燥すると上記状態で一体的に構成さ
れ、軽量で優れた機械的強度を有する成形体を与
える。Porosity (%) = (1-apparent specific gravity of molded body/true specific gravity of molded body) × 100 In particular, the molded bodies of the present invention all have a low bulk density of about 0.1 to 0.4 g/cm 3 and a low bulk density of 3 to 30 kg/cm 3 It has a large bending strength of about cm 2 . Further, the above-mentioned bulk density can be made larger, and the molded article of the present invention has a larger mechanical strength in proportion to this bulk density. for example
20 to 100 for molded bodies with a bulk density of 0.4 g/cm 3 to 1.0 g/cm 3
It has a high bending strength of about Kg/ cm2 . The reason why the molded product of the present invention is so lightweight and has excellent mechanical strength is mainly due to the shape and properties of the secondary particles that make up the molded product. That is, the secondary particles are
As mentioned above, it is formed by irregularly entangling a large number of amorphous silica primary particles with a specific shape and size in a three-dimensional manner, and the inside is hollow or rough, with a diameter of 10 to 150 μm. having a substantially spherical shell-like morphology in the range of , with a porosity of at least 75%;
Based on the fact that the aqueous slurry is preferably about 80 to 98%, when the aqueous slurry is molded, the pressure during molding compresses the secondary particles at least in the direction of the pressure, and the compressed particles are tightly entangled with each other. When these are combined and dried, they are integrally constructed in the above state, giving a molded article that is lightweight and has excellent mechanical strength.
本発明成形体は、上記非晶質シリカ二次粒子の
みから構成されていても良いが、他にガラス繊
維、セラミツクスフアイバー、石綿、岩綿、合成
繊維（ナイロン、ビニロン等）、天然繊維、パル
プ、ステンレスフアイバー、金属繊維、炭素繊
維、充填剤、着色剤、粘土、セメント等の添加剤
を含んでいても良い。 The molded article of the present invention may be composed only of the above amorphous silica secondary particles, but may also be composed of glass fiber, ceramic fiber, asbestos, rock wool, synthetic fiber (nylon, vinylon, etc.), natural fiber, pulp. , stainless fiber, metal fiber, carbon fiber, filler, colorant, clay, cement, and other additives.
本発明成形体は、上記の様な特性を有するが故
に、保温材、断熱材、耐火過材、触媒担体等の
用途に有用である。 Since the molded article of the present invention has the above-mentioned characteristics, it is useful for uses such as heat insulating materials, heat insulating materials, fireproofing materials, catalyst carriers, and the like.
本発明成形体はSiO4四面体の鋼状又は連鎖状
構造を有する各種の天然又は合成珪酸塩結晶の二
次粒子から製造できる。その製造方法は特に制限
されず任意の方法を採用できるが最も有利には該
珪酸カルシウム結晶の二次粒子を原料としてこれ
を水分の存在下に炭酸ガスと接触させて非晶質シ
リカと極微細炭酸カルシウムとに転換させ（炭酸
化）、次いて生成物を酸で処理して炭酸カルシウ
ムを二酸化炭素及びカルシウム塩に分解して非晶
質シリカをカルシウム塩から分離し（酸処理）、
上記炭酸化工程の前、後又は酸処理工程の後のい
ずれかに成形を行なうことにより製造される。 The shaped bodies of the present invention can be produced from secondary particles of various natural or synthetic silicate crystals having a SiO 4 tetrahedral steel-like or chain-like structure. The manufacturing method is not particularly limited and any method can be adopted, but the most advantageous method is to use secondary particles of the calcium silicate crystals as a raw material and contact them with carbon dioxide gas in the presence of moisture to form ultrafine amorphous silica. (carbonation) and then treating the product with acid to decompose the calcium carbonate into carbon dioxide and calcium salts and separate the amorphous silica from the calcium salts (acid treatment);
It is produced by performing molding either before or after the carbonation step or after the acid treatment step.
この製造方法の最大の特徴は、上記炭酸化及び
酸処理工程では珪酸カルシウム結晶二次粒子又は
成形体の外形を実質的に変化させることなく該二
次粒子又は成形体を構成する珪酸カルシウム結晶
を非晶質シリカに転換させる得る点にある。従つ
てこの様にして得られる非晶質シリカは、珪酸カ
ルシウム結晶の形骸を実質的にそのまま有するこ
ととなる。起源結晶として使用できる珪酸カルシ
ウム結晶にはワラストナイト、ゾーノトライト、
フオシヤジヤイト、ヒレブランダイト、ローゼン
ハナイト等のワラストナイト系珪酸カルシウム結
晶、トベルモライト等のトベルモライト系珪酸カ
ルシウム結晶、ジヤイロライト、トラスコタイ
ト、リエライト等のジヤイロライト系珪酸カルシ
ウム結晶、カルシオコンドロダイト、キルコアナ
イト、アフビイライト等のγ―ダイカルシウムシ
リケート系珪酸カルシウム結晶、α―ダイカルシ
ウムシリケートハイドレート等が包含される。之
等結晶から導かれる非晶質シリカは、起源結晶の
外観及び大きさと実質的に一致する種々の外形及
び大きさを有する。例えばワラストナイト、ゾー
ノトライト、フオシヤジヤイト等の短冊状珪酸カ
ルシウム系結晶から導かれる非晶質シリカは短冊
状外形を有する。トベルモライト、ジヤイロライ
ト、α―C2SH等の板状珪酸カルシウム結晶から
導かれるそれは板状の外形を有する。之等短冊
状、板状等を呈する非晶質シリカは、長さ約１〜
500μｍ、厚さ約50Å〜１μｍ及び約100Å〜50μ
ｍの巾を有し且つ長さが厚さの少なくとも10倍で
ある大きさを有する。ゾーノトライト結晶から導
かれる短冊状の非晶質シリカは該結晶の晶癖を保
持し通常約１〜50μｍの長さ、約100Å〜0.5μｍ
の厚さ及び約100Å〜２μｍの巾を有し長さは厚
さの約10〜5000倍である。トベルモライト結晶か
ら導かれる板状のそれは該結晶の晶癖を保持し約
１〜50μｍの長さ、約100Å〜0.5μｍの厚さ及び
約0.2〜20μｍの巾を有し長さが厚さの約10〜
5000倍である。ワラストナイト結晶から導かれる
短冊状のそれはその結晶の晶癖を保持し約１〜
500μｍの長さ、約100Å〜１μｍの厚さ及び約
100Å〜５μｍの巾を有し長さが厚さの約10〜
5000倍である。ジヤイロライト結晶から導かれる
板状のそれは、その結晶の晶癖を保持し約１〜50
μｍの長さ、約100Å〜0.5μｍの厚さ及び約１〜
20μｍの巾を有し長さが厚さの10〜5000倍であ
る。α―ダイカルシウムシリケートハイドレート
結晶から導かれる板状のそれは、その結晶の晶癖
を保持し約１〜300μｍの長さ、約500Å〜１μｍ
の厚さ及び約１〜50μｍの巾を有し長さが厚さの
10〜5000倍である。 The biggest feature of this manufacturing method is that the carbonation and acid treatment steps remove the calcium silicate crystals constituting the secondary particles or the molded product without substantially changing the outer shape of the calcium silicate crystal secondary particles or the molded product. It is at the point where it can be converted to amorphous silica. Therefore, the amorphous silica obtained in this way has the skeleton of calcium silicate crystals substantially intact. Calcium silicate crystals that can be used as origin crystals include wollastonite, zonotrite,
Wollastonite calcium silicate crystals such as phosiyaite, hillebrandite, and rosenhanite, tobermolite calcium silicate crystals such as tobermolite, gyrolite calcium silicate crystals such as gyrolite, trascotite, and lierite, and calciochondrodite. , gamma-dicalcium silicate-based calcium silicate crystals such as circoniaite and ahuvilite, and α-dicalcium silicate hydrate. Amorphous silica derived from these iso-crystals has a variety of shapes and sizes that substantially match those of the source crystals. For example, amorphous silica derived from rectangular calcium silicate crystals such as wollastonite, zonotrite, and phosciasite has a rectangular outer shape. It is derived from plate-like calcium silicate crystals such as tobermolite, gyrolite, α-C 2 SH, etc., and has a plate-like external shape. Amorphous silica having a rectangular shape, plate shape, etc. has a length of about 1 to
500μm, thickness approx. 50Å to 1μm and approx. 100Å to 50μ
m width and a length at least 10 times the thickness. Amorphous silica strips derived from zonotrite crystals retain the crystal habit of the crystals and are usually about 1 to 50 μm in length, about 100 Å to 0.5 μm in length.
It has a thickness of about 100 Å to 2 μm, and a length of about 10 to 5000 times the thickness. A plate-like plate derived from tobermolite crystal retains the crystal habit of the crystal and has a length of about 1 to 50 μm, a thickness of about 100 Å to 0.5 μm, and a width of about 0.2 to 20 μm, and the length is the thickness. Approximately 10~
It is 5000 times more. The rectangular shape derived from wollastonite crystal retains the crystal habit of the crystal and has a crystal habit of about 1~
500μm length, about 100Å~1μm thickness and approx.
The width is 100 Å to 5 μm and the length is about 10 to the thickness.
It is 5000 times more. It is a plate-like material derived from a gyrolite crystal, which retains the crystal habit of the crystal and has a crystallinity of about 1 to 50
μm length, about 100 Å to 0.5 μm thickness and about 1 to
It has a width of 20 μm and a length 10 to 5000 times the thickness. A plate-shaped plate derived from α-dicalcium silicate hydrate crystal retains the crystal habit and has a length of approximately 1 to 300 μm and a length of approximately 500 Å to 1 μm.
It has a thickness of about 1 to 50 μm and a length of about 1 to 50 μm.
It is 10 to 5000 times.
之等結晶は、二次粒子又は成形体の形態で起源
物質として使用される。結晶の外形が損われるこ
となく実質的にそのまま非晶質シリカに受け継が
れる故に、起源結晶の形態も亦実質的に変化を受
けることなく非晶質シリカに受け継がれる。即ち
上記珪酸カルシウム結晶の一次粒子が多数不規則
に三次元的に絡合して形成されている約10〜150
μｍの直径を有する実質的に球殻状の二次粒子か
らは、そのままの形態又は構造を有する非晶質シ
リカ二次粒子が得られる。また珪酸カルシウム結
晶の上記球殻状二次粒子が、相互に絡合して一体
的に構成された珪酸カルシウム結晶の成形体から
は本発明の非晶質シリカ成形体が得られる。 These crystals are used as source material in the form of secondary particles or shaped bodies. Since the outer shape of the crystal is inherited substantially unchanged to the amorphous silica, the morphology of the original crystal is also inherited to the amorphous silica without being substantially changed. That is, approximately 10 to 150 primary particles of the calcium silicate crystals are formed by irregularly entangling them in a three-dimensional manner.
Amorphous silica secondary particles having the same morphology or structure are obtained from substantially spherical secondary particles having a diameter of μm. Further, the amorphous silica molded body of the present invention can be obtained from a molded body of calcium silicate crystals in which the spherical shell-shaped secondary particles of calcium silicate crystals are integrally constituted by intertwining with each other.
本発明の非晶質シリカ成形体を製造する為に用
いられる上記各種の珪酸カルシウムは何れも公知
であり、公知の方法によつて製造出来る。たとえ
ば珪酸カルシウム結晶の前記球殻状二次粒子は、
本出願人が先に開発した特公昭45―25771号に記
載される方法によつて製造出来る。即ち、珪酸原
料及び石灰原料を、必要に応じ補強剤等の添加剤
と共に、水に分散させた原料スラリーを撹拌下に
水熱合成反応に従わせ結晶化させることによつて
珪酸カルシウム結晶の球殻状二次粒子の水性スラ
リーが得られる。また上記球殻状二次粒子から構
成される珪酸カルシウム結晶の成形体も、上記特
公昭45―25771号に記される方法で製造される。
即ち上記方法で得た球殻状二次粒子の水性スラリ
ーを、必要に応じ補強剤等の添加剤を添加し、脱
水成形し、乾燥することによつて二次粒子が相互
に不規則に三次元的に絡合して一体的に構成され
た珪酸カルシウム結晶の成形体が得られる。 The above-mentioned various calcium silicates used for producing the amorphous silica molded body of the present invention are all known and can be produced by known methods. For example, the spherical secondary particles of calcium silicate crystals are
It can be produced by the method described in Japanese Patent Publication No. 45-25771, which was previously developed by the present applicant. That is, a raw material slurry in which a silicic acid raw material and a lime raw material are dispersed in water together with additives such as a reinforcing agent as necessary is subjected to a hydrothermal synthesis reaction while being stirred and crystallized to form spheres of calcium silicate crystals. An aqueous slurry of shell-like secondary particles is obtained. Furthermore, a molded body of calcium silicate crystals composed of the above-mentioned spherical shell-shaped secondary particles is also produced by the method described in the above-mentioned Japanese Patent Publication No. 45-25771.
That is, the aqueous slurry of spherical secondary particles obtained by the above method is added with additives such as a reinforcing agent as necessary, dehydrated, molded, and dried, so that the secondary particles irregularly form tertiary particles. A molded body of calcium silicate crystals which are originally entangled and integrally constituted is obtained.
上記珪酸カルシウム結晶を得る為の原料として
用いられる珪酸原料としては、天然無定形珪酸、
珪砂、珪蘗土、クレー、スラグ、白土、フライア
ツシユ、パーライト、ホワイトカーボン、シリコ
ンダスト等の珪酸分を主成分とする各種のものを
使用出来、これらは単独でまたは２種以上混合し
て使用出来る。また石灰原料としては例えば生石
灰、消石灰、カーバイト残渣、セメント等石灰分
を主成分とする各種のものを夫々例示することが
でき、これ等は単独でもしくは２種以上混合して
使用できる。これ等各原料は通常CaO：SiO2の
モル比を0.5〜3.5：１程度の範囲とする様配合す
るのがよい。上記原料と共に必要に応じガラス繊
維、セラミツクフアイバー、石綿、岩綿、ナイロ
ン、ビニロン、天然繊維、パルプ、ステンレスフ
アイバー、炭素繊維等の補強剤や着色剤等の添加
剤が配合され得る。また上記に於いて使用される
水量は、広い範囲に亘つて変化させ得る。一般に
は固形分の合計重量に対して3.5〜30倍程度とす
るのがよい。反応は好ましくはオートクレーブ中
水蒸気圧の飽和温度で進行し、反応温度は通常
100℃以上好ましくは150℃以上とすればよい。上
記反応は一般に0.5〜20時間程度で完結する。上
記CaO：SiO2のモル比、反応圧力、温度、時間
等に応じて各種結晶化度の異なる珪酸カルシウム
結晶が得られる。該珪酸カルシウム結晶としては
その結晶系により例えばゾーノトライト、トベル
モライト、フオシヤジヤイト、ジヤイロライト、
α―ダイカルシウムシリケートハイドレート等が
挙げられる。また上記ゾーノトライト結晶を更に
1000℃程度で焼成することにより、その形状を変
化させることなく之を構成する結晶をワラストナ
イトとすることが出来る（特公昭50―29493号）。 The silicic acid raw materials used as raw materials for obtaining the above calcium silicate crystals include natural amorphous silicic acid,
Various materials containing silicic acid as a main component such as silica sand, siliceous earth, clay, slag, white clay, fly ash, perlite, white carbon, and silicon dust can be used, and these can be used alone or in a mixture of two or more. . Examples of lime raw materials include quicklime, slaked lime, carbide residue, cement, and other materials whose main component is lime, and these can be used alone or in a mixture of two or more. These raw materials are usually blended so that the molar ratio of CaO:SiO 2 is in the range of about 0.5 to 3.5:1. Additives such as reinforcing agents such as glass fibers, ceramic fibers, asbestos, rock wool, nylon, vinylon, natural fibers, pulp, stainless fibers, carbon fibers, and coloring agents may be blended with the above raw materials as necessary. Also, the amount of water used above can vary over a wide range. Generally, the amount should be about 3.5 to 30 times the total weight of the solids. The reaction preferably proceeds at the saturation temperature of water vapor pressure in the autoclave, and the reaction temperature is usually
The temperature may be 100°C or higher, preferably 150°C or higher. The above reaction is generally completed in about 0.5 to 20 hours. Calcium silicate crystals having various degrees of crystallinity can be obtained depending on the molar ratio of CaO:SiO 2 , reaction pressure, temperature, time, etc. Depending on the crystal system, the calcium silicate crystals include, for example, zonotrite, tobermolite, phosiyaite, gyrolite,
Examples include α-dicalcium silicate hydrate. In addition, the above zonotrite crystals are further added.
By firing at around 1000℃, the crystals that make up this material can be made into wollastonite without changing its shape (Special Publication No. 50-29493).
本発明に於いては上記の如くして得られる球殻
状二次粒子及び成形体の形態にある珪酸カルシウ
ム結晶を水の存在下に炭酸ガスと接触させて強制
的に炭酸化せしめる。該炭酸化は、反応系内に炭
酸ガスを導入し、水分の存在下に於いて上記結晶
と炭酸ガスとを接触せしめることにより行なわれ
る。上記炭酸化は好ましくは例えば各種形態の珪
酸カルシウム結晶を適当な密閉容器中に入れ高湿
度下乃至湿潤下に炭酸ガスを導入するか、更には
各種形態の珪酸カルシウム結晶を水中もしくは炭
酸水中に浸漬後之に炭酸ガスを導入する等の方法
により実施できる。勿論珪酸カルシウム結晶を二
次粒子の水性スラリーの形態で得た場合には之に
直接炭酸ガスを導入すれば良い。この炭酸化は系
内に炭酸ガスを導入する限り常温、常圧下に於い
ても充分進行するが好ましくは加圧下10Kg/cm2程
度迄のゲージ圧下に行なうのがよく、これにより
炭酸化の速度が一層早くなり短時間で反応を完結
することが可能となる。炭酸ガスの使用量は化学
量論量又はそれ以上である。また珪酸カルシウム
結晶を水中に浸漬して炭酸化処理を行なう場合に
は、反応系を撹拌することによつても炭酸化速度
を早めることができる。水対珪酸カルシウム結晶
の使用割合は通常１〜50：１好ましくは１〜25：
１（重量比）とするのがよい。この炭酸化の速度
は原料材料を構成する珪酸カルシウムの結晶化度
によつて若干異なるが、例えばこの炭酸化速度が
最も遅いと認められるゾーノトライト結晶を炭酸
化する場合には、その乾燥重量に対し水分添加量
を２〜６倍程度とすることにより４〜10時間程度
で反応が完結する。また該水分の添加量を５倍と
し反応系を２Kg/cm2（ゲージ圧）に加圧すれば、
反応は通常１時間前後で完結し、この加圧条件を
３Kg/cm2（ゲージ圧）とすれば30分程度という極
めて短時間で反応が完結することが認められてい
る。 In the present invention, the spherical shell-like secondary particles and calcium silicate crystals in the form of molded bodies obtained as described above are brought into contact with carbon dioxide gas in the presence of water to forcibly carbonate them. The carbonation is carried out by introducing carbon dioxide gas into the reaction system and bringing the crystals into contact with the carbon dioxide gas in the presence of moisture. The above carbonation is preferably carried out by, for example, placing calcium silicate crystals in various forms in a suitable closed container and introducing carbon dioxide gas under high humidity or humidity, or further immersing calcium silicate crystals in various forms in water or carbonated water. This can be carried out by a method such as introducing carbon dioxide gas afterwards. Of course, when calcium silicate crystals are obtained in the form of an aqueous slurry of secondary particles, carbon dioxide gas may be directly introduced therein. This carbonation will proceed satisfactorily even at room temperature and pressure as long as carbon dioxide gas is introduced into the system, but it is preferably carried out under pressure of up to about 10 kg/cm 2 , which increases the rate of carbonation. This makes it possible to complete the reaction in a short time. The amount of carbon dioxide used is stoichiometric or more. Furthermore, when carbonating calcium silicate crystals by immersing them in water, the carbonation rate can also be increased by stirring the reaction system. The ratio of water to calcium silicate crystals used is usually 1 to 50:1, preferably 1 to 25:1.
1 (weight ratio). The rate of carbonation differs slightly depending on the crystallinity of the calcium silicate constituting the raw material, but for example, when carbonating zonotrite crystals, which are recognized to have the slowest carbonation rate, By increasing the amount of water by about 2 to 6 times, the reaction can be completed in about 4 to 10 hours. Furthermore, if the amount of water added is increased five times and the reaction system is pressurized to 2Kg/cm 2 (gauge pressure),
The reaction is usually completed in about one hour, and it is recognized that if the pressurization conditions are 3 kg/cm 2 (gauge pressure), the reaction can be completed in an extremely short time of about 30 minutes.
上記炭酸化反応は、原料とする珪酸カルシウム
結晶の種類及び結晶化度により下記反応式で示さ
れる如く進行する。 The carbonation reaction proceeds as shown in the following reaction formula depending on the type and crystallinity of calcium silicate crystals used as raw materials.
xCaO・SiO2・mH2O＋CO2 →CaCO3＋SiO2・nH2O 但し上記式中ｘは0.5〜3.5である。 xCaO·SiO 2 ·mH 2 O+CO 2 →CaCO 3 +SiO 2 ·nH 2 O However, in the above formula, x is 0.5 to 3.5.
いずれの珪酸カルシウム結晶を用いた場合に
も、該珪酸カルシウムは、その一次粒子の外形を
実質的に変化させることなく、従つて形態上の変
化を伴うことなく非晶質シリカと炭酸カルシウム
の極微結晶とに転化される。即ち珪酸カルシウム
一次結晶の骨格構造をなすSiO4四面体の連鎖構
造はそのまま保持され、該連鎖構造によつて結晶
の外観を有する非晶質シリカと之に付着した極微
細炭酸カルシウムとが生成する。 No matter which type of calcium silicate crystal is used, the calcium silicate is made up of microscopic particles of amorphous silica and calcium carbonate without substantially changing the external shape of its primary particles and without any change in morphology. It is converted into crystals. In other words, the chain structure of SiO 4 tetrahedra that forms the skeleton structure of the primary calcium silicate crystal is maintained, and this chain structure produces amorphous silica with a crystalline appearance and ultrafine calcium carbonate attached thereto. .
本発明に於いては上記炭酸化により得られる非
晶質シリカ―炭酸カルシウム複合体を次いで酸処
理する。この酸処理は、上記複合体を構成する非
晶質シリカから炭酸カルシウム分を分離するため
に行なわれるものであり、好ましくはシリカとは
反応性を有さないが炭酸カルシウムを分解して炭
酸ガスと水可溶性のカルシウム塩とを生成し得る
酸を用いて行なうのがよい。該酸としては例え
ば、塩酸、硝酸、酢酸、過塩素酸等が例示でき
る。またこの酸処理は通常上記複合体を例えば上
記各種酸の溶液中に浸漬するかまたは上記複合体
を水に浸漬又は分散させた後之に塩化水素ガス等
の酸性ガスを導入することにより実施できる。上
記において酸は炭酸カルシウムと反応する化学量
論量以上用いればよい。この酸処理は好ましくは
室温で行ない得るが、使用する酸の沸点迄の加温
も可能である。反応圧力は通常常圧が採用される
が、加圧条件でも反応は進行する。反応時間は一
般にきわめて短い。上記酸処理によれば複合体を
構成する非晶質シリカに付着して存在する炭酸カ
ルシウムは上記酸により分解され可溶性カルシウ
ム塩となる。従つて本発明に於いては、上記の如
くして得られるカルシウム塩を次いで例えば水洗
等によつて完全に除去し乾燥する。これにより、
非晶質シリカから成る二次粒子及び成形体が得ら
れる。この炭酸カルシウム除去の工程に於ても非
晶質シリカの一次粒子の外形に変化はなく、球殻
状二次粒子の複合体からはそのままの構造の非晶
質シリカ二次粒子が得られ、また複合体の成形体
からは直接にそのままの構造の本発明成形体が得
られる。 In the present invention, the amorphous silica-calcium carbonate composite obtained by the above carbonation is then treated with an acid. This acid treatment is performed to separate calcium carbonate from the amorphous silica that constitutes the above-mentioned complex, and although it preferably has no reactivity with silica, it decomposes calcium carbonate and produces carbon dioxide gas. It is preferable to use an acid capable of producing a water-soluble calcium salt and a water-soluble calcium salt. Examples of the acid include hydrochloric acid, nitric acid, acetic acid, and perchloric acid. Further, this acid treatment can usually be carried out by immersing the above-mentioned composite in a solution of the various acids mentioned above, or by introducing an acidic gas such as hydrogen chloride gas after immersing or dispersing the above-mentioned composite in water. . In the above, the acid may be used in a stoichiometric amount or more to react with calcium carbonate. This acid treatment can preferably be carried out at room temperature, but heating up to the boiling point of the acid used is also possible. The reaction pressure is usually normal pressure, but the reaction proceeds even under pressurized conditions. Reaction times are generally very short. According to the acid treatment, the calcium carbonate present adhering to the amorphous silica constituting the composite is decomposed by the acid and becomes a soluble calcium salt. Therefore, in the present invention, the calcium salt obtained as described above is then completely removed, for example, by washing with water, and then dried. This results in
Secondary particles and molded bodies made of amorphous silica are obtained. Even in this step of removing calcium carbonate, there is no change in the external shape of the primary amorphous silica particles, and amorphous silica secondary particles with the same structure are obtained from the composite of spherical secondary particles. Moreover, the molded product of the present invention having the same structure can be obtained directly from the composite molded product.
本発明の非晶質シリカ成形体は、また上記の如
くして得られる非晶質シリカ二次粒子を水性スラ
リーの形態とし、該スラリーを常法に従い脱水成
形及び乾燥させることにより製造できる。この成
形に当つて上記水性スラリーは、好ましくは水対
固形分重量比を８〜50：１の範囲に調製される。
また該スラリーには必要に応じて石綿、ガラス繊
維、岩綿、合成繊維、天然繊維、パルプ、炭素繊
維、ステンレスフアイバー等の繊維質補強剤、ア
ルミナゾル、コロイダルシリカゾル、クレー、セ
メント、着色剤、充填剤等の各種添加剤を添加で
き、之によつて更に有用な性質を付与できる。成
形体の嵩密度は成形時の圧力により任意に調節可
能であり広範囲なものとできる。好ましくは該嵩
密度は約0.1g/cm3から約1.0g/cm3とするのがよい。 The amorphous silica molded article of the present invention can also be produced by forming the amorphous silica secondary particles obtained as described above into an aqueous slurry, and dehydrating and drying the slurry according to a conventional method. In this molding, the aqueous slurry is preferably prepared such that the weight ratio of water to solids is in the range of 8 to 50:1.
In addition, the slurry may include asbestos, glass fiber, rock wool, synthetic fiber, natural fiber, pulp, carbon fiber, fibrous reinforcing agent such as stainless fiber, alumina sol, colloidal silica sol, clay, cement, coloring agent, filler, etc. Various additives such as additives can be added, thereby imparting more useful properties. The bulk density of the molded product can be arbitrarily adjusted by adjusting the pressure during molding, and can be adjusted over a wide range. Preferably, the bulk density is about 0.1 g/cm 3 to about 1.0 g/cm 3 .
更に本発明成形体は、前記で得られる非晶質シ
リカ―炭酸カルシウム複合体の球殻状二次粒子
を、上記と同様にして脱水成形し、かくして得ら
れる成形体を前記と同様に酸処理することによつ
ても収得できる。 Furthermore, the molded product of the present invention can be obtained by subjecting the spherical shell-like secondary particles of the amorphous silica-calcium carbonate composite obtained above to dehydration molding in the same manner as described above, and then subjecting the thus obtained molded product to acid treatment in the same manner as described above. You can also earn money by doing so.
実施例
以下本発明を更に詳細に説明するため参考例及
び実施例を挙げる。Examples Reference examples and examples are given below to explain the present invention in more detail.
各参考例及び実施例で得られる物質のＸ線回折
図、電子顕微鏡写真及び走査型電子顕微鏡写真を
図面に示す。 The X-ray diffraction diagram, electron micrograph, and scanning electron micrograph of the substances obtained in each reference example and example are shown in the drawings.
第１図Ａ〜Ｃは夫々出発原料であるゾーノトラ
イト結晶、該結晶を炭酸化処理して得られる非晶
質シリカ―炭酸カルシウム複合粒子及び非晶質シ
リカ一次粒子のＸ線回折図である。これはＸ線回
折計（Ｘ―ray diffractometer）を利用し、Cuタ
ーゲツトで波長が1.5418ÅのＸ線を発生させ、こ
れを試料に照射して、その回折角と回折強度を求
めることにより記録されたものである。回折強度
の最も高い３本の回折線を読み試料の同定を行な
つた。 FIGS. 1A to 1C are X-ray diffraction patterns of zonotrite crystals as starting materials, amorphous silica-calcium carbonate composite particles obtained by carbonating the crystals, and amorphous silica primary particles, respectively. This is recorded by using an X-ray diffractometer to generate X-rays with a wavelength of 1.5418 Å at a Cu target, irradiating the sample with this, and determining the diffraction angle and diffraction intensity. It is something that The sample was identified by reading the three diffraction lines with the highest diffraction intensity.
第２図及び第３図は倍率20000倍の電子顕微鏡
写真であり、各図中Ａは出発原料とする珪酸カル
シウム結晶及びＢは非晶質シリカ一次粒子を表わ
す。 FIGS. 2 and 3 are electron micrographs at a magnification of 20,000 times, and in each figure, A represents calcium silicate crystals used as starting materials, and B represents amorphous silica primary particles.
第４図は倍率5000倍の電子顕微鏡写真であり図
中Ａは出発原料とするα―ダイカルシウムシリケ
ートハイドレート結晶及びＢは該結晶から得られ
た非晶質シリカ一次粒子である。 FIG. 4 is an electron micrograph at a magnification of 5,000 times, in which A is an α-dicalcium silicate hydrate crystal used as a starting material, and B is an amorphous silica primary particle obtained from the crystal.
第５図及び第６図は走査型電子顕微鏡写真であ
り各図中Ａは出発原料とする珪酸カルシウム結晶
の球殻状二次粒子及びＢは該二次粒子から得られ
た非晶質シリカ二次粒子を夫々示す。但し第５図
Ｂは倍率2000倍であり、他はすべて倍率600倍で
ある。 Figures 5 and 6 are scanning electron micrographs. In each figure, A indicates spherical secondary particles of calcium silicate crystals used as starting materials, and B indicates amorphous silica secondary particles obtained from the secondary particles. The following particles are shown respectively. However, Fig. 5B has a magnification of 2000x, and all others have a magnification of 600x.
第７図は成形体の破断面の走査型電子顕微鏡写
真（倍率600倍）であり、Ａは出発原料とする珪
酸カルシウム結晶の二次粒子から構成される成形
体及びＢは本発明の非晶質シリカ成形体を夫々示
す。 FIG. 7 is a scanning electron micrograph (magnification: 600x) of the fractured surface of a molded body, in which A is a molded body composed of secondary particles of calcium silicate crystals used as a starting material, and B is an amorphous body of the present invention. The silica molded bodies are shown respectively.
参考例 １
石灰原料として生石灰及び珪酸原料として350
メツシユ全通の珪石粉を用いる。之等を石灰と珪
酸とのモル比が0.98：１となる割合で水に分散さ
せ、水対固形分比（重量）を12：１として原料ス
ラリーを調製する。該原料スラリーをオートクレ
ーブに装入し191℃に加熱し12Kg/cm2の飽和水蒸気
圧下で８時間撹拌しながら水熱反応させてゾーノ
トライト結晶のスラリーを得る。Reference example 1 Quicklime as lime raw material and 350 as silicic acid raw material
Uses silica powder from Metsuyu. A raw material slurry is prepared by dispersing these in water at a molar ratio of lime to silicic acid of 0.98:1, and setting the water to solids ratio (weight) to 12:1. The raw material slurry is charged into an autoclave, heated to 191°C, and subjected to a hydrothermal reaction under a saturated steam pressure of 12 kg/cm 2 with stirring for 8 hours to obtain a slurry of zonotrite crystals.
得られた結晶のＸ線回折図は第１図Ａの通りで
あり、12.7゜、27.6゜及び29.0°にゾーノトライ
ト結晶特有の回折ピーク（２θ）を示す。その強
熱後の組成は次の通りである。 The X-ray diffraction diagram of the obtained crystal is as shown in FIG. 1A, and shows diffraction peaks (2θ) characteristic of zonotrite crystals at 12.7°, 27.6°, and 29.0°. Its composition after ignition is as follows.
SiO2 48.88％
CaO 45.60
Ａ2O3 0.26
Fe2O3 0.54
Ig.loss 4.51
99.79
上記で得たスラリーは、走査型電子顕微鏡観察
の結果第５図Ａに示される通り、ゾーノトライト
針状結晶が多数不規則に三次元的に絡合して形成
され、約10〜60μｍの範囲の直径を有する実質的
に球殻状のゾーノトライト二次粒子を、多数水中
に分散させて構成されている。該二次粒子は約
95.6％の空隙率を有する。 SiO 2 48.88% CaO 45.60 A 2 O 3 0.26 Fe 2 O 3 0.54 Ig.loss 4.51 99.79 The slurry obtained above contained many needle-like zonotrite crystals as shown in Figure 5A as a result of scanning electron microscopy observation. It is composed of a large number of substantially spherical zonotrite secondary particles, which are irregularly entangled in three dimensions and have a diameter in the range of about 10 to 60 μm, dispersed in water. The secondary particles are approximately
It has a porosity of 95.6%.
次いで上記スラリーを150℃で乾燥後粉砕して
二次粒子を一次粒子に分割し、白色微粉末を得
る。この電子顕微鏡写真は第２図Ａに示される。
該図より上記一次粒子は短冊状の外形をもち、長
さ約１〜20μｍ、厚さ約0.02〜1.0μｍ及び巾約
0.02〜1.0μｍの大きさを有し、長さが厚さの少
なくとも約10倍であることがわかる。該一次粒子
は約50m2/gの比表面積を有する。 Next, the slurry is dried at 150° C. and pulverized to separate secondary particles into primary particles to obtain white fine powder. This electron micrograph is shown in FIG. 2A.
From the figure, the primary particles have a rectangular outer shape, with a length of about 1 to 20 μm, a thickness of about 0.02 to 1.0 μm, and a width of about
It can be seen that the length is at least about 10 times the thickness, with a size of 0.02 to 1.0 μm. The primary particles have a specific surface area of approximately 50 m 2 /g.
また上記スラリーを40×120×120（mm）の型枠
に注入後プレス脱水成形し、乾燥してゾーノトラ
イト結晶の成形体を得る。該成形体の破断面の走
査型電子顕微鏡写真は第７図Ａの通りである。該
図より成形体はこれを構成する球殻状二次粒子が
少なくとも一方向に圧縮され且つ相互に強固に絡
み合つてその球殻状形態を保持したまま一体とな
り形態されていることがわかる。得られる成形体
は嵩密度0.2g/cm3、曲げ強度約４Kg/cm2及び空隙率
約92.7％である。 Further, the above slurry is poured into a mold of 40 x 120 x 120 (mm), press-dehydrated, and dried to obtain a molded body of zonotrite crystals. A scanning electron micrograph of the fractured surface of the molded body is shown in FIG. 7A. It can be seen from this figure that the spherical shell-like secondary particles constituting the molded body are compressed in at least one direction and are tightly intertwined with each other to form an integral body while maintaining the spherical shell shape. The resulting molded body has a bulk density of 0.2 g/cm 3 , a bending strength of about 4 Kg/cm 2 and a porosity of about 92.7%.
参考例 ２
石灰原料として消石灰及び珪酸原料として350
メツシユ全通の珪石粉を用いる。之等を石灰と珪
酸とのモル比が0.80：１となる割合で水に分散さ
せ、水対固形分比（重量）を12：１として原料ス
ラリーを調製する。該原料スラリーをオートクレ
ーブに装入し191℃に加熱し12Kg/cm2の飽和水蒸気
圧下で５時間撹拌しながら水熱反応させてトベル
モライト結晶のスラリーを得る。Reference example 2 Slaked lime as a lime raw material and 350 as a silicate raw material
Uses silica powder from Metsuyu. A raw material slurry is prepared by dispersing these in water at a molar ratio of lime to silicic acid of 0.80:1, and setting the water to solids ratio (weight) to 12:1. The raw material slurry is charged into an autoclave, heated to 191°C, and subjected to a hydrothermal reaction with stirring under a saturated steam pressure of 12 kg/cm 2 for 5 hours to obtain a slurry of tobermolite crystals.
得られた結晶はＸ線回折の解析の結果、7.8
゜、29.0゜及び30.0゜にトベルモライト結晶特有
の回折ピーク（２θ）を示す。その強熱後の組成
は次の通りである。 As a result of X-ray diffraction analysis, the crystal obtained was 7.8
It exhibits diffraction peaks (2θ) characteristic of tobermolite crystals at angles of 29.0°, 29.0°, and 30.0°. Its composition after ignition is as follows.
SiO2 48.88％
CaO 38.55
Ａ2O3 0.31
Fe2O3 0.45
Ig.loss 11.36
99.05
上記で得たスラリーは、走査型電子顕微鏡観察
の結果第６図Ａに示される通り、トベルモライト
の板状結晶が多数不規則に三次元的に絡合して形
成され、約10〜60μｍの範囲の直径を有する実質
的に球殻状のトベルモライト二次粒子を、多数水
中に分散させて構成されている。該二次粒子は約
94.0％の空隙率を有する。 SiO 2 48.88% CaO 38.55 A 2 O 3 0.31 Fe 2 O 3 0.45 Ig.loss 11.36 99.05 As shown in Figure 6A as a result of scanning electron microscopy, the slurry obtained above has a plate-like shape of tobermolite. It is composed of a large number of substantially spherical tobermolite secondary particles, which are formed by irregular three-dimensional entanglement of many crystals and have a diameter in the range of about 10 to 60 μm, dispersed in water. ing. The secondary particles are approximately
It has a porosity of 94.0%.
次いで上記スラリーを150℃で乾燥後粉砕して
二次粒子を一次粒子に分割し、白色微粉末を得
る。その電子顕微鏡写真は第３図Ａに示される。
該図より上記一次粒子は板状の外形をもち、長さ
約１〜20μｍ、厚さ約0.02〜0.1μｍ及び巾約0.2
〜0.5μｍの大きさを有し、長さが厚さの少なく
とも約10倍であることがわかる。該一次粒子は約
61m2/gの比表面積を有する。 Next, the slurry is dried at 150° C. and pulverized to separate secondary particles into primary particles to obtain white fine powder. The electron micrograph is shown in FIG. 3A.
From the figure, the primary particles have a plate-like external shape, a length of about 1 to 20 μm, a thickness of about 0.02 to 0.1 μm, and a width of about 0.2 μm.
It can be seen that the length is at least about 10 times the thickness, with a size of ˜0.5 μm. The primary particles are approximately
It has a specific surface area of 61m 2 /g.
また上記スラリーを40×120×120（mm）の型枠
に注入後プレス脱水成形し、乾燥してトベルモラ
イト結晶の成形体を得る。該成形体の破断面の走
査型電子顕微鏡写真は第７図Ａと同様であり、成
形体はこれを構成する球殻状二次粒子が少なくと
も一方向に圧縮され且つ相互に強固に絡み合つて
その球殻状形態を保持したまま一体となり形成さ
れている。得られる成形体は嵩密度0.3g/cm3、曲
げ強度約12Kg/cm2及び空隙率88.0％である。 Further, the above slurry is poured into a mold of 40 x 120 x 120 (mm), press-dehydrated, and dried to obtain a molded body of tobermolite crystals. The scanning electron micrograph of the fractured surface of the molded body is similar to that shown in FIG. 7A, and the molded body has spherical shell-like secondary particles that are compressed in at least one direction and are tightly intertwined with each other. It is integrally formed while maintaining its spherical shell shape. The obtained molded body has a bulk density of 0.3 g/cm 3 , a bending strength of about 12 Kg/cm 2 and a porosity of 88.0%.
参考例 ３
石灰原料として生石灰及び珪酸原料として市販
のホワイトカーボン（粒子径100μｍ以下、SiO2
含量約88重量％）を用いる。之等を石灰と珪酸と
のモル比が0.57：１となる割合で水に分散させ、
水対固形分比（重量）を12：１として原料スラリ
ーを調製する。該原料スラリーをオートクレーブ
に装入し200℃に加熱し15Kg/cm2の飽和水蒸気圧下
で８時間撹拌しながら水熱反応させてジヤイロラ
イト結晶のスラリーを得る。Reference example 3 Quicklime as a lime raw material and commercially available white carbon as a silicic acid raw material (particle size 100 μm or less, SiO 2
(approximately 88% by weight). Disperse these in water at a molar ratio of lime and silicic acid of 0.57:1,
A raw material slurry is prepared with a water to solids ratio (weight) of 12:1. The raw material slurry is charged into an autoclave, heated to 200°C, and subjected to a hydrothermal reaction with stirring for 8 hours under a saturated steam pressure of 15 kg/cm 2 to obtain a slurry of gyrolite crystals.
得られた結晶はＸ線回析の結果4.0゜、28.2゜
及び28.9゜にジヤイロライト結晶特有の回折ピー
ク（２θ）を示す。その強熱後の組成は次の通り
である。 As a result of X-ray diffraction, the obtained crystal exhibits diffraction peaks (2θ) at 4.0°, 28.2°, and 28.9° that are characteristic of gairolite crystals. Its composition after ignition is as follows.
SiO2 56.88％
CaO 30.75
Ａ2O3 0.39
Fe2O3 0.29
Ig.loss 11.39
99.70
上記で得たスラリーは、走査型電子顕微鏡観察
の結果ジヤイロライトの板状結晶が多数不規則に
三次元的に絡合して形成され、約10〜60μｍの範
囲の直径を有する実質的に球殻状のジヤイロライ
ト二次粒子を、多数水中に分散させて構成されて
いる。該二次粒子は約94.0％の空隙率を有する。 SiO 2 56.88% CaO 30.75 A 2 O 3 0.39 Fe 2 O 3 0.29 Ig.loss 11.39 99.70 As a result of scanning electron microscopy observation, the slurry obtained above showed a large number of plate-shaped crystals of gairolite irregularly intertwined in three dimensions. It is constructed by dispersing in water a large number of substantially spherical gyrolite secondary particles formed together and having a diameter in the range of about 10 to 60 μm. The secondary particles have a porosity of about 94.0%.
次いで上記スラリーを150℃で乾燥後粉砕して
二次粒子を一次粒子に分割し、白色微粉末を得
る。得られた一次粒子は電子顕微鏡観察の結果、
板状の外形をもち、長さ約１〜20μｍ、厚さ約
0.02〜0.1μｍ及び巾約0.2〜５μｍの大きさを有
し、長さが厚さの少なくとも10倍であることがわ
かる。該一次粒子は約60m2/gの比表面積を有す
る。 Next, the slurry is dried at 150° C. and pulverized to separate secondary particles into primary particles to obtain white fine powder. As a result of electron microscopy observation of the obtained primary particles,
It has a plate-like external shape, about 1 to 20 μm in length, and about thickness.
It can be seen that it has a size of 0.02-0.1 μm and a width of about 0.2-5 μm, and the length is at least 10 times the thickness. The primary particles have a specific surface area of about 60 m 2 /g.
また上記スラリーを40×120×120（mm）の型枠
に注入後プレス脱水成形し、乾燥してジヤイロラ
イト結晶の成形体を得る。該成形体の破断面の走
査型電子顕微鏡写真は第７図Ａと同様であり、成
形体はこれを構成する球殻状二次粒子が少なくと
も一方向に圧縮され且つ相互に強固に絡み合つて
その球殻状形態を保持したまま一体となり形成さ
れていることがわかる。得られる成形体は嵩密度
0.3g/cm3、曲げ強度約８Kg/cm2及び空隙率約88.0％
である。 Further, the above slurry is poured into a mold of 40 x 120 x 120 (mm), press-dehydrated, and dried to obtain a molded body of gyrolite crystals. The scanning electron micrograph of the fractured surface of the molded body is similar to that shown in FIG. 7A, and the molded body has spherical shell-like secondary particles that are compressed in at least one direction and are tightly intertwined with each other. It can be seen that they are integrally formed while maintaining their spherical shell shape. The resulting compact has a bulk density
0.3g/cm 3 , bending strength approximately 8Kg/cm 2 and porosity approximately 88.0%
It is.
参考例 ４
石灰原料として生石灰及び珪酸原料として350
メツシユ全通の珪石粉を用いる。之等を石灰と珪
酸とのモル比が2.0：１となる割合で水に分散さ
せ、水対固形分比（重量）を４：１として原料ス
ラリーを調製する。該原料スラリーをオートクレ
ーブに装入し191℃に加熱し12Kg/cm2の飽和水蒸気
圧下で５時間加熱反応させてα―ダイカルシウム
シリケートハイドレート結晶のスラリーを得る。Reference example 4 Quicklime as lime raw material and 350 as silicic acid raw material
Uses silica powder from Metsuyu. These are dispersed in water at a molar ratio of lime to silicic acid of 2.0:1, and a raw material slurry is prepared with a water to solid content ratio (weight) of 4:1. The raw material slurry is charged into an autoclave, heated to 191°C, and reacted by heating for 5 hours under a saturated steam pressure of 12 kg/cm 2 to obtain a slurry of α-dicalcium silicate hydrate crystals.
得られた結晶はＸ線回析の解析の結果16.6゜、
27.3゜及び37.2゜にα―ダイカルシウムシリケー
トハイドレート結晶特有の回折ピーク（２θ）を
示す。その強熱後の組成は次の通りである。 As a result of X-ray diffraction analysis, the obtained crystal has an angle of 16.6°,
It shows diffraction peaks (2θ) characteristic of α-dicalcium silicate hydrate crystals at 27.3° and 37.2°. Its composition after ignition is as follows.
SiO2 30.81％
CaO 57.02
Ａ2O3 0.45
Fe2O3 0.50
Ig.loss 10.05
98.83
上記で得たスラリーを150℃で乾燥後粉砕して
白色微分末一次粉子を得る。その電子顕微鏡写真
を第４図Ａに示す。該図より上記一次粒子は板状
の外形をもち、長さ約１〜300μｍ、厚さ約0.1〜
１μｍ及び巾約１〜30μｍの大きさを有し、長さ
が厚さの少なくとも10倍である板状形態を有する
ことがわかる。該一次粒子は約６g/cm3の比表面
積を有する。 SiO 2 30.81% CaO 57.02 A 2 O 3 0.45 Fe 2 O 3 0.50 Ig.loss 10.05 98.83 The slurry obtained above is dried at 150° C. and then ground to obtain a white differential powder primary powder. The electron micrograph is shown in FIG. 4A. From the figure, the above primary particles have a plate-like external shape, a length of about 1 to 300 μm, and a thickness of about 0.1 to 300 μm.
It can be seen that it has a plate-like form with a size of 1 μm and a width of about 1-30 μm, and a length that is at least 10 times the thickness. The primary particles have a specific surface area of about 6 g/cm 3 .
参考例 ５
参考例１で得たゾーノトライト針状晶一次粒子
を出発原料とする。これを５倍重量の水と共に密
閉型圧力容器内に装入し、室温下該容器内に炭酸
ガスを圧入し、内圧を３Kg/cm2に保持して約80分
間炭酸化を行ない、非晶質シリカ―炭酸カルシウ
ム複合一次粒子を得る。得られた一次粒子のＸ線
回折結果は第１図Ｂに示す通りであり、第１図Ａ
に認められた珪酸カルシウム結晶特有のピークは
すべて消失しており、代りに23.0゜、29.4゜及び
36.0゜に炭酸カルシウム結晶の回折ピーク（２
θ）のみが現出しており、炭酸化により珪酸カル
シウムが非晶質シリカと炭酸カルシウムとに転換
されたことがわかる。Reference Example 5 The zonotrite needle-like primary particles obtained in Reference Example 1 were used as a starting material. This was placed in a closed pressure vessel together with 5 times its weight of water, carbon dioxide gas was pressurized into the vessel at room temperature, and the internal pressure was maintained at 3 kg/cm 2 to carry out carbonation for about 80 minutes. Obtain quality silica-calcium carbonate composite primary particles. The X-ray diffraction results of the obtained primary particles are as shown in Figure 1B, and Figure 1A.
The characteristic peaks of calcium silicate crystals observed in
Diffraction peak of calcium carbonate crystal at 36.0° (2
Only θ) appears, indicating that calcium silicate was converted into amorphous silica and calcium carbonate by carbonation.
次いで上記で得た非晶質シリカ―炭酸カルシウ
ム複合一次粒子を6N―HC溶液に１分間浸漬す
る。炭酸ガスの発生が認められ上記一次粒子中の
炭酸カルシウムが塩化カルシウムに転換される。
次いで上記酸処理後の一次粒子を充分に水洗し生
成した塩化カルシウムを完全に溶出させる。その
後乾燥して非晶質シリカ一次粒子を得る。 Next, the amorphous silica-calcium carbonate composite primary particles obtained above are immersed in a 6N-HC solution for 1 minute. Generation of carbon dioxide gas is observed, and calcium carbonate in the primary particles is converted to calcium chloride.
Next, the primary particles after the acid treatment are thoroughly washed with water to completely dissolve the produced calcium chloride. Thereafter, it is dried to obtain amorphous silica primary particles.
かくして得られた一次粒子の強熱脱水後の元素
分析結果は次の通りであり、これが高純度シリカ
からなつていることがわかる。 The results of elemental analysis of the thus obtained primary particles after ignited dehydration are as follows, and it can be seen that they are made of high purity silica.
化学組成（％）
SiO2 99.1
Ａ2O3 0.35
CaO ＜0.01
（Ig.loss 5.0）
また上記一次粒子のＸ線回折図は第１図ｃに示
す通りであり、出発原料とするゾーノトライト針
状結晶に基づくピーク及びこれを炭酸化後に得た
複合粒子に含有される炭酸カルシウムに基づくピ
ークはいずれも消失しており、該一次粒子が非晶
質のシリカであることが確認される。 Chemical composition (%) SiO 2 99.1 A 2 O 3 0.35 CaO <0.01 (Ig.loss 5.0) The X-ray diffraction pattern of the above primary particles is as shown in Figure 1c, and the zonotrite needle crystals used as the starting material Both the peak based on calcium carbonate and the peak based on calcium carbonate contained in the composite particles obtained after carbonation have disappeared, confirming that the primary particles are amorphous silica.
上記非晶質シリカ一次粒子の電子顕微鏡写真は
第２図Ｂに示す通りである。該図よりこれは同図
Ａと全く同様に短冊状の外形をもつ結晶様外観を
呈することが認められる。その大きさは長さ約１
〜20μｍ、厚さ約0.02〜0.1μｍ及び巾約0.02〜
1.0μｍであり、長さが厚さの10倍以上であり、
酸処理によつても該針状晶様外観は全く損なわれ
ないことがわかる。 An electron micrograph of the amorphous silica primary particles is shown in FIG. 2B. From the figure, it can be seen that it exhibits a crystal-like appearance with a rectangular outer shape, just like A in the same figure. Its size is about 1 in length
~20μm, thickness approx. 0.02~0.1μm, width approx. 0.02~
1.0μm, length is 10 times or more than thickness,
It can be seen that the acicular crystal-like appearance is not impaired at all even by acid treatment.
参考例 ６
参考例２で得たトベルモライト板状結晶一次粒
子を出発原料とする。これを５倍重量の水と共に
密閉型圧力容器内に装入し、室温下該容器内に炭
酸ガスを圧入し、内圧を３Kg/cm2に保持して約30
分間炭酸化を行ない非晶質シリカ―炭酸カルシウ
ム複合一次粒子を得る。そのＸ線回折の解析結果
は第１図Ｂと同様であり、炭酸化により原料であ
る珪酸カルシウムが非晶質シリカと炭酸カルシウ
ムとに転換されたことが確認される。Reference Example 6 The tobermolite plate-like crystal primary particles obtained in Reference Example 2 are used as a starting material. This was placed in a closed pressure vessel along with 5 times its weight of water, and carbon dioxide gas was pressurized into the vessel at room temperature, and the internal pressure was maintained at 3 kg/cm 2 for approximately 30 minutes.
Carbonation is performed for a minute to obtain amorphous silica-calcium carbonate composite primary particles. The X-ray diffraction analysis results are similar to those shown in FIG. 1B, confirming that the raw material calcium silicate was converted into amorphous silica and calcium carbonate by carbonation.
次いで上記で得た非晶質シリカ―炭酸カルシウ
ム複合一次粒子を6N―HC溶液に１分間浸漬す
る。炭酸ガスの発生が認められ上記一次粒子中の
炭酸カルシウムが塩化カルシウムに転換される。
次いで上記酸処理後の一次粒子を充分に水洗し生
成した塩化カルシウムを完全に溶出させる。その
後乾燥して非晶質シリカ一次粒子を得る。 Next, the amorphous silica-calcium carbonate composite primary particles obtained above are immersed in a 6N-HC solution for 1 minute. Generation of carbon dioxide gas is observed, and calcium carbonate in the primary particles is converted to calcium chloride.
Next, the primary particles after the acid treatment are thoroughly washed with water to completely dissolve the produced calcium chloride. Thereafter, it is dried to obtain amorphous silica primary particles.
かくして得られた一次粒子の強熱乾燥後の元素
分析結果は次の通りであり、これが高純度シリカ
からなつていることがわかる。 The results of elemental analysis of the thus obtained primary particles after ignited drying are as follows, and it can be seen that they are made of high purity silica.
化学組成（％）
SiO2 99.3
Ａ2O3 0.23
CaO ＜0.01
（Ig.loss 4.7）
また上記一次粒子のＸ線回折図は第１図ｃに示
したと同様に出発原料とするトベルモライトの板
状結晶に基づくピーク及びこれを炭酸化後に得た
複合粒子に含有される炭酸カルシウムに基づくピ
ークいおずれも消失しており、該一次粒子が非晶
質のシリカであることが確認される。 Chemical composition (%) SiO 2 99.3 A 2 O 3 0.23 CaO <0.01 (Ig.loss 4.7) The X-ray diffraction pattern of the above primary particles is the same as that shown in Figure 1c, using the tobermolite plate as the starting material. Both the peak based on the crystalline crystals and the peak based on the calcium carbonate contained in the composite particles obtained after carbonation have disappeared, confirming that the primary particles are amorphous silica.
上記非晶質シリカ一次粒子の電子顕微鏡写真は
第３図Ｂに示す通りである。該図よりこれは同図
Ａと全く同様に板状の外形をもつ結晶様外観を呈
することが認められる。その大きさは長さ約１〜
20μｍ、厚さ約0.02〜0.1μｍ及び巾約0.2〜5.0μ
ｍであり、長さが厚さの10倍以上であり、酸処理
によつても該結晶様外観は全く損なわれないこと
がわかる。 An electron micrograph of the amorphous silica primary particles is shown in FIG. 3B. From the figure, it can be seen that it exhibits a crystal-like appearance with a plate-like outer shape, just like A in the same figure. Its size is about 1~
20μm, thickness approx. 0.02~0.1μm and width approx. 0.2~5.0μm
m, the length is more than 10 times the thickness, and it can be seen that the crystal-like appearance is not impaired at all even by acid treatment.
参考例 ７
参考例３で得たジヤイロライト板状結晶一次粒
子を出発原料とする。これを５倍重量の水と共に
密閉型圧力容器内に装入し、室温下該容器内に炭
酸ガスを圧入し、内圧を３Kg/cm2に保持して約30
分間炭酸化を行なう。Reference Example 7 The gyirolite plate-like crystal primary particles obtained in Reference Example 3 are used as a starting material. This was placed in a closed pressure vessel along with 5 times its weight of water, and carbon dioxide gas was pressurized into the vessel at room temperature, and the internal pressure was maintained at 3 kg/cm 2 for approximately 30 minutes.
Carry out carbonation for a minute.
かくして非晶質シリカ―炭酸カルシウム複合一
次粒子を得る。そのＸ線回折の解析結果は第１図
Ｂと同様であり、炭酸化により原料である珪酸カ
ルシウムが非晶質シリカと炭酸カルシウムとに転
換されたことが確認される。 In this way, amorphous silica-calcium carbonate composite primary particles are obtained. The X-ray diffraction analysis results are similar to those shown in FIG. 1B, confirming that the raw material calcium silicate was converted into amorphous silica and calcium carbonate by carbonation.
次いで上記で得た非晶質シリカ―炭酸カルシウ
ム複合一次粒子を6N―HC溶液に１分間浸漬す
る。炭酸ガスの発生が認められ上記一次粒子中の
炭酸カルシウムが塩化カルシウムに転換される。
次いで上記酸処理後の一次粒子を充分に水洗し生
成した塩化カルシウムを完全に溶出させる。その
後乾燥して非晶質シリカ一次粒子を得る。 Next, the amorphous silica-calcium carbonate composite primary particles obtained above are immersed in a 6N-HC solution for 1 minute. Generation of carbon dioxide gas is observed, and calcium carbonate in the primary particles is converted to calcium chloride.
Next, the primary particles after the acid treatment are thoroughly washed with water to completely dissolve the produced calcium chloride. Thereafter, it is dried to obtain amorphous silica primary particles.
かくして得られた一次粒子の元素分析結果は次
の通りであり、これが高純度シリカからなつてい
ることがわかる。 The results of elemental analysis of the primary particles thus obtained are as follows, and it can be seen that they are made of high purity silica.
化学組成（％）
SiO2 99.4
Ａ2O3 0.09
CaO ＜0.01
（Ig.logg 5.8）
また上記一次粒子のＸ線回折図は第１図ｃに示
すと同様であり、出発原料とするジヤイロライト
板状結晶に基づくピーク及びこれを炭酸化後に得
た複合粒子に含有される炭酸カルシウムに基づく
ピークはいずれも消失しており、該一次粒子が非
晶質のシリカであることが確認される。 Chemical composition (%) SiO 2 99.4 A 2 O 3 0.09 CaO <0.01 (Ig.logg 5.8) The X-ray diffraction pattern of the above primary particles is the same as shown in Figure 1c, and the gyrolite plate-like starting material Both the peaks based on crystals and the peaks based on calcium carbonate contained in the composite particles obtained after carbonation have disappeared, confirming that the primary particles are amorphous silica.
上記非晶質シリカ一次粒子は電子顕微鏡写真観
察の結果、板状の外形をもつ結晶様外観を呈する
ことが認められる。その大きさは長さ約１〜20μ
ｍ、厚さ約0.02〜0.1μｍ及び巾約0.2〜５μｍで
あり、長さが厚さの10倍以上であり、酸処理によ
つても該結晶様外観は全く損なわれないことがわ
かる。 As a result of electron micrograph observation, it is recognized that the amorphous silica primary particles have a crystal-like appearance with a plate-like outer shape. Its size is about 1 to 20μ in length.
m, thickness of about 0.02 to 0.1 μm, and width of about 0.2 to 5 μm, the length is more than 10 times the thickness, and it can be seen that the crystal-like appearance is not impaired at all even by acid treatment.
参考例 ８
参考例４で得たα―ダイカルシウムシリケート
ハイドレートの板状結晶一次粒子を出発原料とす
る。これを５倍重量の水と共に密閉型圧力容器内
に装入し、室温下該容器内に炭酸ガスを圧入し、
内圧を３Kg/cm2に保持して約30分間炭酸化を行
う。Reference Example 8 The plate-shaped crystal primary particles of α-dicalcium silicate hydrate obtained in Reference Example 4 were used as a starting material. This was placed in a closed pressure vessel together with 5 times its weight of water, and carbon dioxide gas was pressurized into the vessel at room temperature.
Carbonation is carried out for about 30 minutes while maintaining the internal pressure at 3 Kg/cm 2 .
かくして非晶質シリカ―炭酸カルシウム複合一
次粒子を得る。そのＸ線回折の解析結果は第１図
Ｂと同様であり、炭酸化により原料である珪酸カ
ルシウムが非晶質シリカと炭酸カルシウムとに転
換されたことが確認される。 In this way, amorphous silica-calcium carbonate composite primary particles are obtained. The X-ray diffraction analysis results are similar to those shown in FIG. 1B, confirming that the raw material calcium silicate was converted into amorphous silica and calcium carbonate by carbonation.
次いで上記で得た非晶質シリカ―炭酸カルシウ
ム複合一次粒子を6N―HC溶液に１分間浸漬す
る。炭酸ガスの発生が認められ上記一次粒子中の
炭酸カルシウムが塩化カルシウムに転換される。
次いで上記酸処理後の一次粒子を充分に水洗し生
成した塩化カルシウムを完全に溶出させる。その
後乾燥して非晶質シリカ一次粒子を得る。 Next, the amorphous silica-calcium carbonate composite primary particles obtained above are immersed in a 6N-HC solution for 1 minute. Generation of carbon dioxide gas is observed, and calcium carbonate in the primary particles is converted to calcium chloride.
Next, the primary particles after the acid treatment are thoroughly washed with water to completely dissolve the produced calcium chloride. Thereafter, it is dried to obtain amorphous silica primary particles.
かくして得られた一次粒子の強熱乾燥の元素分
析結果は次の通りであり、これが高純度シリカか
らなつていることがわかる。 The results of elemental analysis of the thus obtained primary particles after ignition drying are as follows, and it can be seen that they are made of high-purity silica.
化学組成（％）
SiO2 99.6
Ａ2O3 0.12
CaO ＜0.01
Ig.loss 5.2
また該一次粒子のＸ線回折図は第１図ｃに示す
と同様であり、出発原料とするα―ダイカルシウ
ムシリケートハイドレートの板状結晶に基づくピ
ーク及びこれを炭酸化後に得た複合粒子に含有さ
れる炭酸カルシウムに基づくピークはいずれも消
失しており、該一次粒子が非晶質のシリカである
ことが確認される。 Chemical composition (%) SiO 2 99.6 A 2 O 3 0.12 CaO <0.01 Ig.loss 5.2 The X-ray diffraction pattern of the primary particles is the same as shown in Figure 1c, and the α-dicalcium silicate used as the starting material The peaks based on the plate-shaped crystals of hydrate and the peaks based on the calcium carbonate contained in the composite particles obtained after carbonation both disappeared, confirming that the primary particles were amorphous silica. be done.
上記非晶質シリカ一次粒子の電子顕微鏡写真は
第４図Ｂに示す通り、板状の外形をもつ結晶様外
観を呈することが認められる。その大きさは長さ
約１〜300μｍ、厚さ約0.1〜１μｍ及び巾約１〜
30μｍであり、長さが厚さの10倍以上であり、酸
処理によつても該結晶様外観は全く損なわれない
ことがわかる。 As shown in FIG. 4B, an electron micrograph of the above-mentioned amorphous silica primary particles shows a crystal-like appearance with a plate-like outer shape. Its size is approximately 1 to 300 μm in length, approximately 0.1 to 1 μm in thickness, and approximately 1 to 1 μm in width.
30 μm, the length is more than 10 times the thickness, and it can be seen that the crystal-like appearance is not impaired at all even by acid treatment.
実施例 １
参考例１で得たゾーノトライト結晶のスラリー
を脱水し、水対ゾーノトライト結晶固形分比を
５／１とし、これを湿潤雰囲気の密閉型圧力容器
中に入れ、炭酸ガスを圧入して３Kg/cm2の内圧と
し、約30分間反応させ非晶質シリカ―炭酸カルシ
ウム複合二次粒子を得る。そのＸ線回折の解析結
果は第１図Ｂと同様であり、炭酸化により原料で
ある珪酸カルシウムが非晶質シリカと炭酸カルシ
ウムとに転換されたことが確認される。Example 1 The slurry of zonotrite crystals obtained in Reference Example 1 was dehydrated to a water to zonotrite crystal solids ratio of 5/1, placed in a closed pressure vessel in a humid atmosphere, and carbon dioxide gas was pressurized to produce 3 kg. /cm 2 internal pressure and react for about 30 minutes to obtain amorphous silica-calcium carbonate composite secondary particles. The X-ray diffraction analysis results are similar to those shown in FIG. 1B, confirming that the raw material calcium silicate was converted into amorphous silica and calcium carbonate by carbonation.
次いで上記で得た複合二次粒子を、6N―HC
溶液中に１分間浸漬する。浸漬と同時に炭酸ガス
が発生し、一次粒子中の炭酸カルシウムが塩化カ
ルシウムに転換される。次いで水洗を充分に行な
い、上記で生成した塩化カルシウムを完全に溶出
させる。その後乾燥して非晶質シリカ二次粒子を
得る。 Next, the composite secondary particles obtained above were treated with 6N-HC
Immerse in the solution for 1 minute. Carbon dioxide gas is generated at the same time as the immersion, and calcium carbonate in the primary particles is converted to calcium chloride. Next, the sample is thoroughly washed with water to completely dissolve the calcium chloride produced above. Thereafter, it is dried to obtain amorphous silica secondary particles.
かくして得られた二次粒子のＸ線回折結果は第
１図Ｃに示したと同一であり、珪酸カルシウム結
晶に基づくピーク及び炭酸カルシウムに基づくピ
ークがいずれも消失しており、該二次粒子が非晶
質シリカから構成されることがわかる。 The X-ray diffraction results of the secondary particles obtained in this way are the same as shown in Figure 1C, and the peaks based on calcium silicate crystals and the peaks based on calcium carbonate have both disappeared, indicating that the secondary particles are non-contaminated. It can be seen that it is composed of crystalline silica.
上記非晶質シリカ二次粒子の2000倍走査型電子
顕微鏡観察結果は第５図Ｂに示される通りであ
る。該図よりこの二次粒子はゾーノトライト二次
粒子及びその形態をそのまま保持した非晶質シリ
カ―炭酸カルシウム複合二次粒子と実質的に同一
の形状を有することがわかる。 The results of observation of the above-mentioned amorphous silica secondary particles using a 2000x scanning electron microscope are shown in FIG. 5B. It can be seen from the figure that this secondary particle has substantially the same shape as the zonotrite secondary particle and the amorphous silica-calcium carbonate composite secondary particle that maintains its shape.
以下得られた非晶質シリカ二次粒子の特性を示
す。 The characteristics of the obtained amorphous silica secondary particles are shown below.
嵩密度 0.04g/cm3
比表面積 400m2/g
400℃加熱後 350m2/g
空隙率 98％
耐熱性 950℃で変形なし
吸油量 1100cc／100g
化学分析値SiO2含量 99.1％
但し上記各特性は次の通り求めたものであり、
以下の実施例においても同じである。 Bulk density 0.04g/ cm3 Specific surface area 400m 2 /g After heating to 400℃ 350m 2 /g Porosity 98% Heat resistance No deformation at 950℃ Oil absorption 1100cc/100g Chemical analysis SiO 2 content 99.1% However, the above characteristics are This is what I asked for as follows,
The same applies to the following examples.
嵩密度：50ｇ/cm2荷重ピストンシリンダー法に
よる方法で粉体10gを断面積５cm2の円筒に入
れこれに250gで荷重を与えた後その容積を
求めて次式で求める。 Bulk density: 50 g/cm 2 Using the load piston-cylinder method, 10 g of powder is placed in a cylinder with a cross-sectional area of 5 cm 2 , a load of 250 g is applied to the cylinder, and the volume is determined using the following formula.
１０（ｇ）／容積（cm3）＝嵩密度
真比重：ベツクマン社空気比較式比重計によ
り、Heガス置換で求めた。 10 (g)/Volume (cm 3 )=Bulk Density True Specific Gravity: Determined by He gas substitution using a Beckman air comparison type hydrometer.
比表面積：BET窒素吸着法による。 Specific surface area: Based on BET nitrogen adsorption method.
空隙率：次式により算出した。 Porosity: Calculated using the following formula.
（１−二次粒子の嵩密度／二次粒子の真比重
）×100
吸油量：ジオクチルフタレート（C6H4
（COOC8H17）2）を100gの粉末中に滴下し吸油
させ粘性が急激にあらわれたときの油の量を
示す。 (1-Bulk density of secondary particles/True specific gravity of secondary particles) x 100 Oil absorption: Dioctyl phthalate (C 6 H 4
(COOC 8 H 17 ) 2 ) is dropped into 100 g of powder to absorb oil, and the amount of oil is shown when viscosity suddenly appears.
上記で得た非晶質シリカ二次粒子粉末100重量
部及びガラス繊維２重量部を800重量部の水に分
散せしめスラリー状とし、これを40×120×150
（mm）の型枠に注入した後プレス脱水し型枠から
取外して105℃で24時間乾燥した。かくして本発
明の成形体を得た。その物性は次の通りである。 100 parts by weight of the amorphous silica secondary particles obtained above and 2 parts by weight of glass fiber were dispersed in 800 parts by weight of water to form a slurry.
After pouring into a (mm) mold, it was dehydrated by pressing, removed from the mold, and dried at 105°C for 24 hours. In this way, a molded article of the present invention was obtained. Its physical properties are as follows.
嵩密度 0.11g/cm3
曲げ強度 ６Kg/cm2
圧縮強度 ９Kg/cm2
空隙率 93％
実施例 ２
参考例２で得たトベルモライト結晶のスラリー
を脱水し、水対トベルモライト結晶固形分比を
５／１とし、これを湿潤雰囲気の容器中に入れ、
炭酸ガスを圧入して３Kg/cm2の内圧とし、約30分
間反応させ、非晶質シリカ―炭酸カルシウム複合
二次粒子を得る。そのＸ線回折の解析結果は第１
図Ｂと同様であり、炭酸化により原料である珪酸
カルシウムが非晶質シリカと炭酸カルシウムとに
転換されたことが確認される。 Bulk density 0.11 g/cm 3 Bending strength 6 Kg/cm 2 Compressive strength 9 Kg/cm 2 Porosity 93% Example 2 The tobermolite crystal slurry obtained in Reference Example 2 was dehydrated, and the water to tobermolite crystal solid content was The ratio was set to 5/1, and this was placed in a container with a humid atmosphere.
Carbon dioxide gas is injected under pressure to give an internal pressure of 3 kg/cm 2 , and the mixture is reacted for about 30 minutes to obtain amorphous silica-calcium carbonate composite secondary particles. The X-ray diffraction analysis results are the first
This is the same as in Figure B, confirming that the raw material calcium silicate was converted into amorphous silica and calcium carbonate by carbonation.
次いで上記で得た複合二次粒子を、6N―HC
溶液中に１分間浸漬する。浸漬と同時に炭酸ガス
が発生し、一次粒子中の炭酸カルシウムが塩化カ
ルシウムに転換される。次いで水洗を充分に行な
い、上記で生成した塩化カルシウムを完全に溶出
させる。その後乾燥して非晶質シリカ二次粒子を
得る。 Next, the composite secondary particles obtained above were treated with 6N-HC
Immerse in the solution for 1 minute. Carbon dioxide gas is generated at the same time as the immersion, and calcium carbonate in the primary particles is converted to calcium chloride. Next, the sample is thoroughly washed with water to completely dissolve the calcium chloride produced above. Thereafter, it is dried to obtain amorphous silica secondary particles.
かくして得られた二次粒子はＸ線回折結果によ
れば珪酸カルシウム結晶に基づくピーク及び炭酸
カルシウムに基づくピークがいずれも消失してお
り、該二次粒子が非晶質シリカから構成されるこ
とがわかる。 According to the X-ray diffraction results of the thus obtained secondary particles, both the peaks based on calcium silicate crystals and the peaks based on calcium carbonate have disappeared, indicating that the secondary particles are composed of amorphous silica. Recognize.
上記非晶質シリカ二次粒子の600倍走査型電子
顕微鏡観察結果は第６図Ｂに示される通りであ
る。該図よりこれはトベルモライト二次粒子及び
その形態をそのまま保持した非晶質シリカ―炭酸
カルシウム複合二次粒子と実質的に同一の形状を
有することがわかる。 The results of observation of the amorphous silica secondary particles with a 600x scanning electron microscope are shown in FIG. 6B. From the figure, it can be seen that these particles have substantially the same shape as the tobermolite secondary particles and the amorphous silica-calcium carbonate composite secondary particles that maintain their morphology.
以下得られた非晶質シリカ二次粒子の特性を示
す。 The characteristics of the obtained amorphous silica secondary particles are shown below.
嵩密度 0.04g/cm3
比表面積 430m2/g
400℃加熱後 380m2/g
空隙率 98％
耐熱性 950℃変形なし
吸油量 980cc／100g
化学分析値SiO2含量 99.3％
上記で得た非晶質シリカ二次粒子を、実施例１
と同様に成形して本発明の成形体を得た。その物
性は次の通りである。 Bulk density 0.04g/cm 3 Specific surface area 430m 2 /g After heating at 400℃ 380m 2 /g Porosity 98% Heat resistance No deformation at 950℃ Oil absorption 980cc/100g Chemical analysis SiO 2 content 99.3% Amorphous obtained above Example 1
A molded article of the present invention was obtained by molding in the same manner as described above. Its physical properties are as follows.
嵩密度 0.15g/cm3
曲げ強度 4.5Kg/cm2
圧縮強度 ７Kg/cm2
空隙率 91％
実施例 ３
参考例１で得たゾーノトライト成形体（嵩密度
0.2g/cm3）を水対固形分重量比２：１の割合で密
閉容器内に入れ、炭酸ガスを圧入し容器内圧を３
Kg/cm2に保持しつつ約80分間反応させる。 Bulk density 0.15 g/cm 3 Bending strength 4.5 Kg/cm 2 Compressive strength 7 Kg/cm 2 Porosity 91% Example 3 Zonotrite molded body obtained in Reference Example 1 (bulk density
0.2g/cm 3 ) was placed in a sealed container at a water to solid weight ratio of 2:1, and carbon dioxide was pressurized to reduce the internal pressure of the container to 3:1.
React for about 80 minutes while maintaining the temperature at Kg/cm 2 .
かくして得られる非晶質シリカ―炭酸カルシウ
ム複合成形体を次いで6N―HCl溶液中に１分間浸
漬する。浸漬と同時に炭酸ガスが発生し、成形体
中の炭酸カルシウムが塩化カルシウムに転換され
る。次いで充分に水洗して生成した塩化カルシウ
ムを完全に溶出させる。その後乾燥して本発明の
成形体を得る。 The thus obtained amorphous silica-calcium carbonate composite molded body is then immersed in a 6N-HCl solution for 1 minute. Carbon dioxide gas is generated at the same time as the immersion, and calcium carbonate in the compact is converted to calcium chloride. Then, it is thoroughly washed with water to completely dissolve the produced calcium chloride. Thereafter, the molded product of the present invention is obtained by drying.
かくして得られる本発明成形体はＸ線回折の解
析結果より非晶質であることが確認される。また
走査型電子顕微鏡観察結果は第７図Ｂに示される
通りであり、出発原料としたゾーノトライト成形
体の構造（第７図Ａ）と実質的に変化のないこと
がわかる。即ち該成形体は約10〜60μｍの範囲の
直径を有し実質的に球殻状を呈する非晶質シリカ
二次粒子が、少なくとも一方向に圧縮され且つ相
互に不規則に三次元的に絡合して一体的に構成さ
れている。 The molded article of the present invention thus obtained is confirmed to be amorphous from the results of X-ray diffraction analysis. The results of scanning electron microscopy are shown in FIG. 7B, and it can be seen that there is no substantial change in the structure of the zonotrite molded body used as the starting material (FIG. 7A). That is, the molded body is made of amorphous silica secondary particles having a diameter in the range of about 10 to 60 μm and having a substantially spherical shell shape, which are compressed in at least one direction and irregularly intertwined with each other in a three-dimensional manner. It is integrally constructed.
以下、上記で得た本発明成形体の物性を示す。 The physical properties of the molded article of the present invention obtained above are shown below.
嵩密度 0.09g/cm3
比表面積 288m2/g
圧縮強度 ６Kg/cm2
空隙率 95％
上記で得た本発明成形体は、これを電気炉内で
1000℃で１時間焼成すると約12％の収縮が認めら
れたが、成形体を構成する二次粒子の球殻状形態
には何ら変化は認められなかつた。焼成後に得た
成形体の特性は次の通りである。 Bulk density 0.09g/cm 3 Specific surface area 288m 2 /g Compressive strength 6Kg/cm 2 Porosity 95% The molded article of the present invention obtained above was heated in an electric furnace.
After firing at 1000°C for 1 hour, about 12% shrinkage was observed, but no change was observed in the spherical shell-like morphology of the secondary particles constituting the molded body. The properties of the molded body obtained after firing are as follows.
嵩密度 0.085g/cm3
圧縮強度 10Kg/cm2
空隙率 95％
また上記焼成品の熱膨張係数は5.7×10-7／℃
であり、更にこれは950℃以下での繰返し加熱試
験によつても実質的に無膨張及び無収縮を示し
た。 Bulk density 0.085g/cm 3 Compressive strength 10Kg/cm 2 Porosity 95% The coefficient of thermal expansion of the above fired product is 5.7×10 -7 /℃
Furthermore, it showed virtually no expansion or contraction even in repeated heating tests at temperatures below 950°C.
更に上記において、参考例１における成形圧力
を増加させた以外は同様にして得た嵩密度が0.62
g/cm3であるゾーノトライト結晶の成形体を出発
原料として、同様の方法により嵩密度が0.3g/cm3
である本発明成形体を製造した。この成形体の成
形圧力方向水平方向に切断した面の走査型電子顕
微鏡観察によれば、成形体を構成する非晶質シリ
カ二次粒子は圧縮された成形圧方向と水平方向に
オリエントされた針状の非晶質シリカ一次粒子か
らなつており、出発原料としたゾーノトライトの
成形体と同様の構造を有することが確認された。 Furthermore, in the above, the bulk density obtained in the same manner as in Reference Example 1 except that the molding pressure was increased was 0.62.
Using the same method as a starting material, using a molded body of zonotrite crystals with a bulk density of 0.3 g/cm 3
A molded article of the present invention was manufactured. According to a scanning electron microscope observation of a surface cut horizontally in the molding pressure direction of this molded product, it was found that the amorphous silica secondary particles constituting the molded product had needles oriented in the compressed molding pressure direction and in the horizontal direction. It was confirmed that the material was composed of amorphous silica primary particles having a similar structure to that of the zonotrite molded material used as the starting material.
得られた成形体の物性を次に示す。 The physical properties of the obtained molded article are shown below.
嵩密度 0.3g/cm3
比表面積 290m2/g
圧縮強度 15Kg/cm2
空隙率 85％
実施例 ４
参考例２で得たトベルモライト成形体（嵩密度
0.3g/cm3）を水対固形分重量比２：１の割合で密
閉容器内に入れ、炭酸ガスを圧入し容器内圧を３
Kg/cm2に保持しつつ約30分間反応させる。 Bulk density 0.3g/cm 3 Specific surface area 290m 2 /g Compressive strength 15Kg/cm 2 Porosity 85% Example 4 Tobermolite molded body obtained in Reference Example 2 (bulk density
0.3g/cm 3 ) was placed in a sealed container at a water to solid weight ratio of 2:1, and carbon dioxide was pressurized to reduce the internal pressure of the container to 3.
React for about 30 minutes while maintaining the temperature at Kg/cm 2 .
かくして得られる非晶質シリカ―炭酸カルシウ
ム複合成形体を次いで6N―HCl溶液中に１分間浸
漬する。浸漬と同時に炭酸ガスが発生し、成形体
中の炭酸カルシウムが塩化カルシウムに転換され
る。次いで充分に水洗して生成した塩化カルシウ
ムを完全に溶出させる。その後乾燥して本発明の
成形体を得る。 The thus obtained amorphous silica-calcium carbonate composite molded body is then immersed in a 6N-HCl solution for 1 minute. Carbon dioxide gas is generated at the same time as the immersion, and calcium carbonate in the compact is converted to calcium chloride. Then, it is thoroughly washed with water to completely dissolve the produced calcium chloride. Thereafter, the molded product of the present invention is obtained by drying.
かくして得られる成形体はＸ線回折の解析結果
より非晶質であることが確認される。また走査型
電子顕微鏡観察結果は第７図Ｂに示されると同様
であり、出発原料としたトベルモライト成形体の
構造と実質的に変化のないことがわかる。即ち該
成形体は約10〜60μｍの範囲の直径を有し実質的
に球殻状を呈する非晶質シリカ二次粒子が、少な
くとも一方向に圧縮され且つ相互に不規則に三次
元的に絡合して一体的に構成されている。 The molded article thus obtained is confirmed to be amorphous from the results of X-ray diffraction analysis. Furthermore, the results of scanning electron microscopy are similar to those shown in FIG. 7B, and it can be seen that there is no substantial change in the structure of the tobermolite molded body used as the starting material. That is, the molded body is made of amorphous silica secondary particles having a diameter in the range of about 10 to 60 μm and having a substantially spherical shell shape, which are compressed in at least one direction and irregularly intertwined with each other in a three-dimensional manner. It is integrally constructed.
以下、上記で得た本発明成形体の物性を示す。 The physical properties of the molded article of the present invention obtained above are shown below.
嵩密度 0.13g/cm3
比表面積 277m2/g
圧縮強度 ４Kg/cm2
空隙率 93％
実施例 ５
実施例１の前半で得た非晶質シリカ―炭酸カル
シウム複合二次粒子の水分散スラリーを、水対固
形分比（重量）を10／１とし40×120×150（mm）
の型枠に注入後プレス脱水成形し、非晶質シリカ
―炭酸カルシウム複合成形体を得た。 Bulk density 0.13g/cm 3 Specific surface area 277m 2 /g Compressive strength 4Kg/cm 2 Porosity 93% Example 5 The water-dispersed slurry of the amorphous silica-calcium carbonate composite secondary particles obtained in the first half of Example 1 was , 40 x 120 x 150 (mm) with a water to solid content ratio (weight) of 10/1.
After pouring into a mold, dehydration molding was performed to obtain an amorphous silica-calcium carbonate composite molded body.
次いで得られた成形体を実施例３と同様に6N
―HC溶液に浸漬して酸処理し、生成した塩化
カルシウムを水洗により完全に溶出させ、乾燥後
本発明の成形体を得る。 Next, the obtained molded body was heated to 6N in the same manner as in Example 3.
- The molded product of the present invention is obtained by immersing it in an HC solution and treating it with an acid, completely eluting the produced calcium chloride by washing with water, and drying it.
かくして得られた成形体は実施例３で得られた
それと実質的に同様の構造及び形態を有するもの
であつた。その物性は次の通りである。 The molded article thus obtained had substantially the same structure and form as that obtained in Example 3. Its physical properties are as follows.
嵩密度 0.13g/cm3 曲げ強度 ５Kg/cm2 圧縮強度 10Kg/cm2 空隙率 92％ Bulk density 0.13g/cm 3 Bending strength 5Kg/cm 2 Compressive strength 10Kg/cm 2 Porosity 92%
第１図Ａ〜Ｃは夫々ゾーノトライト結晶、該結
晶を炭酸化処理して得られる非晶質シリカ―炭酸
カルシウム複合粒子、及び該複合粒子から得られ
る非晶質シリカ一次粒子のＸ線回折図である。第
２図及び第３図は倍率20000倍の電子顕微鏡写真
であり、各図中Ａは出発原料とする珪酸カルシウ
ム結晶、及びＢは該結晶からの非晶質シリカ一次
粒子を表わす。第４図は倍率5000倍の電子顕微鏡
写真であり図中Ａは出発原料とするα―ダイカル
シウムシリケートハイドレート結晶及びＢは該結
晶から得られる非晶質シリカ一次粒子である。第
５図及び第６図は走査型電子顕微鏡写真であり各
図中Ａは出発原料とする珪酸カルシウム結晶の球
殻状二次粒子及びＢは該二次粒子からの非晶質シ
リカ二次粒子を夫々示す。第７図は成形体の破断
面の走査型電子顕微鏡写真（倍率600倍）であ
り、Ａは出発原料とする珪酸カルシウム結晶の二
次粒子から構成される成形体及びＢは本発明の非
晶質シリカ成形体を夫々示す。
Figures 1A to 1C are X-ray diffraction diagrams of zonotrite crystals, amorphous silica-calcium carbonate composite particles obtained by carbonating the crystals, and amorphous silica primary particles obtained from the composite particles, respectively. be. FIGS. 2 and 3 are electron micrographs at a magnification of 20,000 times, and in each figure, A represents the calcium silicate crystal used as the starting material, and B represents the amorphous silica primary particles from the crystal. FIG. 4 is an electron micrograph at a magnification of 5,000 times, in which A is an α-dicalcium silicate hydrate crystal used as a starting material, and B is an amorphous silica primary particle obtained from the crystal. Figures 5 and 6 are scanning electron micrographs, and in each figure, A is a spherical secondary particle of calcium silicate crystal used as a starting material, and B is an amorphous silica secondary particle from the secondary particle. are shown respectively. FIG. 7 is a scanning electron micrograph (magnification: 600x) of the fractured surface of a molded body, in which A is a molded body composed of secondary particles of calcium silicate crystals as a starting material, and B is an amorphous body of the present invention. The silica molded bodies are shown respectively.
Claims (1)
保有し約１〜500μｍの長さ、約50Å〜約１μｍ
の厚さおよび約100Å〜50μｍの巾を有し且つ長
さが厚さの少なくとも10倍である外観結晶様非晶
質シリカ一次粒子が、多数不規則に三次元的に絡
合して形成された約10〜150μｍの直径を有し実
質的に球殻状を呈する二次粒子から主として構成
され、該二次粒子が少なくとも一方向に圧縮さ
れ、且つ相互に絡合されていることを特徴とする
非晶質シリカ成形体。1 Possesses the crystal habit of the calcium silicate crystal that is the origin crystal, and has a length of approximately 1 to 500 μm and approximately 50 Å to approximately 1 μm.
A large number of crystal-like amorphous silica primary particles having a thickness of approximately 100 Å to 50 μm and a length at least 10 times the thickness are irregularly entangled in a three-dimensional manner. The secondary particles are mainly composed of secondary particles having a diameter of about 10 to 150 μm and having a substantially spherical shell shape, and the secondary particles are compressed in at least one direction and entangled with each other. Amorphous silica molded body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4408576A JPS52126695A (en) | 1976-04-16 | 1976-04-16 | Crystatallic appearance amorphus silica and method of producing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4408576A JPS52126695A (en) | 1976-04-16 | 1976-04-16 | Crystatallic appearance amorphus silica and method of producing same |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP971284A Division JPS59141414A (en) | 1984-01-23 | 1984-01-23 | Formed amorphous silica |
| JP971384A Division JPS59141415A (en) | 1984-01-23 | 1984-01-23 | Aqueous slurry of amorphous silica |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS52126695A JPS52126695A (en) | 1977-10-24 |
| JPS6158436B2 true JPS6158436B2 (en) | 1986-12-11 |
Family
ID=12681769
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4408576A Granted JPS52126695A (en) | 1976-04-16 | 1976-04-16 | Crystatallic appearance amorphus silica and method of producing same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS52126695A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991004225A1 (en) * | 1989-09-25 | 1991-04-04 | Japan Insulation Co., Ltd. | Composite primary particle of noncrystalline silica, composite secondary particle of noncrystalline silica, shaped form thereof and production thereof |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6233121Y2 (en) * | 1979-10-18 | 1987-08-25 | ||
| JPS59141414A (en) * | 1984-01-23 | 1984-08-14 | Osaka Packing Seizosho:Kk | Formed amorphous silica |
| JPS60180977A (en) * | 1984-02-28 | 1985-09-14 | 日本インシュレーション株式会社 | Silica-inactive substance composite formed body |
| IT1307743B1 (en) * | 1999-02-03 | 2001-11-19 | Italcementi Spa | PROCEDURE FOR THE PREPARATION OF SILICA STARTING FROM SILICATI DICALCIO. |
| JP4729725B2 (en) * | 2004-07-07 | 2011-07-20 | 独立行政法人産業技術総合研究所 | Silica-based highly active adsorbent material and method for producing the same |
| CA3114751A1 (en) * | 2018-10-05 | 2020-04-09 | Fuji Chemical Industries Co., Ltd. | Porous silica particle composition |
-
1976
- 1976-04-16 JP JP4408576A patent/JPS52126695A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991004225A1 (en) * | 1989-09-25 | 1991-04-04 | Japan Insulation Co., Ltd. | Composite primary particle of noncrystalline silica, composite secondary particle of noncrystalline silica, shaped form thereof and production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS52126695A (en) | 1977-10-24 |
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