JP5831572B2 - 補修用非水系圧入材 - Google Patents
補修用非水系圧入材 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims description 91
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 75
- 239000011230 binding agent Substances 0.000 claims description 51
- 239000007788 liquid Substances 0.000 claims description 46
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 42
- 239000005011 phenolic resin Substances 0.000 claims description 27
- 150000005846 sugar alcohols Polymers 0.000 claims description 22
- 239000011134 resol-type phenolic resin Substances 0.000 claims description 21
- 229920003987 resole Polymers 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 20
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 4
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 27
- 239000002245 particle Substances 0.000 description 23
- 238000010276 construction Methods 0.000 description 15
- 229920001971 elastomer Polymers 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 229910052742 iron Inorganic materials 0.000 description 13
- 239000011449 brick Substances 0.000 description 11
- 238000005086 pumping Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 7
- 229920003986 novolac Polymers 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 229920001568 phenolic resin Polymers 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000011819 refractory material Substances 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910003465 moissanite Inorganic materials 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- -1 carbide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 210000002808 connective tissue Anatomy 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
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- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- 230000035515 penetration Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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Description
上述の特許文献1ないし4に開示されている圧入材は、いずれもバインダーに水を用いないことから、非水系圧入材と称されている。
また、圧入材による高炉での圧入作業、例えば上述のステーブや冷却板の背面などに圧入材を圧入する場合、圧入箇所の温度が100℃以上となる場合が多い。特許文献5に開示されている水系圧入材を用いて施工箇所の温度が100℃以上になると、多量の水が瞬時に蒸発して、圧入作業の途中で圧入不能な状態にならざるを得なくなり、また、蒸気圧により圧入材が形成した組織が破壊される。更に、圧入材に多量の水が添加されているので圧入後すなわち水分が蒸発した後の組織は気孔率が高く、強度が低くなるなどの問題点があった。
表1に記載する配合割合にて本発明の補修用非水系圧入材を、表2に記載する配合割合にて比較品の圧入材を調製した。
なお、耐火骨材は、粒径1000〜75μmの粒子35質量%と、粒径75μm未満の粒子65質量%の粒度構成とした。また、粒径1000〜75μmの粒子にはアルミナを用い、粒径75μm未満の粒子は、アルミナ25質量%、炭化珪素20質量%、シリカ10質量%、炭素10質量%とした。
圧送性及び水洗浄性の評価は以下のように行った:
まず、表1,表2の配合割合に従ってモルタルミキサーにより混練して本発明品及び比較品の圧入材を得た。
圧送性は、スクイズ式ポンプを圧送機として使用し、内径20mm、長さ5mのゴムホースを圧送機に接続し、得られた圧入材を8kg/分の速度で圧送し、その時に圧送機とゴムホースの接続部(吐出部)の吐出圧力を測定した。吐出圧力は1.5MPa以下であると良好であり、また、より狭い隙間に圧入する場合を考慮すると、吐出圧力は1.0MPa以下がより良好となる。吐出圧力が1.5MPaを超える場合または圧送機、ホース内で材料が詰まった場合は圧送が不可能と判断した;
圧送性を評価した後、ゴムホース内には圧送材が残っていた。それを用いて、水洗浄性を評価した。圧入材の充填されているゴムホースを圧送機から取り外し、水配管に付け替え、水配管から水圧3kgf/cm2の水を1分間流した後、ゴムホース内に残っていた圧入材の質量を測定した。なお、ゴムホース内に残っていた圧入材の質量を測定する前に、洗浄に用いゴムホース内に残存する水をできるだけ除去するため、ゴムホースを傾けて除去した。水洗浄後のゴムホースへ圧入材の付着率を、水洗浄後のゴムホースに残存する圧入材質量/水洗浄前ゴムホース内圧入材質量×100(%)として評価した。水洗浄後のゴムホースへ圧入材の付着率が、5質量%以下(好ましくは3質量%以下)であれば、水洗浄可能な圧入材であると評価できる;
500℃−3時間加熱後の圧縮強さを以下の方法で評価した。混練後の圧入材を40×40×160mmの金枠に流し込み、200℃で24時間加熱して硬化させ、試験片を作成した。次に、得られた試験片を電気炉に入れ、5℃/分で昇温し、500℃にて3時間加熱した。冷却後、圧縮強度を、JIS R 2553 「キャスタブル耐火物の強さ試験方法」に準拠して測定し、500℃−3時間加熱後の圧縮強さとした。500℃−3時間圧縮強さは、圧入後、内張りれんがと鉄皮の動いた時に容易に崩壊しないため、10MPa以上であり、20MPa以上であればより好ましい;
更に、臭気について、ビーカーに100gの圧入材を入れて臭気を嗅ぎ、著しく気になるかどうかを判定した。臭気は、圧入材の特性には特には影響しないが、作業環境上臭気がない方が好ましい。
本発明品6〜10は、水溶性60質量%の水溶性液状レゾール型フェノール樹脂を用い、エチレングリコールの配合量をバインダー量の30質量%に固定し、バインダーの添加量を外掛けで20質量%から120質量%まで変化させたものである。いずれの場合も、水洗浄性は5.0質量%以下で、吐出圧力は1.5MPa以下で、500℃−3時間加熱後の圧縮強度は10MPa以上であり、臭気もなく、良好な結果が得られた。
本発明品11〜13は、水溶性液状レゾール型フェノール樹脂の水溶性範囲を変化させたものである。バインダーの添加量を外掛けで50質量%に固定し、エチレングリコールの配合量をバインダー量の30質量%に固定したものであるが、いずれの場合も、水洗浄性は5.0質量%以下で、吐出圧力は1.5MPa以下で、500℃−3時間加熱後の加熱後の圧縮強度は10MPa以上であった。しかし、本発明例13は、補修用非水系圧入材としての特性には問題がないものの、臭気が認められた。
本発明例14は、水溶性60質量%の水溶性液状レゾール型フェノール樹脂を用い、バインダーの添加量を外掛けで50質量%に固定し、プロパンジオールの配合量をバインダー量の30質量%としたものである。水洗浄性は5.0質量%以下で、吐出圧力は1.5MPa以下で、500℃−3時間加熱後の圧縮強度は10MPa以上であり、臭気もなく、良好な結果を得た。
上述のように、本発明品は、いずれも水洗浄性に優れ、補修用非水系圧入材としての施工特性も優れ、圧縮強度が十分に高く、優れたものであることが解る。
比較品7は、水溶性0質量%の液状レゾール型フェノール樹脂とエチレングリコールを用いたものであるが、エチレングリコールの配合量をバインダー量の30質量%としても、十分な水洗浄性は得られなかった。
比較品8は、水溶性60質量%の水溶性液状レゾール型フェノール樹脂のみを用い、エチレングリコールを含有しないものであるが、この場合も、十分な水洗浄性は得られなかった。
比較品9は、水溶性60質量%の水溶性液状レゾール型フェノール樹脂とエチレングリコールを用い、エチレングリコールの配合量をバインダー量の80質量%とし、バインダーの添加量を外掛けで50質量%としたものであり、水洗浄性は高いが、500℃−3時間加熱後の圧縮強度が低いものであった。
比較例10及び11は、水溶性60質量%の水溶性液状レゾール型フェノール樹脂とエチレングリコールを用い、エチレングリコールの配合量をバインダー量の30質量%とし、それぞれバインダーの添加量を外掛けで5質量%並びに180質量%とした場合である。比較品10では、水洗浄性と、500℃−3時間加熱後の圧縮強度は十分であったが、圧送詰まりが発生した。これは、バインダーの添加量が過少で、十分な流動性が得られなかったものと思われる。一方、比較品11では、水洗浄性と500℃−3時間加熱後の圧縮強度は十分であったが、圧送詰まりが発生した。これは、バインダーの添加量が多すぎて、耐火骨材とバインダーの分離が発生して圧送詰りが発生したものと考えられる。
Claims (3)
- 耐火骨材及びバインダーを含有してなる補修用非水系圧入材において、バインダーが水溶性液状レゾール型フェノール樹脂と、多価アルコールを含有してなり、水溶性液状レゾール型フェノール樹脂の、25℃で液状レゾール型フェノール樹脂100質量%に対して溶解できる水の量(質量%)で表される水溶性が5〜100質量%の範囲内にあり、水溶性液状レゾール型フェノール樹脂及び多価アルコールの合計量を100質量%とした場合に、多価アルコールの配合量が5〜60質量%の範囲内にあることを特徴とする補修用非水系圧入材。
- 多価アルコールは、エチレングリコール、ジエチレングリコール、プロパンジオール、ブタンジオール、ペンタンジオール及びグリセリンからなる群から選択される1種または2種以上である、請求項1記載の補修用非水系圧入材。
- バインダーの添加量が、耐火骨材100質量部に対し、外掛けで15〜120質量%の範囲内である、請求項1または2記載の補修用非水系圧入材。
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