JP3635289B2 - Volcanic ejecta foam particles having excellent whiteness and heat resistance, aggregated cured products of the same, and methods for producing the same - Google Patents
Volcanic ejecta foam particles having excellent whiteness and heat resistance, aggregated cured products of the same, and methods for producing the same Download PDFInfo
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- 239000006260 foam Substances 0.000 title claims description 129
- 239000002245 particle Substances 0.000 title claims description 93
- 238000000034 method Methods 0.000 title description 7
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 181
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 146
- 239000013078 crystal Substances 0.000 claims description 91
- 239000008187 granular material Substances 0.000 claims description 91
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 60
- 239000000377 silicon dioxide Substances 0.000 claims description 47
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 46
- 239000007864 aqueous solution Substances 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 39
- 238000010304 firing Methods 0.000 claims description 33
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 32
- 238000004519 manufacturing process Methods 0.000 claims description 31
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- 238000005187 foaming Methods 0.000 claims description 20
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 17
- 229910052742 iron Inorganic materials 0.000 description 13
- 230000005484 gravity Effects 0.000 description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- 238000010586 diagram Methods 0.000 description 10
- 239000001569 carbon dioxide Substances 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000004568 cement Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000004111 Potassium silicate Substances 0.000 description 6
- 229910052913 potassium silicate Inorganic materials 0.000 description 6
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 6
- 235000019353 potassium silicate Nutrition 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
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- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 5
- 229910052912 lithium silicate Inorganic materials 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
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- 235000011010 calcium phosphates Nutrition 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000010079 rubber tapping Methods 0.000 description 4
- CCEKAJIANROZEO-UHFFFAOYSA-N sulfluramid Chemical group CCNS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CCEKAJIANROZEO-UHFFFAOYSA-N 0.000 description 4
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 150000003016 phosphoric acids Chemical class 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000008262 pumice Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 206010033546 Pallor Diseases 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009412 basement excavation Methods 0.000 description 2
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- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- -1 nacre Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
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- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 235000014653 Carica parviflora Nutrition 0.000 description 1
- 241000243321 Cnidaria Species 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 238000001669 Mossbauer spectrum Methods 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
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- 239000008119 colloidal silica Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
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- 238000001723 curing Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 229910000393 dicalcium diphosphate Inorganic materials 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
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- 238000010298 pulverizing process Methods 0.000 description 1
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- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
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- 229910052682 stishovite Inorganic materials 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000005335 volcanic glass Substances 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は、ガラス質火山噴出物発泡粒体から得られた白色度及び耐熱性に優れ、軽量高強度な火山噴出物発泡粒体及び集合硬化物並びにそれらの製造方法に関する。
【０００２】
【従来の技術】
ガラス質火山噴出物の発泡粒体の一種であるシラスバルーンの一般的な製造法は、火山噴出物（シラス）→粒度調整→焼成発泡（媒体流動層炉使用）→回収→製品である。媒体流動層炉によるガラス質火山噴出物の焼成発泡処理は、酸素濃度の少ない燃焼ガス雰囲気で１分間以下（特に１０秒間以下、１秒間以下でもよい）の短期滞留時間での急速焼成発泡が可能であるため、白色度の高い製品が得られやすく、効率よく発泡させやすく処理量が多くできるため、シラスバルーンの工業的製造に用いられている。
シラスバルーンの白色度は、Ｊｏｕｒｎａｌ ｏｆ Ｍａｔｅｒｉａｌｓ Ｓｃｉｅｎｃｅ、Ｖｏｌ．３４，ｐｐ．２４６１−２４６８（１９９９）．で本発明者が述べているように、高温焼成時におけるガラス質火山噴出物（シラス等）中の鉄分の酸化着色に影響される。媒体流動層炉は、焼成発泡時の酸素濃度が低く熱処理時間も短いため、火山噴出物中の鉄分が酸化着色し難く、大気中で加熱する電気炉などより白色度の高いシラスバルーンが製造できる。
しかし、ある程度の鉄分の酸化は避けられず、シラスバルーン製品は薄い肌色を呈してしまい、その白色度は最大限８５程度であり、その向上には限界があった。
【０００３】
そこで、シラスバルーン製造企業では、高白色度を求めるユーザーに対しては、原料を水簸または磁力選鉱して鉄分を含むガラス質以外の不純物を除去したり、焼成発泡したシラスバルーンを水簸して比較的白色度の高い水浮揚物を出荷するなどの工夫を行ってきた。
しかし、こうした処理をしても白色度向上は僅かであり、製品が薄い肌色を呈するという問題や処理コストがかさむなどの問題もあり、媒体流動層炉を使う現状の製造方法では、白色度向上には限界があるという根本的かつ重要な問題は残ったままであった。
そのため、必死の企業努力にもかかわらず、シラスバルーンの主要ユーザーであった紙粘土業界では、高白色度のプラスチックバルーンに市場を奪われつつあるのが現状である。
また、現状のシラスバルーンは、原料を粒度選別後、焼成発泡しただけであり、その軟化温度は、原料とほぼ同程度の９００℃前後であり、高耐熱性を要求される磁器や高温用断熱材などへの用途については、更なる耐熱性の向上が求められているが、その要求を満たす製品が存在していなかった。シラスバルーンの破壊強度についても、媒体流動層炉を用いた急速加熱による焼成発泡過程で破裂し易いため、破裂物や亀裂の入ったものがものが多く混入した製品があり、より高強度の製品に対する需要も多くなってきている。
【０００４】
【発明が解決しようとする課題】
よって、本発明の解決課題は、シラスバルーンの製造における着色（薄い肌色のシラスバルーンとなる）の問題を根本的に解決すること、また、市場の要求の高い耐熱性向上と高強度化を同時に達成することである。そして、これらガラス質火山噴出物発泡粒体を原料とした成形品（２次製品）として、白色度に優れ軽量高強度の耐熱性に優れた従来にない新製品（火山噴出物発泡粒体集合硬化物）を開発し提供することを課題としている。
【０００５】
【課題を解決するための手段】
本願発明は上記従来技術の課題を解決するもので、白色度及び耐熱性に優れた火山噴出物発泡粒体及び同発泡粒体集合硬化物の提供に係り、下記構成の発明である。
（１）平均粒径６μｍ〜５ｍｍのシリカとアルミナを主成分とするガラス質火山噴出物発泡粒体１００重量部に、リン酸アルミニウムをＰ2Ｏ5換算で３〜１１０重量部をまぶし付け、炉内で８００〜１５００℃で焼成して得られた、組織中にクリストバライト型リン酸アルミニウム結晶が混在してなり、軟化温度が１１００℃〜１５００℃であることを特徴とする白色度及び耐熱性に優れた火山噴出物発泡粒体。
【０００６】
（２）平均粒径６μｍ〜５ｍｍのシリカとアルミナを主成分とするガラス質火山噴出物発泡粒体１００重量部に、リン酸アルミニウムをＰ 2 Ｏ 5 換算で３〜１１０重量部をまぶし付け、炉内で８００〜１５００℃で焼成して得られた、組織中にクリストバライト型リン酸アルミニウム結晶及びトリジマイト型リン酸アルミニウム結晶が混在してなり、軟化温度が１１００℃〜１５００℃であることを特徴とする白色度及び耐熱性に優れた火山噴出物発泡粒体。
（３）平均粒径６μｍ〜５ｍｍのシリカとアルミナを主成分とするガラス質火山噴出物発泡粒体１００重量部に、リン酸アルミニウム及びリン酸の混合物をＰ 2 Ｏ 5 換算で３〜１１０重量部、Ａｌ 2 Ｏ 3 換算で０．０１〜４０重量部をまぶし付け、炉内で８００〜１５００℃で焼成して得られた、組織中にクリストバライト型リン酸アルミニウム結晶が混在してなり、軟化温度が１１００℃〜１５００℃であることを特徴とする白色度及び耐熱性に優れた火山噴出物発泡粒体。
（４）平均粒径６μｍ〜５ｍｍのシリカとアルミナを主成分とするガラス質火山噴出物発泡粒体１００重量部に、リン酸アルミニウム及びリン酸の混合物をＰ 2 Ｏ 5 換算で３〜１１０重量部、Ａｌ 2 Ｏ 3 換算で０．０１〜４０重量部をまぶし付け、炉内で８００〜１５００℃で焼成して得られた、組織中にクリストバライト型リン酸アルミニウム結晶及びトリジマイト型リン酸アルミニウム結晶が混在してなり、軟化温度が１１００℃〜１５００℃であることを特徴とする白色度及び耐熱性に優れた火山噴出物発泡粒体。
（５）平均粒径６μｍ〜５ｍｍの火山噴出物発泡粒体が、平均粒径６μｍ〜５ｍｍのシラスバルーンであることを特徴とする（１）〜（４）のいずれか１項に記載の白色度及び耐熱性に優れた火山噴出物発泡粒体。
【０００７】
（６）平均粒径６μｍ〜５ｍｍのシリカとアルミナを主成分とするガラス質火山噴出物発泡粒体１００重量部に、リン酸アルミニウムをＰ2Ｏ5換算で３．０〜１１０重量部添加混合した混合物を加圧成形し、乾燥後、８００〜１５００℃で焼成して得られた、組織中に クリストバライト型リン酸アルミニウム結晶が混在してなり、軟化温度が１２００℃〜１５００℃であることを特徴とする白色度及び耐熱性に優れた火山噴出物発泡粒体の集合硬化物。
（７）平均粒径６μｍ〜５ｍｍのシリカとアルミナを主成分とするガラス質火山噴出物発泡粒体１００重量部に、リン酸アルミニウムをＰ 2 Ｏ 5 換算で３．０〜１１０重量部添加混合した混合物を加圧成形し、乾燥後、８００〜１５００℃で焼成して得られた、組織中にクリストバライト型リン酸アルミニウム結晶及びトリジマイト型リン酸アルミニウム結晶が混在してなり、軟化温度が１２００℃〜１５００℃であることを特徴とする白色度及び耐熱性に優れた火山噴出物発泡粒体の集合硬化物。
（８）平均粒径６μｍ〜５ｍｍのシリカとアルミナを主成分とするガラス質火山噴出物発泡粒体１００重量部に、リン酸アルミニウム及びリン酸の混合物をＰ 2 Ｏ 5 換算で３．０〜１１０重量部、Ａｌ 2 Ｏ 3 換算で０．０１〜４０重量部を添加混合した混合物を加圧成形し、乾燥後、８００〜１５００℃で焼成して得られた、組織中にクリストバライト型リン酸アルミニウム結晶が混在してなり、軟化温度が１２００℃〜１５００℃であることを特徴とする白色度及び耐熱性に優れた火山噴出物発泡粒体の集合硬化物。
【０００８】
（９）前記（１）〜（５）のいずれか１項に記載の白色度及び耐熱性に優れた火山噴出物発泡粒体１００重量部に、リン酸アルミニウムをＰ 2 Ｏ 5 換算で３．０〜１１０重量部添加混合した混合物を加圧成形し、乾燥後、８００〜１５００℃で焼成して得られた、組織中にクリストバライト型リン酸アルミニウム結晶が混在してなり、軟化温度が１２００℃〜１５００℃であることを特徴とする白色度及び耐熱性に優れた火山噴出物発泡粒体の集合硬化物。
（１０）前記（１）〜（５）のいずれか１項に記載の白色度及び耐熱性に優れた火山噴出物発泡粒体１００重量部に、リン酸アルミニウムをＰ2Ｏ5換算で３．０〜１１０重量部添加混合した混合物を加圧成形し、乾燥後、８００〜１５００℃で焼成して得られた、組織中にクリストバライト型リン酸アルミニウム結晶及びトリジマイト型リン酸アルミニウム結晶が混在してなり、軟化温度が１２００℃〜１５００℃であることを特徴とする白色度及び耐熱性に優れた火山噴出物発泡粒体の集合硬化物。
（１１）平均粒径６μｍ〜５ｍｍのシリカとアルミナを主成分とするガラス質火山噴出物発泡粒体１００重量部に、リン酸アルミニウム水溶液をＰ2Ｏ5換算で３〜１１０重量部を添加・混練してまぶし付け、乾燥処理した後、炉内で８００〜１５００℃で焼成して、組織中にクリストバライト型リン酸アルミニウム結晶が混在してなり、軟化温度が１１００℃〜１５００℃である発泡粒体を得ることを特徴とする白色度及び耐熱性に優れた火山噴出物発泡粒体の製造方法。
（１２）平均粒径６μｍ〜５ｍｍのシリカとアルミナを主成分とするガラス質火山噴出物発泡粒体１００重量部に、リン酸アルミニウム水溶液をＰ2Ｏ5換算で３〜１１０重量部を添加・混練してまぶし付け、乾燥処理した後、炉内で８００〜１５００℃で焼成して、組織中にクリストバライト型リン酸アルミニウム結晶及びトリジマイト型リン酸アルミニウム結晶が混在してなり、軟化温度が１１００℃〜１５００℃である発泡粒体を得ることを特徴とする白色度及び耐熱性に優れた火山噴出物発泡粒体の製造方法。
（１３）平均粒径６μｍ〜５ｍｍのシリカとアルミナを主成分とするガラス質火山噴出物発泡粒体１００重量部に、リン酸アルミニウム及びリン酸の混合物水溶液をＰ2Ｏ5換算で３〜１１０重量部、Ａｌ 2 Ｏ 3 換算で０．０１〜４０重量部を添加混練してまぶし付け、乾燥処理した後、炉内で８００〜１５００℃で焼成して、組織中にクリストバライト型リン酸アルミニウム結晶が混在してなり、軟化温度が１１００℃〜１５００℃の発泡粒体を得ることを特徴とする白色度及び耐熱性に優れた火山噴出物発泡粒体の製造方法。
【０００９】
（１４）平均粒径６μｍ〜５ｍｍのシリカとアルミナを主成分とするガラス質火山噴出物発泡粒体１００重量部に、リン酸アルミニウム及びリン酸の混合物水溶液をＰ2Ｏ5換算で３．０〜１１０重量部、Ａｌ 2 Ｏ 3 換算で０．０１〜４０重量部を添加混練してまぶし付け 、乾燥処理した後、炉内で８００〜１５００℃で焼成して、組織中にクリストバライト型リン酸アルミニウム結晶及びトリジマイト型リン酸アルミニウム結晶が混在してなり、軟化温度が１１００℃〜１５００℃の発泡粒体を得ることを特徴とする白色度及び耐熱性に優れた火山噴出物発泡粒体の製造方法。
（１５）前記（１１）〜（１４）のいずれか１項に記載の平均粒径６μｍ〜５ｍｍのシリカとアルミナを主成分とするガラス質火山噴出物発泡粒体が、平均粒径２〜１０００μｍのガラス質火山噴出物粉粒体１００重量部に、リン酸アルミニウム水溶液をＰ2Ｏ5換算で０．３〜２８．０重量部添加・混練してまぶし付け、乾燥処理した後、流動層炉中で９００〜１２００℃で焼成発泡させて得られたものであることを特徴とする白色度及び耐熱性に優れた火山噴出物発泡粒体の製造方法。
【００１０】
（１６）前記（１１）〜（１４）のいずれか１項に記載の平均粒径６μｍ〜５ｍｍのシリカとアルミナを主成分とするガラス質火山噴出物発泡粒体が、平均粒径２〜１０００μｍのガラス質火山噴出物粉粒体１００重量部に、リン酸アルミニウム及びリン酸の混合物水溶液をＰ2Ｏ5換算で０．３〜２８．０重量部、Ａｌ2Ｏ3換算で０．０１〜２０重量部を添加・混練してまぶし付け、乾燥処理した後、流動層炉中で９００〜１２００℃で焼成発泡させて得られたものであることを特徴とする白色度及び耐熱性に優れた火山噴出物発泡粒体の製造方法。
（１７）乾燥処理が、２００〜８００℃で行われることを特徴とする（１１）〜（１６）のいずれか１項に記載の白色度及び耐熱性に優れた火山噴出物発泡粒体の製造方法。
（１８）平均粒径６μｍ〜５ｍｍのシリカとアルミナを主成分とするガラス質火山噴出物発泡粒体がシラスバルーンであることを特徴とする（１１）〜（１７）のいずれか１項に記載の白色度及び耐熱性に優れた火山噴出物発泡粒体の製造方法。
（１９）平均粒径６μｍ〜５ｍｍのシリカとアルミナを主成分とするガラス質火山噴出物発泡粒体１００重量部に、リン酸アルミニウム水溶液をＰ 2 Ｏ 5 換算で３．０〜１１０重量部添加混合した混合物を加圧成形し、乾燥処理した後、８００〜１５００℃で焼成して、組織中にクリストバライト型リン酸アルミニウム結晶が混在してなり、軟化温度が１２００℃〜１５００℃である火山噴出物発泡粒体の集合硬化物を得ることを特徴とする白色度及び耐熱性に優れた火山噴出物発泡粒体の集合硬化物の製造方法。
【００１１】
（２０）平均粒径６μｍ〜５ｍｍのシリカとアルミナを主成分とするガラス質火山噴出物発泡粒体１００重量部に、リン酸アルミニウム水溶液をＰ2Ｏ5換算で３．０〜１１０重量部添加混合した混合物を加圧成形し、乾燥処理した後、８００〜１５００℃で焼成して、組織中にクリストバライト型リン酸アルミニウム結晶及びトリジマイト型リン酸アルミニウム結晶が混在してなり、軟化温度が１２００℃〜１５００℃である火山噴出物発泡粒体の集合硬化物を得ることを特徴とする白色度及び耐熱性に優れた火山噴出物発泡粒体の集合硬化物の製造方法。
（２１）乾燥処理が、２００〜８００℃で行われることを特徴とする請求項１９〜２０のいずれか１項に記載の白色度及び耐熱性に優れた火山噴出物発泡粒体の集合硬化物の製造方法。
【００１２】
さらに別の下記の形態も有利である。
（２２）平均粒径６μｍ〜５ｍｍのシリカとアルミナを主成分とするガラス質火山噴出物発泡粒体１００重量部に、リン酸アルミニウム水溶液をＰ2Ｏ5換算で３．０〜１１０重量部及びアルミナセメント５〜２００重量部を添加混合した混合物を加圧成形し、乾燥処理した後、８００〜１５００℃で焼成して、組織中にクリストバライト型リン酸アルミニウム結晶が混在してなる火山噴出物発泡粒体の集合硬化物を得ることを特徴とする白色度及び耐熱性に優れた火山噴出物発泡粒体の集合硬化物の製造方法。
【００１３】
（２３）平均粒径６μｍ〜５ｍｍのシリカとアルミナを主成分とするガラス質火山噴出物発泡粒体１００重量部に、リン酸アルミニウム水溶液をＰ2Ｏ5換算で３．０〜１１０重量部及び炭酸カルシウム１０〜１００重量部を添加混合した混合物を加圧成形し、乾燥処理した後、８００〜１５００℃で焼成して、組織中にクリストバライト型リン酸アルミニウム結晶が混在してなる火山噴出物発泡粒体の集合硬化物を得ることを特徴とする白色度及び耐熱性に優れた火山噴出物発泡粒体の集合硬化物の製造方法。
（２４）平均粒径６μｍ〜５ｍｍのシリカとアルミナを主成分とするガラス質火山噴出物発泡粒体１００重量部に、アルカリ金属珪酸塩水溶液を固形物換算で１０．０〜７０．０重量部を添加・混練し、成形した後、同成形体中へ炭酸ガスを注入して硬化し、同硬化物にリン酸アルミニウム水溶液をＰ2Ｏ5換算で３．０〜１１０重量部含浸させ、乾燥処理した後、８００〜１５００℃で焼成して、組織中にクリストバライト型リン酸アルミニウム結晶が混在してなる火山噴出物発泡粒体の集合硬化物を得ることを特徴とする白色度及び耐熱性に優れた火山噴出物発泡粒体の集合硬化物の製造方法。
（２５）平均粒径６μｍ〜５ｍｍのシリカとアルミナを主成分とするガラス質火山噴出物発泡粒体１００重量部に、濃度１９．５〜３０％の珪酸リチウム水溶液５０〜２００重量部を添加・混練した後、その混練物中へ炭酸ガスを注入して硬化し、同硬化物にリン酸アルミニウム水溶液をＰ2Ｏ5換算で３．０〜１１０重量部含浸させ、乾燥処理した後、８００〜１５００℃で焼成して、組織中にクリストバライト型リン酸アルミニウム結晶が混在してなる火山噴出物発泡粒体の集合硬化物を得ることを特徴とする白色度及び耐熱性に優れた火山噴出物発泡粒体の集合硬化物の製造方法。
【００１４】
【発明の実施の形態】
本願発明では、シラス、黒曜石、真珠岩、軽石等のシリカとアルミナを主成分とするガラス質火山噴出物の粉粒状原料に、リン酸アルミニウムの水溶液を添加・混練し、９００℃以下、好ましくは２００〜８００℃で乾燥処理した後、加熱炉、好ましくは流動層炉で９００〜１２００℃で短時間、特に好ましくは１０秒間以下、最も好ましくは１秒間以下、焼成発泡させることにより、白色度及び耐熱性に優れた火山噴出物発泡粒体が取得される。
前記リン酸アルミニウムをまぶした原料粉粒体の焼成発泡処理は、８００〜１２００℃、好ましくは９００〜１２００℃であり、８００℃より低い温度では、発泡率が著しく低く熱履歴が不充分であり、１２００℃より高い温度では過発泡して破裂し易くなったり、原料粉体同志が融着し易くなって好ましくない。
【００１５】
前記乾燥処理は、ロータリーキルン内で１０〜６０分間行うことが好ましく、そして乾燥処理された原料粉体の焼成発泡処理は媒体流動層炉内で行うことが好ましい。そうすることにより、粒体同士が相互に接着して塊状体とならず、容易に独立した発泡粒体が取得される。
また、本発明で取得された高白色度の火山噴出物の発泡粒体の好適例では白色度が８５〜９８を示すが、市販のシラスバルーンの白色度は６０〜８５である。 また該高白色度のシラスバルーンは、従来のシラスバルーンよりも耐熱性（軟化温度）が約１００〜５００℃向上する。なお、上記シラス原料に、リン酸アルミニウム水溶液を添加することなく、単に媒体流動層炉を用いて９６０℃で焼成発泡させて得られたシラスバルーンは、白色度が７８．４であって、薄い肌色を呈していた。
【００１６】
平均粒径２〜１０００μｍのガラス質火山噴出物粉粒体に添加・混練するリン酸アルミニウムの量は、ガラス質火山噴出物の粒状原料１００重量部に対して、リン酸アルミニウム水溶液をＰ2Ｏ5換算で０．３〜２８．０重量部が好ましい。
そして、上記好適温度範囲で乾燥処理した後、流動層炉中で９００〜１２００℃で焼成発泡させることにより白色度及び耐熱性に優れた火山噴出物発泡粒体が製造される。また、前記方法においては、平均粒径２〜１０００μｍのガラス質火山噴出物粉粒体１００重量部に、リン酸アルミニウム及びリン酸の混合物水溶液をＰ2Ｏ5換算で０．３〜２８．０重量部、Ａｌ2Ｏ3換算で０．０１〜２０重量部を添加・混練してまぶし付けることが好ましい。
なお、前記混合処理剤は、粘度（２０℃）５００ｃｐ以下のものが好ましく、特に４０〜８０ｃｐのものが好ましく、粘度が５００ｃｐを越えると、平均粒径２〜１０００μｍのガラス質火山噴出物粉粒体同士が凝集して団子を生じるおそれがある。
【００１７】
また、ガラス質火山噴出物の焼成発泡処理により得られた平均粒径６μｍ〜５ｍｍのシリカとアルミナを主成分する火山噴出物発泡粒体１００重量部に、リン酸アルミニウム水溶液をＰ2Ｏ5換算で３〜１１０重量部を添加・混練してまぶし付け、乾燥処理した後、ガス焼成炉、流動層炉、ロータリーキルン等の炉内で８００〜１５００℃で焼成すると、白色度及び格段に耐熱性に優れた、例えば耐熱性（軟化温度）が１００〜５００℃高められた火山噴出物発泡粒体が得られる。
【００１８】
また、前記により得られた火山噴出物発泡粒体に、リン酸アルミニウム、リン酸アルミニウムとリン酸の混合物、リン酸アルミニウムとアルミナセメントとの混合物、又はリン酸アルミニウムと炭酸カルシウムとの混合物の粘着性水溶液を、添加・混練して、加圧成形したものを、８００〜１５００℃で焼成すると、白色度及び格段に耐熱性に優れた火山噴出物発泡粒体の集合硬化物を製造することもできる。
また、前記火山噴出物発泡粒体に、アルカリ金属珪酸塩水溶液を添加・混練し、成形した後、同成形体中へ炭酸ガスを注入して硬化し、同硬化物にリン酸アルミニウム水溶液を含浸させ、乾燥処理した後、８００〜１５００℃、（好ましくは９００〜１２００℃）で焼成することによっても白色度及び耐熱性に優れた火山噴出物発泡粒体の集合硬化物が製造できる。
【００１９】
本発明者は良質な火山噴出物発泡粒体を製造する研究を種々行った結果、シラスバルーンの着色の原因は、焼成前後のメスバウワースペクトルの解析によって、焼成発泡時の火山ガラス（シラス等）原料中の鉄分の酸化にあることを解明した。しかし、媒体流動層炉の焼成温度や滞留時間（熱処理時間）などの焼成条件を変えても、鉄分の酸化着色を完全に防止することは不可能であった。
また、コロイダルシリカゾルやアルミナゾルといった処理剤を用いて物理的に表面をコーティングする方法を用いたが、鉄分の酸化を防止することは出来ず白色度は向上しなかった。
そこで、化学的にシラス中の鉄分の酸化を防止する方法として、種々の酸化防止剤を検討した。有機物系の酸化防止剤やキレート化合物は、高温焼成時に焼失してしまい鉄分の酸化は防止できなかったので、高温焼成時でも効果の期待できる（焼失しない）無機系の化学処理剤を種々検討した。
そして、ついにリン酸塩処理剤、特に好ましくはリン酸アルミニウムで、ガラス質火山噴出物、特にシラス原料粉粒体の表面をまぶした後、媒体流動層炉を用いて９６０℃で焼成発泡した結果、鉄分の酸化をほぼ完全に防止でき、薄い肌色が消え、従来のシラスバルーンと比較にならぬほどの高白色度の白色度９８のシラスバルーンを製造することができた。その理由は明らかではないが、リン酸が洗剤に使われていたように金属イオン（鉄イオン等）とキレートをつくりやすく酸化を防止できる性質をもつことと、高温加熱で反応して鉄分の酸化を高温でも防止する性質の両方を兼ね備えていることであるものと推測される。
【００２０】
また、本発明における媒体流動層炉を用いた焼成発泡過程において、リン酸塩の高温加熱時にリン酸塩と火山ガラスが反応して耐熱性と強度に優れたリン酸アルミニウムＡｌＰＯ4に改善されることにより、シラスの過発泡を抑制する働きがあり、シラスバルーンの破壊強度が向上することを確認している。
本発明によれば、これまでシラスバルーン原料として使用できなかった鉄分の多いシラス原料や軽石原料（粉砕して使用）も市販のシラスバルーンと同等以上の白色度を発現できるため、南九州に９０ｋｍ3以上賦存すると言われている普通のシラスがシラスバルーン原料として使用可能となり、低コスト化も同時に達成できる。上記のリン酸塩としては、リン酸アルミニウムを用いているが、この他にもリン酸ナトリウム、リン酸カルシウム、リン酸カリウム等の五酸化リンを高濃度で含む各水溶液を用いた場合でも同様な高白色度を示すことを確認している。そして、シラスバルーンの後処理として、粒体表面にリン酸アルミニウムをまぶし付けてコーティングした後、大気中で１５００℃以下で焼成した場合、焼成温度が上がるほど白色度が向上し、更に耐熱性も大幅に向上することを確認した。
【００２１】
また、本発明の火山噴出物発泡粒体を用いた二次製品化の例として、火山噴出物発泡粒体に珪酸リチウム水溶液を添加・混練した混練物中へ炭酸ガスを注入して得られる火山噴出物発泡粒体集合硬化物がある。
この集合硬化物は従来のシラスバルーンを用いた集合硬化物よりも耐熱性が向上している。さらに、その集合硬化物表面にリン酸アルミニウム水溶液を塗布し、８００〜１５００℃で熱処理した火山噴出物発泡粒体集合硬化物は、更に耐熱性が向上（軟化温度が１２００℃〜１５００℃となる）することがわかった。
【００２２】
次に、Ｘ線回折測定結果を示すＸ線回折図に基づいて、本発明に係る火山噴出物発泡粒体、火山噴出物発泡粒体の集合硬化物と関連事項について説明する。
図１に示すＸ線回折図は、単なるガラス質シリカ（ＳｉＯ2・ｎＨ2Ｏ）（Ａ）と、少量のリン酸アルミニウムを含有するリン酸溶液の蒸発乾固物の１２００℃加熱処理品（Ｂ−１）と、ガラス質シリカとこのリン酸溶液との混合物の１３００℃加熱処理品（Ｃ）の各Ｘ線回折図であり、ガラス質シリカとリン酸溶液との混合物の１３００℃加熱処理品（Ｃ）であっても殆ど非晶質であり、各物質ともに結晶の存在は確認できない。すなわち、ガラス質火山噴出物でないガラス質シリカとリン酸を高温反応させても、耐熱性の高い結晶質の物質は生成しないことが解る。
【００２３】
図２は、単なるガラス質シリカ（ＳｉＯ2・ｎＨ2Ｏ）（Ａ）と、リン酸アルミニウム溶液の蒸発乾固物の１３００℃加熱処理品（Ｂ−２）と、ガラス質シリカとリン酸アルミニウム溶液との混合物の１３００℃加熱処理品（Ｄ）の各Ｘ線回折図であり、ガラス質シリカとリン酸アルミニウムとの混合物の１３００℃加熱処理品（Ｄ）であっても殆ど非晶質である。
なお（Ｂ−２）グラフ線のほとんどが全てのピークがリン酸アルミニウムの型のうち、ＡＬ（ＰＯ3）3の結晶を示すにすぎない。すなわち、ガラス質火山噴出物でないガラス質シリカとリン酸アルミニウムを高温反応させても、結晶質の物質は殆ど生成しないことが解る。
【００２４】
図３は、シリカとアルミナを主成分とするガラス質火山噴出物のシラス（非晶質）（Ｆ−１）と、少量のリン酸アルミニウムを含有（Ａｌ2Ｏ3として１％含有）するリン酸溶液（Ｐ2Ｏ5として５５％含有）の蒸発乾固物の１２００℃加熱処理品（Ｂ−１）と、シラスとこのリン酸溶液との混合物の１３００℃加熱処理品（Ｅ）の各Ｘ線回折図であり、２θが２２°、３６°付近に特徴的なクリストバライト型リン酸アルミニウム結晶ＡｌＰＯ4が認められる。
【００２５】
図４は、ガラス質火山噴出物のシラス（非晶質）（Ｆ−１）と、リン酸アルミニウムの蒸発乾固物の１３００℃加熱処理品（Ｂ−２）と、シラスとリン酸アルミニウム溶液との混合物の１３００℃加熱処理品（Ｇ）の各Ｘ線回折図であり、２θが２２°と３６°付近に特徴的なクリストバライト型リン酸アルミニウム結晶（ＡｌＰＯ4）と２０°と２３°付近に特徴的なトリジマイト型リン酸アルミニウム結晶（ＡｌＰＯ4）の混在が認められる。すなわち、シラスとリン酸アルミニウムとの混合物の１３００℃加熱処理品（Ｇ）では、トリジマイト型リン酸アルミニウム結晶とクリストバライト型リン酸アルミニウム結晶が認められ、それら結晶の特性からして、焼成反応製品は耐熱性と強度に優れるものとなることが推定できる。
【００２６】
図５は、シラスバルーン（シリカとアルミナを主成分とするガラス質火山噴出物の発泡粒体）（Ｆ−２）と、少量のリン酸アルミニウムを含有するリン酸溶液の蒸発乾固物の１２００℃加熱処理品（Ｂ−１）と、シラスバルーンと少量のリン酸アルミニウムを含有するリン酸溶液との混合物の１４００℃加熱処理品（Ｈ）の各Ｘ線回折図であり、２θが２２°と３６°付近に特徴的なクリストバライト型リン酸アルミニウム結晶（ＡｌＰＯ4）と２０°、２３°付近に特徴的なトリジマイト型リン酸アルミニウムＡｌＰＯ4結晶の混在が認められる。すなわち、シラスバルーンとリン酸アルミニウムとの混合物の１４００℃加熱処理品（Ｈ）でも、トリジマイト型リン酸アルミニウム結晶ＡｌＰＯ4とクリストバライト型リン酸アルミニウム結晶ＡｌＰＯ4が認められ、それら結晶の特性からして、焼成反応製品は耐熱性と強度に優れるものとなることが推定できる。
【００２７】
図６は、シラスバルーン（ガラス質火山噴出物の発泡粒体）（Ｆ−２）と、リン酸アルミニウム溶液の蒸発乾固物の１３００℃加熱処理品（Ｂ−２）と、シラスバルーンとリン酸アルミニウム溶液との混合物の１５００℃加熱処理品（Ｊ−１）の各Ｘ線回折図であり、２θが２２°と３６°付近に特徴的なクリストバライト型リン酸アルミニウム結晶と２０°、２３°付近に特徴的なトリジマイト型リン酸アルミニウム結晶の混在が認められる。
すなわち、シラスバルーンとリン酸アルミニウムとの混合物の１５００℃加熱処理品（Ｊ−１）では、トリジマイト型リン酸アルミニウム結晶ＡｌＰＯ4とクリストバライト型リン酸アルミニウム結晶ＡｌＰＯ4が認められ、それら結晶の特性からして、焼成反応製品は耐熱性と強度に優れるものとなることが推定できる。
【００２８】
図７は、シラスバルーンとリン酸アルミニウム溶液との混合物の１４００℃加熱処理品（Ｊ−２）のＸ線回折図であり、２θが２０°と２３°付近にトリジマイト型リン酸アルミニウム結晶ＡｌＰＯ4と２２°と３６°付近に特徴的なクリストバライト型リン酸アルミニウム結晶ＡｌＰＯ4の混在が認められる。
すなわち、シラスバルーンとリン酸アルミニウム溶液との混合物の１４００℃加熱処理品（Ｊ−２）でも、トリジマイト型リン酸アルミニウム結晶とクリストバライト型リン酸アルミニウム結晶が認められる。それら結晶の特性からして、焼成反応製品は耐熱性に優れるものとなることが推定できる。
【００２９】
図８は、シラスバルーンとアルミナセメントとリン酸アルミニウム溶液との混合物の１３００℃加熱処理品（Ｋ）のＸ線回折図であり、２θが２０°と２３°付近に特徴的なトリジマイト型リン酸アルミニウム結晶ＡｌＰＯ4と２２°と３６°付近に特徴的なクリストバライト型リン酸アルミニウム結晶の混在が認められ、特にトリジマイト型リン酸アルミニウム結晶の多量が確認される。
すなわち、シラスバルーンとアルミナセメントとリン酸アルミニウムとの混合物の１３００℃加熱処理品（Ｋ）では、クリストバライト型リン酸アルミニウム結晶と多量に存在するトリジマイト型リン酸アルミニウム結晶が認められ、それら結晶の特性からして、焼成反応製品は耐熱性に優れるものとなることが推定できる。
【００３０】
図９は、シラスバルーンと炭酸カルシウムとリン酸アルミニウム溶液との混合物の１４００℃加熱処理品（Ｌ）のＸ線回折図であり、２θが２０°と２３°付近に特徴的なトリジマイト型リン酸アルミニウム結晶と２２°と３６°付近に特徴的なクリストバライト型リン酸アルミニウム結晶の混在が認められる。
さらに、２７°〜３４°までの２９°付近をピークとするリン酸カルシウムの結晶も認められる。すなわち、該製品においても、トリジマイト型リン酸アルミニウム結晶とクリストバライト型リン酸アルミニウム結晶が認められ、それらにプラスしてリン酸カルシウムの結晶も認められ、それら結晶の特性からして、焼成反応製品は耐熱性に優れるものとなることが推定できる。
【００３１】
図１０は、シラスバルーンと珪酸リチウム溶液との混合物に炭酸ガスを注入して硬化させた硬化物にリン酸アルミニウム溶液を含浸させ、乾燥後、１２００℃で加熱処理して得られた焼成品（Ｍ）のＸ線回折図であり、この例でも２θが２０°と２３°付近に特徴的なトリジマイト型リン酸アルミニウム結晶ＡｌＰＯ4と２２°と３６°付近に特徴的なクリストバライト型リン酸アルミニウム結晶の混合が認められ、それら結晶の特性からして、焼成反応製品は耐熱性に優れるものとなることが推定できる。
【００３２】
【実施例】
以下に本願発明の実施例について説明する。
実施例１：
鹿児島県薩摩郡吉田町産シラス原料（平均粒径３５．０μｍのシラス）１００ｋｇに対しリン酸アルミニウム水溶液（「アシドホス７５」商品名：多木化学（株）製、五酸化リン５０％、酸化アルミニウム９％、残部水からなるリン酸アルミニウム水溶液）を１０ｋｇを添加してまぶし全体に沁みわたるように攪拌機で混合攪拌した。
次いで、該混合攪拌された原料をロータリーキルンで６５０℃で乾燥し、その原料粉体を媒体流動層炉を用いて９６０℃で焼成発泡させ、白色度８７．３、タッピングかさ比重０．１４、平均粒径５１．７μｍの高白色度のシラスバルーンが製造できた。また、この高白色度のシラスバルーンは、従来のシラスバルーンよりも耐熱性が向上した。なお、上記シラス原料に、リン酸アルミニウム水溶液を添加することなく、単に媒体流動層炉を用いて９６０℃で焼成発泡させて得られたシラスバルーンは、白色度が７８．４であって、薄い肌色を呈していた。
【００３３】
実施例２：
鹿児島県薩摩郡吉田町産シラス原料（シラス平均粒径３５．０μｍ）１００ｋｇに対し重リン酸アルミニウム水溶液（五酸化リン５０％含有水溶液、日本化学工業（株）製）を１０ｋｇを添加してまぶし全体に沁みわたるように攪拌機で混合攪拌した。次いで、該混合攪拌された原料をロータリーキルンで６５０℃で乾燥し、その原料粉体を媒体流動層炉を用いて９６０℃で焼成発泡させ、白色度８３．５、タッピングかさ比重０．１７、平均粒径５１．２μｍの高白色度のシラスバルーンが製造できた。
【００３４】
参考試験例１：
鹿児島県薩摩郡吉田町産シラス原料１００ｋｇに対しリン酸水溶液（Ｈ3ＰＯ4９８％含有水溶液、関東化学（株）製）を１０ｋｇを添加してまぶし全体に沁みわたるように攪拌機で混合攪拌する。次いで、該混合攪拌された原料をロータリーキルンで６５０℃で乾燥し、その原料粉体を媒体流動層炉を用いて、９６０℃で焼成発泡させ、白色度８１．５、タッピングかさ比重０．１３、平均粒径５１．５μｍの高白色度のシラスバルーンが製造できた。
【００３５】
実施例３：
鹿児島県垂水産の軽石原料の粉砕物（平均粒径０．２〜３ｍｍ）１００ｋｇに対し、リン酸アルミニウム水溶液（「アシドホス７５」商品名：多木化学（株）製の五酸化リン５０％、酸化アルミニウム９％、残部水からなるリン酸アルミニウム水溶液）を１０ｋｇを添加してまぶし全体に沁みわたるように攪拌機で混合攪拌した。
次いで、該混合攪拌された原料をロータリーキルンで６５０℃で乾燥し、その原料粉体を媒体流動層炉を用いて、９６０℃で焼成発泡させ、白色度８１．１、タッピングかさ比重０．３５、平均粒径５０．９μｍの従来のシラスバルーンと同等以上の白色度をもつシラスバルーンが製造できた。
【００３６】
参考試験例２：
シラス原料粉体をリン酸アルミニウムでまぶして被覆した後、媒体流動層炉で焼成発泡して得た高白色度の火山噴出物発泡粒体（実施例２で得られたもの）１００重量部に珪酸カリウム水溶液（「Ａ珪酸カリウム」商品名：日本化学工業（株）製の二酸化珪素２５．５〜２７．５％、酸化カリウム１２．５〜１４．５％を含む珪酸カリウム水溶液）１００重量部を加えて、密閉型混練機内で混練した。次いで、その混練物を方形の型枠に投入してプレス成形した。
その後、型枠から取り出した成形体の表面に樹脂フィルムを貼り、その上から細い長棒（錐）を深部まで挿し、かつ狭間隔（１００〜１５０ｍｍ間隔）で他数箇所に多数の掘削孔を穿設する。次いで、掘削孔へ細管を差し込み、その細管へ炭酸ガスを圧力２〜５ｋｇｆ／ｃｍ2で１０〜８０秒間、圧送注入する。
これにより、珪酸カリウムと炭酸ガスを反応せしめ、珪酸ゲルと炭酸カリウムを生成させ、この珪酸ゲルの強力な結合力により成形体の強度を増大させる。
また、生成した炭酸カリウムは徐々に火山噴出物の珪酸分と反応して安定な固形の珪酸カリウムを形成する。炭酸ガス注入を終えた掘削孔に対しては、火山噴出物発泡粒体と結合材（例えば、珪酸カリウム等の無機バインダ）の混練物を押入して目詰めすることが好ましい。
最後に、炭酸ガス注入処理済みの成形体を型枠から脱型し、表面の樹脂フィルムを剥がして白色度に優れ軽量高強度の耐熱性に優れた火山噴出物発泡粒体の集合硬化物ができた。更に、得られた火山噴出物発泡粒体の集合硬化物の表面にリン酸アルミニウムを含浸し、４５０℃〜１０００℃で熱処理すれば、更に耐熱性が向上し、高強度化した集合硬化物が生成できた。
【００３７】
実施例４：
シラスバルーン（「ＳＹＢ−５００５」商品名：平均粒径９０μｍ、かさ比重０．１４〜０．１７、豊和直株式会社製、）１００ｇに、第一リン酸アルミニウム（重リン酸アルミニウム）５０％水溶液（Ｐ2Ｏ5：３３．４％、Ａｌ2Ｏ3：８．１％、比重１．４７、粘度（２０℃）７０〜８０ｃｐ）１５０ｇを均一に混合し、それを型枠に入れ、５０ｋｇｆ／ｃｍ2のプレス圧力で加圧成形する。 型枠から外した成型品を３００℃で３０分間乾燥し、９００〜１４００℃で加熱硬化処理を行う。得られた焼成品は、大気中で１４００℃の耐熱性（軟化温度）を示した。Ｘ線回折の結果、図７に示すＪ−２のＸ線回折図が得られた。
【００３８】
参考試験例３：
シラスバルーン（「ＳＳＢ−４０００ＳＳ」商品名：平均粒径７５μｍ、かさ比重０．１８〜０．２１、豊和直株式会社製、）３００ｇに、アルミナセメント（「デンカアルミナセメントスーパー９０」商品名：Ａｌ2Ｏ3：９０％、ＣａＯ：１０％、耐火温度１８８０℃、電気化学工業株式会社製）１２０ｇを均一に攪拌・混合し、それに第一リン酸アルミニウム（重リン酸アルミニウム）５０％水溶液（Ｐ2Ｏ5：３３．４％、Ａｌ2Ｏ3：８．１％、比重１．４７、粘度（２０℃）７０〜８０ｃｐ）４２０ｇを添加・混合し、均一になるように攪拌する。良く攪拌したものを原料として、型枠に入れ、５０ｋｇｆ／ｃｍ2のプレス圧力で加圧成形する。型枠から外した成型品を３００℃で３０分間乾燥し、９００〜１４００℃で加熱硬化処理を行う。得られた焼成品は、大気中で１４００℃の耐熱性（軟化温度）を示した。Ｘ線回折の結果、図８に示すＫのＸ線回折図が得られた。
【００３９】
参考試験例４：
シラスバルーン（「ＳＹＢ−５０００」商品名：平均粒径７０μｍ、かさ比重０．１７〜０．２１、豊和直株式会社製、）２００ｇに、炭酸カルシウム（有限会社コーラル石産社製のサンゴ粉）２００ｇ、第一リン酸アルミニウム（重リン酸アルミニウム）５０％水溶液（Ｐ2Ｏ5：３３．４％、Ａｌ2Ｏ3：８．１％、比重１．４７、粘度（２０℃）７０〜８０ｃｐ）４００ｇを添加・混合し、それを型枠に入れ、５０ｋｇｆ／ｃｍ2のプレス圧力で加圧成形する。
さらに、前記成型品を３００℃で３０分間乾燥し、９００〜１４００℃で加熱硬化処理を行って得られた焼成品は、大気中で１４００℃の耐熱性（軟化温度）を示した。Ｘ線回折の結果、図９に示すＬのＸ線回折図が得られた。すなわち、クリストバライト型リン酸アルミニウムＡｌＰＯ4結晶とトリジマイト型リン酸アルミニウムＡｌＰＯ4結晶とリン酸カルシウムＣａ2Ｐ2Ｏ7結晶の３つの結晶構造が確認された。該焼成品の耐熱性（軟化温度）は、１４００℃であった。
【００４０】
参考試験例５：
シラスバルーン（「ＳＳＢ−４０００ＳＳ」商品名：平均粒径７５μｍ、かさ比重０．１８〜０．２１、豊和直株式会社製、）２００ｇに、珪酸リチウム溶液（ＳｉＯ2：２０％、Ｌｉ2Ｏ：２０％、日本化学工業株式会社製）２００ｇを添加・混合し、それを型枠に入れ、５０ｋｇｆ／ｃｍ2のプレス圧力で加圧成形し、炭酸ガスを注入して硬化する。型枠から外し３００℃で３０分間乾燥し、リン酸溶液（Ｐ2Ｏ5：５３．５〜５５％、Ａｌ2Ｏ3：１．０％、比重１．６、粘度（２０℃）４０ｃｐ、ｐＨ０．５以下）に２〜５秒間浸して成型品と同重量を含浸させる。
この成型品を３００℃で３０分間乾燥し、９００〜１２００℃で加熱硬化処理を行って得られた焼成品は、大気中で１２００℃の耐熱性（軟化温度）を示した。Ｘ線回折の結果、図１０に示すＭのＸ線回折図が得られた。すなわち、クリストバライト型リン酸アルミニウムＡｌＰＯ4結晶とトリジマイト型リン酸アルミニウムＡｌＰＯ4結晶の２つの結晶構造が確認された。
【００４１】
【発明の効果】
以上のとおり、本願発明によれば、優れた白色度及び耐熱性の火山噴出物焼成発泡粒体と、発泡粒体の集合硬化物が低コストで提供される。このような性質を持つ火山噴出物焼成発泡粒体（シラスバルーン等）及び火山噴出物発泡粒体集合硬化物は、環境にやさしく、付加価値の高い無機質の素材となる。
シラスバルーンの主要ユーザーである紙粘土メーカーとしては、紙粘土製品の安全性や環境への負荷を考慮して出来るだけ人工の有機系素材を避けて天然無機系素材を使いたい意向があるところ、本発明に係るシラスバルーンは高白色度であって、同紙粘土製品に好適に使用でき、また、耐熱性に優れることから、耐熱塗料、断熱材、耐熱タイルなどの新規の需要にも適用できる。
【図面の簡単な説明】
【図１】単なるガラス質シリカ（ＳｉＯ2・ｎＨ2Ｏ）（Ａ）と、少量のリン酸アルミニウムを含有するリン酸溶液の蒸発乾固物の１２００℃加熱処理品（Ｂ−１）と、ガラス質シリカとリン酸アルミニウムを含有するリン酸溶液との混合物の１３００℃加熱処理品（Ｃ）の各Ｘ線回折図である。
【図２】単なるガラス質シリカ（ＳｉＯ2・ｎＨ2Ｏ）（Ａ）と、リン酸アルミニウム溶液の蒸発乾固物の１３００℃加熱処理品（Ｂ−２）と、ガラス質シリカとリン酸アルミニウム溶液との混合物の１３００℃加熱処理品（Ｄ）の各Ｘ線回折図である。
【図３】ガラス質火山噴出物のシラス（非晶質）（Ｆ−１）と、少量のリン酸アルミニウムを含有（Ａｌ2Ｏ3として１％）するリン酸溶液（Ｐ2Ｏ5として５５％）の蒸発乾固物の１２００℃加熱処理品（Ｂ−１）と、シラスとこのリン酸溶液との混合物の１３００℃加熱処理品（Ｅ）の各Ｘ線回折図である。
【図４】ガラス質火山噴出物のシラス（非晶質）（Ｆ−１）と、リン酸アルミニウムの蒸発乾固物の１３００℃加熱処理品（Ｂ−２）と、シラスとリン酸アルミニウムとの混合物の１３００℃加熱処理品（Ｇ）の各Ｘ線回折図である。
【図５】シラスバルーン（ガラス質火山噴出物の発泡粒体）（Ｆ−２）と、少量のリン酸アルミニウムを含有するリン酸溶液の蒸発乾固物の１２００℃加熱処理品（Ｂ−１）と、シラスバルーンと少量のリン酸アルミニウムを含有するリン酸溶液との混合物の１４００℃加熱処理品（Ｈ）の各Ｘ線回折図である。
【図６】シラスバルーン（ガラス質火山噴出物の発泡粒体）（Ｆ−２）と、リン酸アルミニウム溶液の蒸発乾固物の１３００℃加熱処理品（Ｂ−２）と、シラスバルーンとリン酸アルミニウム溶液との混合物の１５００℃加熱処理品（Ｊ−１）の各Ｘ線回折図である。
【図７】シラスバルーンとリン酸アルミニウム溶液との混合物の１４００℃加熱処理品（Ｊ−２）のＸ線回折図である。
【図８】シラスバルーンとアルミナセメントとリン酸アルミニウム溶液との混合物の１３００℃加熱処理品（Ｋ）のＸ線回折図である。
【図９】シラスバルーンと炭酸カルシウムとリン酸アルミニウム溶液との混合物の１４００℃加熱処理品（Ｌ）のＸ線回折図である。
【図１０】シラスバルーンと珪酸リチウム溶液との混合物に炭酸ガスを注入して硬化させた硬化物にリン酸アルミニウム溶液を含浸させ、乾燥後、１２００℃で加熱処理して得られた焼成品（Ｍ）のＸ線回折図である。[0001]
BACKGROUND OF THE INVENTION
The present invention is a glassy volcanic ejecta.Foam granulesThe present invention relates to a light and high-strength volcanic ejecta foam and aggregate hardened product, and a method for producing them.
[0002]
[Prior art]
A general manufacturing method of Shirasu Balloon, which is a kind of foam particles of glassy volcanic ejecta, is volcanic ejecta (shirasu) → particle size adjustment → fired foaming (using medium fluidized bed furnace) → recovery → product. Firing and foaming of glassy volcanic ejecta in a medium fluidized bed furnace enables rapid firing and foaming in a short-term residence time of 1 minute or less (especially 10 seconds or less or 1 second or less) in a combustion gas atmosphere with low oxygen concentration. Therefore, it is easy to obtain a product with high whiteness, it is easy to foam efficiently, and the amount of treatment can be increased, so that it is used for industrial production of shirasu balloons.
The whiteness of the shirasu balloon can be measured by Journal of Materials Science, Vol. 34, pp. 2461-2468 (1999). As described by the present inventors, it is influenced by the oxidation coloring of iron in glassy volcanic ejecta (such as shirasu) during high-temperature firing. The medium fluidized bed furnace has a low oxygen concentration at the time of firing foaming and a short heat treatment time, so that the iron content in the volcanic ejecta is difficult to oxidize and color, and can produce a shirasu balloon with higher whiteness than an electric furnace heated in the atmosphere. .
However, oxidation of iron to some extent is inevitable, and the Shirasu balloon product has a light skin color, its whiteness is about 85 at the maximum, and its improvement is limited.
[0003]
For this reason, Shirasu Balloon Manufacturing Companies, for users who require high whiteness, can remove impurities other than vitreous materials containing iron by elutriation or magnetic separation of raw materials, or elutriate baked and foamed Shirasu balloons. Have been devised to ship water floats with relatively high whiteness.
However, even with these treatments, there is a slight increase in whiteness, and there are problems such as the product exhibiting a pale skin color and increased processing costs. With the current production method using a medium fluidized bed furnace, whiteness is improved. The fundamental and important problem that there is a limit remains.
Therefore, in spite of desperate corporate efforts, the paper clay industry, which was the main user of Shirasu Balloon, is currently being deprived of the market by high whiteness plastic balloons.
In addition, the current Shirasu balloon is only fired and foamed after selecting the particle size of the raw material, and its softening temperature is about 900 ° C., which is almost the same as the raw material. For applications to materials, etc., further improvement in heat resistance is required, but no product that satisfies the requirement has existed. With regard to the breaking strength of Shirasu balloons, it is easy to burst during the firing and foaming process by rapid heating using a medium fluidized bed furnace, so there are products that contain a lot of ruptured or cracked products, and higher strength products. The demand for is also increasing.
[0004]
[Problems to be solved by the invention]
Therefore, the problem to be solved by the present invention is to fundamentally solve the problem of coloring (becomes a light skin-colored shirasu balloon) in the manufacture of shirasu balloons, and at the same time to improve the heat resistance and increase the strength that are highly demanded by the market. Is to achieve. And theseGlassyDeveloped a new unprecedented product (volcanic ejecta foam aggregated cured product) with excellent whiteness, light weight and high strength heat resistance as a molded product (secondary product) made from volcanic ejecta foam granules It is an issue to provide.
[0005]
[Means for Solving the Problems]
The present invention solves the above-mentioned problems of the prior art, and relates to the provision of a volcanic ejecta foam granule and an aggregated cured product of the foam granule excellent in whiteness and heat resistance.
(1) Average particle sizeMainly composed of silica and alumina of 6 μm to 5 mmAluminum phosphate is added to 100 parts by weight of glassy volcanic ejecta.2OFiveIn conversion3 to 110 parts by weight is applied and fired at 800 to 1500 ° C. in a furnace.Obtained, Cristobalite-type aluminum phosphate crystals are mixed in the structure, and the softening temperature is 1100 ° C. to 1500 ° C.Volcanic ejecta foam granules having excellent whiteness and heat resistance.
[0006]
(2) Average particle sizeMainly composed of silica and alumina of 6 μm to 5 mmGlassy volcanic ejectaAluminum phosphate is added to 100 parts by weight of the foam granules. 2 O Five 3 to 110 parts by weight in terms of dust is applied and fired at 800 to 1500 ° C. in a furnace.ObtainedThe cristobalite type aluminum phosphate crystal and the tridymite type aluminum phosphate crystal are mixed in the structure, and the softening temperature is 1100 ° C to 1500 ° C.Volcanic ejecta foam granules having excellent whiteness and heat resistance.
(3)Mainly composed of silica and alumina having an average particle diameter of 6 μm to 5 mmGlassy volcanic ejectaA mixture of aluminum phosphate and phosphoric acid is added to 100 parts by weight of foam granules. 2 O Five 3 to 110 parts by weight, Al 2 O Three A cristobalite type aluminum phosphate crystal is mixed in the structure obtained by applying 0.01 to 40 parts by weight in terms of conversion and firing at 800 to 1500 ° C. in a furnace, and the softening temperature is 1100 to 1500 ° C. ℃Volcanic ejecta foam granules having excellent whiteness and heat resistance.
(4)Vitreous mainly composed of silica and alumina with an average particle diameter of 6 μm to 5 mmVolcanic ejecta foam granulesIn 100 parts by weight, P is a mixture of aluminum phosphate and phosphoric acid. 2 O Five 3 to 110 parts by weight, Al 2 O Three 0.01-40 parts by weight in terms of conversion, and obtained by baking at 800-1500 ° C. in a furnace, cristobalite type aluminum phosphate crystals and tridymite type aluminum phosphate crystals are mixed in the structure, Softening temperature is 1100 ° C-1500 ° CVolcanic ejecta foam granules having excellent whiteness and heat resistance.
(5) Volcanic ejecta foam granules having an average particle size of 6 μm to 5 mmIs a shirasu balloon with an average particle size of 6 μm to 5 mmIt is characterized by(1) to any one of (4)Volcanic ejecta foam granules with excellent whiteness and heat resistance.
[0007]
(6) Average particle diameter of 6 μm to 5 mmVitreous based on silica and aluminaAluminum phosphate is added to 100 parts by weight of volcanic ejecta foam.2OFive3.0 to 110 parts by weight in terms of conversionAddition-mixed mixture is pressure-molded, dried, and then fired at 800-1500 ° C. Cristobalite-type aluminum phosphate crystals are mixed, and the softening temperature is 1200 ° C to 1500 ° C.Volcanic ejecta foam granules with excellent whiteness and heat resistanceSet of cured products.
(7) Average particle diameter of 6 μm to 5 mmA glassy volcano composed mainly of silica and aluminaEjectaAluminum phosphate is added to 100 parts by weight of the foam granules. 2 O Five Cristobalite-type aluminum phosphate crystals and tridymite-type aluminum phosphate crystals in the structure obtained by pressure-molding a mixture obtained by adding 3.0 to 110 parts by weight in terms of conversion, drying and firing at 800-1500 ° C. And the softening temperature is 1200 ° C to 1500 ° CVolcanic ejecta foam granules with excellent whiteness and heat resistanceSet of cured products.
(8)A glassy volcano composed mainly of silica and alumina with an average particle size of 6 μm to 5 mmEjectaA mixture of aluminum phosphate and phosphoric acid is added to 100 parts by weight of foam granules. 2 O Five 3.0 to 110 parts by weight, Al 2 O Three Cristobalite-type aluminum phosphate crystals are mixed in the structure obtained by pressure-molding a mixture obtained by adding 0.01 to 40 parts by weight in terms of conversion, drying, and firing at 800 to 1500 ° C., Softening temperature 1200 ° CVolcanic ejecta foam granule excellent in whiteness and heat resistance, characterized by being ˜1500 ° C.Set of cured products.
[0008]
(9) The aboveAluminum phosphate is added to 100 parts by weight of volcanic ejecta foam granules having excellent whiteness and heat resistance according to any one of (1) to (5). 2 O Five The mixture obtained by adding 3.0 to 110 parts by weight in terms of pressure is pressure-molded, dried and then fired at 800 to 1500 ° C., and the cristobalite-type aluminum phosphate crystals are mixed in the structure to soften. The temperature is 1200 to 1500 ° CVolcanic ejecta foam granules with excellent whiteness and heat resistanceSet of cured products.
(10)The whiteness and heat resistance according to any one of (1) to (5) above are excellent.Aluminum phosphate is added to 100 parts by weight of volcanic ejecta foam.2OFiveThe mixture prepared by adding 3.0 to 110 parts by weight in terms of pressure is pressure-molded, dried, and calcined at 800 to 1500 ° C.Cristobalite type aluminum phosphate crystal and tridymite type aluminum phosphate crystal are mixed in the obtained structure, and the softening temperature is 1200 ° C to 1500 ° C.An aggregate cured product of volcanic ejecta foam particles having excellent whiteness and heat resistance.
(11)Vitreous mainly composed of silica and alumina with an average particle diameter of 6 μm to 5 mmAn aqueous solution of aluminum phosphate is added to 100 parts by weight of volcanic ejecta foam.2OFiveAdd 3-110 parts by weight in terms of conversion-After kneading, spraying, and drying treatment, firing at 800-1500 ° C in a furnace, cristobalite-type aluminum phosphate crystals are mixed in the structure, and softening temperature is 1100 ° C-1500 ° C Get granulesOf volcanic ejecta foam with excellent whiteness and heat resistanceProduction method.
(12)Vitreous mainly composed of silica and alumina with an average particle diameter of 6 μm to 5 mmTo 100 parts by weight of volcanic ejecta foam particles, aluminum phosphateAqueous solutionP2OFive3 to 110 parts by weight in terms of conversionIs added, kneaded and sprayed, dried, and then fired in a furnace at 800-1500 ° C., and the structure contains a mixture of cristobalite-type aluminum phosphate crystals and tridymite-type aluminum phosphate crystals. Obtains foamed granules having a temperature of 1100 ° C. to 1500 ° C.Volcanic ejecta foam granules with excellent whiteness and heat resistanceManufacturing method.
(13)Vitreous mainly composed of silica and alumina with an average particle diameter of 6 μm to 5 mmTo 100 parts by weight of volcanic ejecta foam particles, aluminum phosphateAnd an aqueous solution of phosphoric acid mixtureP2OFive3 to 110 parts by weight in terms of conversion, Al 2 O Three In addition, 0.01 to 40 parts by weight in terms of addition are kneaded and sprayed.Baked at 800-1500 ° C, Cristobalite-type aluminum phosphate crystals are mixed in the structure, and foam particles having a softening temperature of 1100 ° C. to 1500 ° C. are obtained.Volcanic ejecta foam granules with excellent whiteness and heat resistanceManufacturing method.
[0009]
(14)Vitreous mainly composed of silica and alumina with an average particle diameter of 6 μm to 5 mmTo 100 parts by weight of volcanic ejecta foam, A mixture of aluminum phosphate and phosphoric acidP solution2OFive3.0 to 110 parts by weight in terms of conversion, Al 2 O Three Add 0.01-40 parts by weight in terms of kneading and spraying In the furnace after drying,Baked at 800-1500 ° C, Cristobalite-type aluminum phosphate crystals and tridymite-type aluminum phosphate crystals are mixed in the structure to obtain foam particles having a softening temperature of 1100 ° C. to 1500 ° C.Volcanic ejecta foam granules with excellent whiteness and heat resistanceManufacturing method.
(15)A glassy volcanic ejecta foam granule mainly composed of silica and alumina having an average particle diameter of 6 μm to 5 mm according to any one of (11) to (14),An aqueous solution of aluminum phosphate is added to 100 parts by weight of a glassy volcanic ejecta powder having an average particle size of 2 to 1000 μm.2OFiveAdd 0.3 to 28.0 parts by weight in terms of conversion, knead and spray, dry, and then bake and foam at 900 to 1200 ° C in a fluidized bed furnace.It is obtained byA method for producing volcanic ejecta foam granules having excellent whiteness and heat resistance.
[0010]
(16)A glassy volcanic ejecta foam granule mainly composed of silica and alumina having an average particle diameter of 6 μm to 5 mm according to any one of (11) to (14),An aqueous solution of a mixture of aluminum phosphate and phosphoric acid is added to 100 parts by weight of a glassy volcanic ejecta powder having an average particle diameter of 2 to 1000 μm.2OFive0.3 to 28.0 parts by weight, Al2OThree0.01 to 20 parts by weight in terms of addition, kneading and spraying, drying treatment, and firing and foaming at 900 to 1200 ° C. in a fluidized bed furnaceIt was obtainedThe manufacturing method of the volcanic ejecta foam granule excellent in the whiteness and heat resistance characterized by the above-mentioned.
(17)A drying process is performed at 200-800 degreeC.It is characterized by(11) to (16)A method for producing volcanic ejecta foam granules having excellent whiteness and heat resistance.
(18)Mainly composed of silica and alumina having an average particle diameter of 6 μm to 5 mmGlassy volcanic ejectaFoam granules are shirasu balloonIt is characterized by(11)The manufacturing method of the volcanic ejecta foam granule excellent in the whiteness and heat resistance of any one of-(17).
(19)An aqueous solution of aluminum phosphate is added to 100 parts by weight of a glassy volcanic ejecta foam granule mainly composed of silica and alumina having an average particle diameter of 6 μm to 5 mm. 2 O Five The mixture prepared by adding 3.0 to 110 parts by weight in terms of pressure is pressure-molded and dried, and then calcined at 800 to 1500 ° C., so that cristobalite-type aluminum phosphate crystals are mixed in the structure, and the softening temperature Obtains an aggregate cured product of volcanic ejecta foam granules having a temperature of 1200 to 1500 ° COf volcanic ejecta foam with excellent whiteness and heat resistanceCollective curedProduction method.
[0011]
(20) Average particle diameter of 6 μm to 5 mmVitreous based on silica and aluminaAn aqueous solution of aluminum phosphate is added to 100 parts by weight of volcanic ejecta foam.2OFiveAddition of 3.0 to 110 parts by weight in terms of conversionAfter the mixed mixture is pressure-molded and dried, it is fired at 800 to 1500 ° C., and the cristobalite type aluminum phosphate crystal and the tridymite type aluminum phosphate crystal are mixed in the structure, and the softening temperature is 1200 ° C. Obtaining an aggregate hardened product of volcanic ejecta foam particles of ~ 1500 ° CThe manufacturing method of the aggregate hardened | cured material of the volcanic ejecta foam granule excellent in the whiteness and heat resistance characterized by the above-mentioned.
(21)A drying process is performed at 200-800 degreeC.It is characterized byThe method according to any one of claims 19 to 20.Volcanic ejecta foam with excellent whiteness and heat resistanceCollective curedProduction method.
[0012]
Further alternatives are also advantageous:
(22) Vitreous mainly composed of silica and alumina having an average particle diameter of 6 μm to 5 mmAn aqueous solution of aluminum phosphate is added to 100 parts by weight of volcanic ejecta foam.2OFiveAfter pressure-molding a mixture obtained by adding 3.0 to 110 parts by weight and 5 to 200 parts by weight of alumina cement in terms of conversion and drying, the mixture was fired at 800 to 1500 ° C.,Obtaining an aggregate hardened product of volcanic ejecta foam granules in which cristobalite-type aluminum phosphate crystals are mixed in the structureThe manufacturing method of the aggregate hardened | cured material of the volcanic ejecta foam granule excellent in the whiteness and heat resistance characterized by the above-mentioned.
[0013]
(23) Vitreous mainly composed of silica and alumina having an average particle diameter of 6 μm to 5 mmAn aqueous solution of aluminum phosphate is added to 100 parts by weight of volcanic ejecta foam.2OFiveAfter pressure-molding and drying the mixture in which 3.0 to 110 parts by weight and 10 to 100 parts by weight of calcium carbonate are added and mixed, the mixture is baked at 800 to 1500 ° C.,Obtaining an aggregate hardened product of volcanic ejecta foam granules in which cristobalite-type aluminum phosphate crystals are mixed in the structureThe manufacturing method of the aggregate hardened | cured material of the volcanic ejecta foam granule excellent in the whiteness and heat resistance characterized by the above-mentioned.
(24) Vitreous mainly composed of silica and alumina having an average particle diameter of 6 μm to 5 mmAfter adding and kneading 10.0 to 70.0 parts by weight of an alkali metal silicate aqueous solution in terms of solid matter to 100 parts by weight of volcanic ejecta foam particles, carbon dioxide is injected into the molded body. The aluminum phosphate aqueous solution is added to the cured product.2OFiveAfter impregnating 3.0 to 110 parts by weight in terms of conversion and drying, firing at 800 to 1500 ° C.,Obtaining an aggregate hardened product of volcanic ejecta foam granules in which cristobalite-type aluminum phosphate crystals are mixed in the structureThe manufacturing method of the aggregate hardened | cured material of the volcanic ejecta foam granule excellent in the whiteness and heat resistance characterized by the above-mentioned.
(25) Vitreous mainly composed of silica and alumina having an average particle diameter of 6 μm to 5 mmAfter adding and kneading 50 to 200 parts by weight of a lithium silicate aqueous solution with a concentration of 19.5 to 30% to 100 parts by weight of volcanic ejecta foam, the carbonic acid gas is injected into the kneaded product and cured. Add aluminum phosphate aqueous solution to the product.2OFiveAfter impregnation of 3.0 to 110 parts by weight in terms of conversion and drying treatment, firing at 800 to 1500 ° C.As a result, an aggregate hardened product of volcanic ejecta foam particles in which cristobalite type aluminum phosphate crystals are mixed in the structure is obtained.The manufacturing method of the aggregate hardened | cured material of the volcanic ejecta foam granule excellent in the whiteness and heat resistance characterized by the above-mentioned.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, shirasu, obsidian, nacre, pumice, etc.Mainly composed of silica and aluminaAn aqueous solution of aluminum phosphate is added and kneaded to the powdery raw material of the glassy volcanic ejecta, dried at 900 ° C. or lower, preferably 200 to 800 ° C., and then heated to 900 to 1200 in a fluidized bed furnace. By firing and foaming at ℃ for a short time, particularly preferably for 10 seconds or less, most preferably for 1 second or less, volcanic ejecta foam granules having excellent whiteness and heat resistance are obtained.
The firing and foaming treatment of the raw material granules covered with aluminum phosphate is 800 to 1200 ° C., preferably 900 to 1200 ° C. At temperatures lower than 800 ° C., the foaming rate is remarkably low and the heat history is insufficient. A temperature higher than 1200 ° C. is not preferable because it excessively foams and easily bursts, and the raw material powders are easily fused.
[0015]
The drying treatment is preferably performed for 10 to 60 minutes in a rotary kiln, and the firing foaming treatment of the dried raw material powder is preferably performed in a medium fluidized bed furnace. By doing so, the particles adhere to each other and do not form a lump, and an independent foamed particle is easily obtained.
Moreover, although the whiteness shows 85-98 in the suitable example of the foaming granular material of the volcanic ejecta of the high whiteness acquired by this invention, the whiteness of a commercially available shirasu balloon is 60-85. Further, the high whiteness shirasu balloon has a heat resistance (softening temperature) of about 100 to 500 ° C. higher than that of the conventional shirasu balloon. The Shirasu balloon obtained by baking and foaming at 960 ° C. using a medium fluidized bed furnace without adding an aluminum phosphate aqueous solution to the Shirasu raw material has a whiteness of 78.4 and is thin. The skin color was exhibited.
[0016]
The amount of aluminum phosphate added and kneaded to the glassy volcanic ejecta powder granules having an average particle diameter of 2 to 1000 μm is determined by adding an aluminum phosphate aqueous solution to 100 parts by weight of the granular raw material of the glassy volcanic ejecta.2OFive0.3 to 28.0 parts by weight in terms of conversion is preferable.
And after carrying out a drying process in the said suitable temperature range, the volcanic ejecta foam granule excellent in whiteness and heat resistance is manufactured by baking and foaming at 900-1200 degreeC in a fluidized bed furnace. Moreover, in the said method, the mixture aqueous solution of aluminum phosphate and phosphoric acid is added to 100 weight part of glassy volcanic ejecta granular material with an average particle diameter of 2-1000 micrometers.2OFive0.3 to 28.0 parts by weight, Al2OThreeIt is preferable to add and knead 0.01 to 20 parts by weight in terms of conversion.
The mixed treating agent preferably has a viscosity (20 ° C.) of 500 cp or less, particularly preferably 40 to 80 cp, and when the viscosity exceeds 500 cp, the glassy volcanic ejecta particles having an average particle diameter of 2 to 1000 μm The bodies may agglomerate to form dumplings.
[0017]
Moreover, average particle diameter obtained by baking foaming processing of glassy volcanic ejecta is 6 μm to 5 mm.Mainly composed of silica and aluminaAn aqueous solution of aluminum phosphate is added to 100 parts by weight of volcanic ejecta foam.2OFive3 to 110 parts by weight in terms of addition, kneading and spraying, drying, and then firing at 800 to 1500 ° C. in a furnace such as a gas firing furnace, fluidized bed furnace, rotary kiln, etc. For example, a volcanic ejecta foam granule having excellent heat resistance (softening temperature) of 100 to 500 ° C. is obtained.
[0018]
Further, the volcanic ejecta foam particles obtained as described above are adhered to aluminum phosphate, a mixture of aluminum phosphate and phosphoric acid, a mixture of aluminum phosphate and alumina cement, or a mixture of aluminum phosphate and calcium carbonate. When an aqueous solution is added, kneaded, and pressure-molded, and calcined at 800-1500 ° C., it is possible to produce an aggregate cured product of volcanic ejecta foam granules that are excellent in whiteness and heat resistance. it can.
Also,SaidAfter adding and kneading the alkali metal silicate aqueous solution to the foam particles of volcanic ejecta, molding, injecting carbon dioxide into the molded product and curing it, impregnating the cured product with an aluminum phosphate aqueous solution and drying After the treatment, an aggregated cured product of volcanic ejecta foam granules having excellent whiteness and heat resistance can be produced by firing at 800 to 1500 ° C. (preferably 900 to 1200 ° C.).
[0019]
As a result of various researches for producing high-quality volcanic ejecta foam granules, the present inventor found that the cause of the coloration of the shirasu balloon was volcano glass (shirasu, etc.) at the time of calcination foaming by analysis of a Mossbauer spectrum before and after calcination Clarified that the iron content in the raw material is oxidized. However, even if the firing conditions such as the firing temperature and residence time (heat treatment time) of the medium fluidized bed furnace are changed, it has been impossible to completely prevent oxidation coloring of iron.
In addition, although a method of physically coating the surface with a treatment agent such as colloidal silica sol or alumina sol was used, oxidation of iron could not be prevented and whiteness was not improved.
Therefore, various antioxidants were examined as a method for chemically preventing the oxidation of iron in shirasu. Since organic antioxidants and chelate compounds were burned off during high-temperature firing and could not prevent the oxidation of iron, various inorganic chemical treatment agents that could be expected to be effective even during high-temperature firing (not burned out) were studied. .
Finally, after the surface of the glassy volcanic ejecta, particularly the shirasu raw material granule, is coated with a phosphating agent, particularly preferably aluminum phosphate, it is fired and foamed at 960 ° C. using a medium fluidized bed furnace. Thus, oxidation of iron was almost completely prevented, the pale skin color disappeared, and a shirasu balloon with a whiteness of 98, which had a high whiteness comparable to that of a conventional shirasu balloon, could be produced. The reason is not clear, but phosphoric acid has the property that it can easily oxidize metal ions (iron ions, etc.) and chelate as used in detergents, and it reacts with high temperature heating to oxidize iron. It is presumed that it has both of the properties of preventing even at high temperatures.
[0020]
In addition, in the firing foaming process using the medium fluidized bed furnace in the present invention, the aluminum phosphate AlPO excellent in heat resistance and strength due to the reaction between the phosphate and the volcanic glass during the high temperature heating of the phosphate.FourAs a result of this improvement, it has been confirmed that the shirasu balloon has a function of suppressing excessive foaming, and the breaking strength of the shirasu balloon is improved.
According to the present invention, since the iron-containing shirasu raw material and pumice raw material (used after pulverization) that could not be used as a shirasu balloon raw material can express whiteness equal to or higher than that of a commercially available shirasu balloon, 90 km in southern Kyushu.ThreeOrdinary shirasu, which is said to exist, can be used as a shirasu balloon material, and cost reduction can be achieved at the same time. As the above-mentioned phosphate, aluminum phosphate is used, but in addition to this, even when each aqueous solution containing high concentration of phosphorus pentoxide such as sodium phosphate, calcium phosphate, potassium phosphate, etc. is used, the same high Confirmed to show whiteness. And as a post-treatment of shirasu balloon, after coating with aluminum phosphate on the surface of the granule, when firing at 1500 ° C. or less in the air, the whiteness is improved as the firing temperature is increased, and the heat resistance is also improved. It was confirmed that it improved significantly.
[0021]
In addition, as an example of a secondary product using the volcanic ejecta foam granules of the present invention, a volcano obtained by injecting carbon dioxide gas into a kneaded product obtained by adding and kneading a lithium silicate aqueous solution to volcanic ejecta foam granules There are ejected foam aggregate aggregates.
This aggregated cured product has improved heat resistance as compared to the aggregated cured product using a conventional shirasu balloon. Furthermore, the volcanic ejecta foam aggregated cured product obtained by applying an aluminum phosphate aqueous solution to the surface of the aggregated cured product and heat-treating at 800-1500 ° C. is further improved in heat resistance (softening temperature becomes 1200 ° C.-1500 ° C. )
[0022]
Next, based on the X-ray diffraction diagram showing the X-ray diffraction measurement result, the volcanic ejecta foam granules, the hardened foam of the volcanic ejecta foam granules and related matters will be described.
The X-ray diffraction diagram shown in FIG.2・ NH2O) (A), 1200 ° C heat-treated product (B-1) of an evaporating dry product of a phosphoric acid solution containing a small amount of aluminum phosphate, and 1300 ° C of a mixture of vitreous silica and this phosphoric acid solution It is each X-ray diffraction pattern of the heat-treated product (C), and even the 1300 ° C. heat-treated product (C) of a mixture of vitreous silica and phosphoric acid solution is almost amorphous, and each substance is crystalline. Existence cannot be confirmed. That is, it can be seen that even if glassy silica that is not a glassy volcanic ejecta and phosphoric acid are reacted at a high temperature, a crystalline material with high heat resistance is not generated.
[0023]
FIG. 2 shows simple glassy silica (
(B-2) Almost all graph lines are aluminum phosphates in which all peaks are aluminum phosphate (PO).Three)ThreeIt only shows the crystals of That is, it can be understood that even if glassy silica that is not a glassy volcanic ejecta and aluminum phosphate are reacted at a high temperature, almost no crystalline substance is generated.
[0024]
FIG.Mainly composed of silica and aluminaContains glassy volcanic eruption shirasu (amorphous) (F-1) and a small amount of aluminum phosphate (Al2OThreePhosphoric acid solution (P2OFiveX-ray diffraction patterns of a 1200 ° C heat-treated product (B-1) of an evaporative dried product (containing 55% as) and a 1300 ° C heat-treated product (E) of a mixture of Shirasu and this phosphoric acid solution, Cristobalite type aluminum phosphate crystal AlPO characterized by 2θ around 22 ° and 36 °FourIs recognized.
[0025]
FIG. 4 shows a glassy volcanic ejecta shirasu (amorphous) (F-1), an aluminum phosphate evaporate 1300 ° C. heat-treated product (B-2), and a shirasu and aluminum phosphate solution. X-ray diffractograms of a 1300 ° C. heat-treated product (G) of the mixture of the cristobalite type aluminum phosphate crystal (AlPO characterized by 2θ of around 22 ° and 36 °Four) And tridymite-type aluminum phosphate crystals (AlPO) characteristic around 20 ° and 23 °Four). That is, in the 1300 ° C. heat-treated product (G) of a mixture of shirasu and aluminum phosphate, tridymite type aluminum phosphate crystals and cristobalite type aluminum phosphate crystals are observed. It can be estimated that heat resistance and strength are excellent.
[0026]
FIG. 5 shows a shirasu balloon (Mainly composed of silica and aluminaFoamed particles of glassy volcanic products (F-2), 1200 ° C heat-treated product (B-1) of evaporated and dried phosphoric acid solution containing a small amount of aluminum phosphate, Shirasu balloon and small amount FIG. 2 is an X-ray diffraction diagram of a 1400 ° C. heat-treated product (H) of a mixture with a phosphoric acid solution containing aluminum phosphate, and cristobalite-type aluminum phosphate crystals characterized by 2θ around 22 ° and 36 ° ( AlPOFour) And tridymite-type aluminum phosphate AlPO characteristic around 20 ° and 23 °FourA mixture of crystals is observed. That is, even in a 1400 ° C. heat-treated product (H) of a mixture of shirasu balloon and aluminum phosphate, the tridymite type aluminum phosphate crystal AlPOFourAnd cristobalite type aluminum phosphate crystal AlPOFourFrom the characteristics of the crystals, it can be estimated that the fired reaction product is excellent in heat resistance and strength.
[0027]
FIG. 6 shows a shirasu balloon (foam particles of glassy volcanic ejecta) (F-2), a 1300 ° C. heat-treated product (B-2) of an evaporated and dried aluminum phosphate solution, a shirasu balloon and phosphorus. It is each X-ray diffraction diagram of a 1500 ° C. heat-treated product (J-1) of a mixture with an aluminum acid solution, and cristobalite type aluminum phosphate crystals characteristic of 2θ around 22 ° and 36 ° and 20 ° and 23 °. A characteristic mixture of tridymite-type aluminum phosphate crystals is observed in the vicinity.
That is, in a 1500 ° C. heat-treated product (J-1) of a mixture of shirasu balloon and aluminum phosphate, tridymite type aluminum phosphate crystal AlPOFourAnd cristobalite type aluminum phosphate crystal AlPOFourFrom the characteristics of the crystals, it can be estimated that the fired reaction product is excellent in heat resistance and strength.
[0028]
FIG. 7 is an X-ray diffraction pattern of a 1400 ° C. heat-treated product (J-2) of a mixture of a shirasu balloon and an aluminum phosphate solution, with 2θ being 20 ° and 23 ° around tridymite type aluminum phosphate crystal AlPO.FourAnd cristobalite-type aluminum phosphate crystals AlPO characteristic around 22 ° and 36 °FourMixed.
That is, tridymite type aluminum phosphate crystals and cristobalite type aluminum phosphate crystals are also observed in a 1400 ° C. heat-treated product (J-2) of a mixture of shirasu balloon and aluminum phosphate solution. From the characteristics of these crystals, it can be estimated that the fired reaction product has excellent heat resistance.
[0029]
FIG. 8 is an X-ray diffraction pattern of a 1300 ° C. heat-treated product (K) of a mixture of shirasu balloon, alumina cement, and aluminum phosphate solution. Characteristic tridymite phosphoric acid with 2θ around 20 ° and 23 ° Aluminum crystal AlPOFourIn addition, characteristic cristobalite type aluminum phosphate crystals are mixed in the vicinity of 22 ° and 36 °, and a large amount of tridymite type aluminum phosphate crystals is confirmed.
That is, in the 1300 ° C heat-treated product (K) of a mixture of shirasu balloon, alumina cement and aluminum phosphate, cristobalite type aluminum phosphate crystals and abundant tridymite type aluminum phosphate crystals are observed, and the characteristics of these crystals are observed. Therefore, it can be estimated that the fired reaction product is excellent in heat resistance.
[0030]
FIG. 9 is an X-ray diffraction pattern of a 1400 ° C. heat-treated product (L) of a mixture of shirasu balloon, calcium carbonate and aluminum phosphate solution, which is characteristic of tridymite type phosphoric acid having 2θ around 20 ° and 23 °. A mixture of aluminum crystals and cristobalite-type aluminum phosphate crystals characteristic around 22 ° and 36 ° is observed.
Furthermore, crystals of calcium phosphate having a peak near 29 ° from 27 ° to 34 ° are also observed. That is, also in the product, tridymite type aluminum phosphate crystal and cristobalite type aluminum phosphate crystal are recognized, and in addition to them, calcium phosphate crystal is also recognized. It can be estimated that it will be excellent.
[0031]
FIG. 10 shows a fired product obtained by impregnating a cured product obtained by injecting carbonic acid gas into a mixture of a shirasu balloon and a lithium silicate solution and impregnating the aluminum phosphate solution with the mixture, drying, and heat-treating at 1200 ° C. M) is an X-ray diffraction diagram, and in this example too, a tridymite type aluminum phosphate crystal AlPO characterized by 2θ around 20 ° and 23 °FourMixing of cristobalite-type aluminum phosphate crystals characteristic around 22 ° and 36 ° was observed. From the characteristics of these crystals, it can be estimated that the fired reaction product has excellent heat resistance.
[0032]
【Example】
Examples of the present invention will be described below.
Example 1:
100 kg of shirasu raw material (shirasu with an average particle size of 35.0 μm) from Yoshida-cho, Satsuma-gun, Kagoshima Prefecture. Aluminum phosphate aqueous solution (“Acidphos 75”, manufactured by Taki Chemical Co., Ltd., 50% phosphorus pentoxide, aluminum oxide 10 kg of an aluminum phosphate aqueous solution (9%, balance water) was added, and the mixture was stirred with a stirrer so as to spread over the entire screen.
Next, the mixed and stirred raw material was dried at 650 ° C. in a rotary kiln, and the raw material powder was fired and foamed at 960 ° C. using a medium fluidized bed furnace. The whiteness was 87.3, the tapping bulk specific gravity was 0.14, and the average A high whiteness shirasu balloon with a particle size of 51.7 μm could be produced. Further, this high whiteness shirasu balloon has improved heat resistance compared to the conventional shirasu balloon. The Shirasu balloon obtained by baking and foaming at 960 ° C. using a medium fluidized bed furnace without adding an aluminum phosphate aqueous solution to the Shirasu raw material has a whiteness of 78.4 and is thin. The skin color was exhibited.
[0033]
Example 2:
10 kg of aluminum biphosphate aqueous solution (aqueous solution containing 50% phosphorus pentoxide, manufactured by Nippon Chemical Industry Co., Ltd.) is added to 100 kg of shirasu raw material (shirasu average particle size 35.0 μm) from Yoshida-cho, Satsuma-gun, Kagoshima Prefecture. The mixture was mixed and stirred with a stirrer so as to spread throughout. Next, the mixed and stirred raw material was dried at 650 ° C. in a rotary kiln, and the raw material powder was baked and foamed at 960 ° C. using a medium fluidized bed furnace. The whiteness was 83.5, the tapping bulk specific gravity was 0.17, the average A high whiteness shirasu balloon with a particle size of 51.2 μm could be produced.
[0034]
Reference test example 1:
Phosphoric acid aqueous solution (H) to 100 kg of shirasu raw material from Yoshida-cho, Satsuma-gun, KagoshimaThreePOFour10 kg of a 98% aqueous solution (manufactured by Kanto Chemical Co., Inc.) is added and mixed and stirred with a stirrer so as to spread over the entire screen. Next, the mixed and stirred raw material is dried in a rotary kiln at 650 ° C., and the raw material powder is fired and foamed at 960 ° C. using a medium fluidized bed furnace, and has a whiteness of 81.5, a tapping bulk specific gravity of 0.13, A high whiteness shirasu balloon with an average particle size of 51.5 μm was produced.
[0035]
Example 3:
For 100 kg of pumice raw material (average particle size 0.2 to 3 mm) from Tarumi, Kagoshima Prefecture, aluminum phosphate aqueous solution (“Acidophos 75”, trade name: 50% phosphorus pentoxide manufactured by Taki Chemical Co., Ltd., 10 kg of an aluminum phosphate aqueous solution consisting of 9% aluminum oxide and the remaining water was added and mixed and stirred with a stirrer so as to spread over the entire screen.
Next, the mixed and stirred raw material is dried in a rotary kiln at 650 ° C., and the raw material powder is fired and foamed at 960 ° C. using a medium fluidized bed furnace, and has a whiteness of 81.1, a tapping bulk specific gravity of 0.35, A shirasu balloon having an average particle size of 50.9 μm and a whiteness equal to or higher than that of a conventional shirasu balloon could be manufactured.
[0036]
Reference test example 2:
After covering the shirasu raw material powder with aluminum phosphate and covering it with 100 parts by weight of high whiteness volcanic ejecta foam (obtained in Example 2) obtained by firing and foaming in a medium fluidized bed furnace 100 parts by weight of potassium silicate aqueous solution ("A potassium silicate" trade name: potassium silicate aqueous solution containing 25.5 to 27.5% silicon dioxide and 12.5 to 14.5% potassium oxide manufactured by Nippon Chemical Industry Co., Ltd.) And kneaded in a closed kneader. Next, the kneaded product was put into a square mold and press-molded.
After that, a resin film is pasted on the surface of the molded body taken out from the mold, and a thin long bar (cone) is inserted to the deep part from there, and a number of excavation holes are formed at a few other intervals at narrow intervals (100 to 150 mm intervals). Drill. Next, a thin tube is inserted into the borehole, and carbon dioxide gas is introduced into the thin tube at a pressure of 2 to 5 kgf / cm.2Pump for 10 to 80 seconds.
Thereby, potassium silicate and a carbon dioxide gas are made to react, a silicate gel and potassium carbonate are produced | generated, and the intensity | strength of a molded object is increased by the strong binding force of this silicate gel.
In addition, the produced potassium carbonate gradually reacts with the silicic acid content of the volcanic ejecta to form stable solid potassium silicate. It is preferable to insert a kneaded mixture of volcanic eruption foam granules and a binder (for example, an inorganic binder such as potassium silicate) into the excavation hole after the carbon dioxide gas injection is finished.
Finally, the molded product after the carbon dioxide injection treatment is removed from the mold, and the resin film on the surface is peeled off, and the aggregate cured product of the volcanic ejecta foam granules with excellent whiteness, light weight, high strength and excellent heat resistance is obtained. did it. Furthermore, if the surface of the aggregate cured product of the resulting volcanic ejecta foam granules is impregnated with aluminum phosphate and heat treated at 450 ° C. to 1000 ° C., the heat resistance is further improved, and the aggregate cured product with increased strength is obtained. I was able to generate.
[0037]
Example 4:
Shirasu Balloon (“SYB-5005” product name: average particle size 90 μm, bulk specific gravity 0.14 to 0.17, manufactured by Howa Naoshi Co., Ltd.) 100 g, primary aluminum phosphate (aluminum biphosphate) 50% aqueous solution (P2OFive: 33.4%, Al2OThree: 8.1%, specific gravity 1.47, viscosity (20 ° C.) 70-80 cp) 150 g is uniformly mixed, put in a mold, 50 kgf / cm2Press molding at a pressing pressure of The molded product removed from the mold is dried at 300 ° C. for 30 minutes, and heat-cured at 900 to 1400 ° C. The obtained fired product exhibited heat resistance (softening temperature) of 1400 ° C. in the air. As a result of X-ray diffraction, an X-ray diffraction pattern of J-2 shown in FIG. 7 was obtained.
[0038]
Reference test example 3:
Shirasu Balloon (“SSB-4000SS” product name: average particle size 75 μm, bulk specific gravity 0.18 to 0.21, manufactured by Nao Toyowa Co., Ltd.) 300 g, alumina cement (“Denka Alumina Cement Super 90” product name: Al2OThree: 90%, CaO: 10%, refractory temperature 1880 ° C, manufactured by Denki Kagaku Kogyo Co., Ltd.) 120 g are uniformly stirred and mixed, and 50% aqueous solution of primary aluminum phosphate (heavy aluminum phosphate) (P2OFive: 33.4%, Al2OThree: 8.1%, specific gravity 1.47, viscosity (20 ° C.) 70-80 cp) 420 g is added and mixed, and stirred uniformly. A well-stirred material is placed in a mold and 50 kgf / cm2Press molding at a pressing pressure of The molded product removed from the mold is dried at 300 ° C. for 30 minutes, and heat-cured at 900 to 1400 ° C. The obtained fired product exhibited heat resistance (softening temperature) of 1400 ° C. in the air. As a result of X-ray diffraction, an X-ray diffraction diagram of K shown in FIG. 8 was obtained.
[0039]
Reference test example 4:
Shirasu Balloon ("SYB-5000" trade name: average particle size 70 μm, bulk specific gravity 0.17 to 0.21, manufactured by Howa Naoshi Co., Ltd.) 200 g, calcium carbonate (coral powder manufactured by Coral Stone Co., Ltd.) 200 g, 50% aqueous solution of primary aluminum phosphate (aluminum biphosphate) (P2OFive: 33.4%, Al2OThree: 8.1%, specific gravity 1.47, viscosity (20 ° C.) 70-80 cp) 400 g is added and mixed, put into a mold, 50 kgf / cm2Press molding at a pressing pressure of
Further, the fired product obtained by drying the molded product at 300 ° C. for 30 minutes and heat-curing at 900 to 1400 ° C. exhibited heat resistance (softening temperature) of 1400 ° C. in the atmosphere. As a result of X-ray diffraction, an X-ray diffraction diagram of L shown in FIG. 9 was obtained. That is, cristobalite type aluminum phosphate AlPOFourCrystal and tridymite type aluminum phosphate AlPOFourCrystal and calcium phosphate Ca2P2O7Three crystal structures of crystals were confirmed. The heat resistance (softening temperature) of the fired product was 1400 ° C.
[0040]
Reference test example 5:
To 200 g of Shirasu Balloon (“SSB-4000SS” trade name: average particle size 75 μm, bulk specific gravity 0.18 to 0.21, manufactured by Nao Toyowa Co., Ltd.), lithium silicate solution (SiO 22: 20%, Li2O: 20%, manufactured by Nippon Kagaku Kogyo Co., Ltd.) 200 g is added and mixed, put in a mold, and 50 kgf / cm2The material is pressure-molded with a press pressure of, and then cured by injecting carbon dioxide. Remove from the mold and dry at 300 ° C. for 30 minutes.2OFive: 53.5 to 55%, Al2OThree: 1.0%, specific gravity 1.6, viscosity (20 ° C.) 40 cp, pH 0.5 or less) for 2 to 5 seconds to impregnate the same weight as the molded product.
This molded product was dried at 300 ° C. for 30 minutes, and a fired product obtained by heat curing at 900 to 1200 ° C. exhibited heat resistance (softening temperature) of 1200 ° C. in the atmosphere. As a result of X-ray diffraction, an X-ray diffraction pattern of M shown in FIG. 10 was obtained. That is, cristobalite type aluminum phosphate AlPOFourCrystal and tridymite type aluminum phosphate AlPOFourTwo crystal structures of the crystal were confirmed.
[0041]
【The invention's effect】
As described above, according to the present invention, an excellent whiteness and heat-resistant volcanic erupted product fired foam particles and an aggregate cured product of the foam particles are provided at low cost. The volcanic ejecta fired foam particles (such as shirasu balloon) and the volcanic ejecta foam granule aggregate cured product having such properties are environmentally friendly and have high added-value inorganic materials.
As a paper clay manufacturer who is the main user of Shirasu Balloon, there is a desire to use natural inorganic materials avoiding artificial organic materials as much as possible considering the safety of paper clay products and the burden on the environment. The shirasu balloon according to the present invention has high whiteness, can be suitably used for the paper clay product, and is excellent in heat resistance, so that it can be applied to new demands such as heat resistant paints, heat insulating materials and heat resistant tiles.
[Brief description of the drawings]
FIG. 1 is simply vitreous silica (
[Fig. 2] Simple glassy silica (SiO2)2・ NH2O) (A), a 1300 ° C heat-treated product (B-2) of an evaporated and dried product of an aluminum phosphate solution, and a 1300 ° C heat-treated product (D) of a mixture of glassy silica and an aluminum phosphate solution. It is each X-ray diffraction diagram.
FIG. 3 contains glassy volcanic ejecta shirasu (amorphous) (F-1) and a small amount of aluminum phosphate (Al2OThreeAs 1% phosphoric acid solution (P2OFiveAre 55%) evaporative dry products of 1200 ° C heat-treated product (B-1) and 1300 ° C heat-treated product (E) of a mixture of Shirasu and this phosphoric acid solution.
FIG. 4 is a glassy volcanic eruption shirasu (amorphous) (F-1), an aluminum phosphate evaporative dried product at 1300 ° C. (B-2), shirasu and aluminum phosphate. It is each X-ray-diffraction figure of the 1300 degreeC heat processing goods (G) of the mixture of.
FIG. 5 is a 1200 ° C. heat-treated product (B-1) of Shirasu balloon (foamed particles of glassy volcanic ejecta) (F-2) and an evaporated dry product of a phosphoric acid solution containing a small amount of aluminum phosphate. ) And a 1400 ° C. heat-treated product (H) of a mixture of Shirasu balloon and a phosphoric acid solution containing a small amount of aluminum phosphate.
FIG. 6: Shirasu balloon (foamed particles of glassy volcanic ejecta) (F-2), 1300 ° C. heat-treated product of evaporated and dried aluminum phosphate solution (B-2), Shirasu balloon and phosphorus It is each X-ray-diffraction figure of the 1500 degreeC heat processing goods (J-1) of a mixture with an acid aluminum solution.
FIG. 7 is an X-ray diffraction pattern of a 1400 ° C. heat-treated product (J-2) of a mixture of a shirasu balloon and an aluminum phosphate solution.
FIG. 8 is an X-ray diffraction pattern of a 1300 ° C. heat-treated product (K) of a mixture of shirasu balloon, alumina cement and aluminum phosphate solution.
FIG. 9 is an X-ray diffraction pattern of a 1400 ° C. heat-treated product (L) of a mixture of shirasu balloon, calcium carbonate and aluminum phosphate solution.
FIG. 10 is a baked product obtained by impregnating a cured product obtained by injecting carbonic acid gas into a mixture of a shirasu balloon and a lithium silicate solution and then impregnating the cured product with an aluminum phosphate solution, followed by drying at 1200 ° C. It is an X-ray diffraction diagram of M).
Claims (21)
ガラス質火山噴出物発泡粒体１００重量部に、リン酸アルミニウム及びリン酸の混合物水溶液をＰ2Ｏ5換算で３〜１１０重量部、Ａｌ 2 Ｏ 3 換算で０．０１〜４０重量部を添加混練してまぶし付け、乾燥処理した後、炉内で８００〜１５００℃で焼成して、組織中にクリストバライト型リン酸アルミニウム結晶が混在してなり、軟化温度が１１００℃〜１５００℃の発泡粒体を得ることを特徴とする白色度及び耐熱性に優れた火山噴出物発泡粒体の製造方法。 Mainly composed of silica and alumina having an average particle diameter of 6 μm to 5 mm
Added to vitreous volcanic materials foamed granules 100 parts by weight, 3-110 parts by weight of aqueous mixture of phosphoric acid and aluminum phosphate in terms of P 2 O 5, a 0.01 to 40 parts by weight in terms of Al 2 O 3 After kneading, spraying, and drying treatment, it is fired at 800-1500 ° C. in a furnace , cristobalite type aluminum phosphate crystals are mixed in the structure, and the softening temperature is 1100 ° C.-1500 ° C. A method for producing foamed foam of volcanic ejecta excellent in whiteness and heat resistance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000376697A JP3635289B2 (en) | 1999-11-04 | 2000-11-06 | Volcanic ejecta foam particles having excellent whiteness and heat resistance, aggregated cured products of the same, and methods for producing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11-314303 | 1999-11-04 | ||
| JP31430399 | 1999-11-04 | ||
| JP2000376697A JP3635289B2 (en) | 1999-11-04 | 2000-11-06 | Volcanic ejecta foam particles having excellent whiteness and heat resistance, aggregated cured products of the same, and methods for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001192281A JP2001192281A (en) | 2001-07-17 |
| JP3635289B2 true JP3635289B2 (en) | 2005-04-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000376697A Expired - Fee Related JP3635289B2 (en) | 1999-11-04 | 2000-11-06 | Volcanic ejecta foam particles having excellent whiteness and heat resistance, aggregated cured products of the same, and methods for producing the same |
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| Country | Link |
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| JP (1) | JP3635289B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013209253A (en) * | 2012-03-30 | 2013-10-10 | Daiken Corp | Inorganic foam and method for producing the same |
| RU2513799C1 (en) * | 2013-01-15 | 2014-04-20 | Юлия Алексеевна Щепочкина | Mixture for making porous aggregate |
| RU2627510C1 (en) * | 2016-07-11 | 2017-08-08 | Юлия Алексеевна Щепочкина | Burden for producing aggregate |
| CN109020597A (en) * | 2018-07-02 | 2018-12-18 | 刘思汉 | A kind of preparation method of a fuel-saving type pelelith beading |
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| Publication number | Publication date |
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| JP2001192281A (en) | 2001-07-17 |
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