JPS63107852A - Sea water-resistant cement material and manufacture of sea water-resistant mortar or concrete - Google Patents
Sea water-resistant cement material and manufacture of sea water-resistant mortar or concreteInfo
- Publication number
- JPS63107852A JPS63107852A JP61253225A JP25322586A JPS63107852A JP S63107852 A JPS63107852 A JP S63107852A JP 61253225 A JP61253225 A JP 61253225A JP 25322586 A JP25322586 A JP 25322586A JP S63107852 A JPS63107852 A JP S63107852A
- Authority
- JP
- Japan
- Prior art keywords
- cement
- seawater
- concrete
- resistant
- parts
- 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.)
- Granted
Links
- 239000004568 cement Substances 0.000 title claims description 59
- 239000013535 sea water Substances 0.000 title claims description 51
- 239000000463 material Substances 0.000 title claims description 33
- 239000004570 mortar (masonry) Substances 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 23
- 230000002378 acidificating effect Effects 0.000 claims description 22
- 239000000378 calcium silicate Substances 0.000 claims description 17
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 17
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 17
- 239000011398 Portland cement Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims 4
- 235000012239 silicon dioxide Nutrition 0.000 claims 4
- 239000000047 product Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000920 calcium hydroxide Substances 0.000 description 8
- 235000011116 calcium hydroxide Nutrition 0.000 description 8
- 239000011575 calcium Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000001506 calcium phosphate Substances 0.000 description 4
- 229910000389 calcium phosphate Inorganic materials 0.000 description 4
- 235000011010 calcium phosphates Nutrition 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000003628 erosive effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000012360 testing method Methods 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
- 230000009471 action Effects 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- -1 S04 ions Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000004901 spalling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011882 ultra-fine particle Substances 0.000 description 2
- IBZGBXXTIGCACK-UHFFFAOYSA-N 6,7,9,11-tetrahydroxy-9-(2-hydroxyacetyl)-4-methoxy-8,10-dihydro-7h-tetracene-5,12-dione Chemical compound C1C(O)(C(=O)CO)CC(O)C2=C1C(O)=C1C(=O)C(C=CC=C3OC)=C3C(=O)C1=C2O IBZGBXXTIGCACK-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910000091 aluminium hydride Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- RPUZVWKKWXPKIP-UHFFFAOYSA-H dialuminum;hydrogen phosphate Chemical compound [Al+3].[Al+3].OP([O-])([O-])=O.OP([O-])([O-])=O.OP([O-])([O-])=O RPUZVWKKWXPKIP-UHFFFAOYSA-H 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229910001653 ettringite Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000011396 hydraulic cement Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry 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
- 239000007787 solid Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、耐海水性セメント材、特に海水の侵食に対し
て抵抗性の大きいセメント材及び耐海水性モルタル又は
コンクリ−１−の製造方法に関する。Detailed Description of the Invention (Industrial Application Field) The present invention relates to a seawater-resistant cement material, particularly a cement material with high resistance to seawater erosion, and a method for producing seawater-resistant mortar or concrete. Regarding.
（従来の技術）
従来、海水によるコンクリート構造物の侵食被害が各地
で発生しており、海水のコンクリート内浸入は内部鉄筋
をも腐食、損傷し、コンクリート構造物の崩壊を招来す
る結果となる。(Prior Art) Conventionally, concrete structures have been damaged by seawater erosion in various places, and seawater intrusion into concrete corrodes and damages internal reinforcing bars, resulting in the collapse of concrete structures.
各種セメントを用いた硬化物コンクリートを海水に浸漬
した場合、時間経過にともなって侵食が進行し、１０年
間浸漬試験では第２図に図示のごとく侵食による残存強
度比率がかなり低下する。When hardened concrete made with various types of cement is immersed in seawater, erosion progresses over time, and in a 10-year immersion test, the residual strength ratio due to erosion decreases considerably as shown in Figure 2.
このため、海水がコンクリート内へ入ることのないよう
な手段が種々試みられており、例えば、セメントに耐食
性の優れたゴムラテックスや合成樹脂エマルジョンを添
加する方法、硬化コンクリートに珪フッ化水素酸、珪フ
ッ化亜鉛等を塗布、浸透させるか、高分子プレポリマー
を含浸させたｆ＆ｆｆ１合させる方法、あるいは硬化コ
ンクリートに無機質材料、例えば珪酸ソーダ混合物で被
覆する方法などがある。For this reason, various methods have been tried to prevent seawater from entering concrete, such as adding rubber latex or synthetic resin emulsion with excellent corrosion resistance to cement, adding hydrofluorosilicic acid to hardened concrete, etc. There are methods such as coating and infiltrating zinc silicofluoride, combining f&ff1 impregnated with a polymeric prepolymer, or coating hardened concrete with an inorganic material such as a sodium silicate mixture.
（発明が解決しようとする問題点）
しかしながら、前記従来の耐海水処理方法では特殊な高
分子剤を必要としたり、手数のかがる工程を要し、コス
ト的にも不利なものであった。(Problems to be Solved by the Invention) However, the conventional seawater resistance treatment method described above requires a special polymer agent, requires a time-consuming process, and is disadvantageous in terms of cost.
ところで、ポルトランドセメントは珪酸カルシウム系組
成物で最も一般的なセメントであるが、ポルトランドセ
メントは水和、硬化の際に多量にＣａ（ＯＨ）２を生成
し、これが海水成分と反応すると、セメント水和硬化物
の組織劣化を招く結果、海水が浸透し、耐海水性が劣る
こととなる。By the way, Portland cement is the most common cement with a calcium silicate composition, but when it hydrates and hardens, it produces a large amount of Ca(OH)2, and when this reacts with seawater components, cement water As a result of structural deterioration of the Japanese cured product, seawater penetrates and the seawater resistance becomes poor.
このポルトランドセメントに微粉末（超微粒）のＳｉＯ
□を添加、混合した、例えば化学組成 ＳｉＯ，：４４
．１％、Ａ １．０ 、：８．８％、Ｆ ｅ２ｏ ＝＋
３．０％、Ｃａ。Fine powder (ultra-fine particles) of SiO is added to this Portland cement.
Added and mixed □, for example, chemical composition SiO,: 44
．． 1%, A 1.0 , :8.8%, Fe2o =+
3.0%, Ca.
：３８．６％、ＭｇＯ：１．４％、Ｎ ａｇｏ ：Ｏ，
’１％、Ｋ ２ｏ ：０．７％、灼熱減ｆｉ ：１．９
％で、比１ｉ２．６８からなるセメント材が市販されて
いる。:38.6%, MgO:1.4%, Nago:O,
'1%, K2o: 0.7%, scorching reduction fi: 1.9
%, a cement material consisting of a ratio 1i2.68 is commercially available.
該セメント材は下記反応式によりＣａ（ＯＨ）２を５ｉ
Ｏｚで捕捉、安定化するものであるため、該セメント材
を使用することは好適であると考えられる。The cement material contains 5i of Ca(OH)2 according to the following reaction formula.
Since it is captured and stabilized by Oz, it is considered suitable to use this cement material.
Ｃａ（ＯＨ）ｚ＋５ｉ０２→Ｃｘ５ｙＨｚ（ただし、Ｃ
：ＣａＯ，Ｓ：ＳｉＯ，、Ｈ：ＴｌｚＯ）しかしながら
、本発明者は実験の結果このようにしたものであっても
、なお若干景のポルトランダイト：Ｃａ（ＯＨ）２が残
存し、第１図にグラフ（ｂ）として図示のごとく海水（
熱海水）に対しては８週間の浸漬試験の結果、耐海水性
が満足し得るものでないことを知見した。Ca(OH)z+5i02→Cx5yHz (however, C
:CaO, S:SiO, H:TlzO) However, as a result of experiments, the present inventor found that even with this method, some portlandite:Ca(OH)2 still remains, and the first As shown in graph (b), seawater (
As a result of an 8-week immersion test (hot sea water), it was found that the seawater resistance was not satisfactory.
（問題点を解決するための手段）
本発明者は以上に鑑み研究の結果、セメント中に生成、
！！離する水酸化カルシウムを強固に捕捉することによ
って珪酸カルシウム系セメントの耐海水性を格段に向上
し得る耐海水性セメント材を提供することに成功した。(Means for solving the problem) In view of the above, the present inventor has conducted research and found that
! ! We have succeeded in providing a seawater-resistant cement material that can significantly improve the seawater resistance of calcium silicate cement by firmly capturing the calcium hydroxide that is released.
すなわち本発明は、珪酸カルシウム系セメントに酸性リ
ン酸アルミニウムを添加、混合してなることを特徴とす
る耐海水性セメント材、及び珪酸カルシウム系セメント
に酸性リン酸アルミニウムを添加、混合することを特徴
とする耐海水性モルタル又はコンクリートの製造方法で
ある。That is, the present invention provides a seawater-resistant cement material characterized by adding and mixing acidic aluminum phosphate to calcium silicate cement, and a seawater-resistant cement material characterized by adding and mixing acidic aluminum phosphate to calcium silicate cement. This is a method for producing seawater-resistant mortar or concrete.
珪酸カルシウム系セメントであるポルトランドセメント
は常用のセメントであって価格も低く入手しやすいもの
であるが、前述のごとく珪酸カルシウムはモルタル又は
コンクリートを製造する際の水和時において、下記のよ
うな反応で多量のＣａ（ＯＨ）、を生成する。Portland cement, which is a calcium silicate-based cement, is a commonly used cement that is inexpensive and easy to obtain. However, as mentioned above, calcium silicate undergoes the following reactions during hydration when manufacturing mortar or concrete. produces a large amount of Ca(OH).
２ＣｓＳ＋６ＨｚＯ−’Ｃ＝ＦｚＨ＊＋３Ｃａ（ＯＨ）
ｚ２Ｃ２Ｓ＋４ＨｚＯ−ＣｚＳ２Ｈｔ＋Ｃａ（ＯＨ）ｚ
そして上記のように生成したポルトランダイトは、海水
中のＭ、イオンとＳ０４イオンと反応して石膏（ＣａＳ
Ｏ＜）を生成し、さらにこれがコンクリート中のＣ、ｌ
Ａ （ただしＡ ＝ Ａ ＋ｚｏ ３）と反応して、エ
トリンガイト（Ｃ３Ａ ・３ＣａＳＯ４・３Ｈ２０）を
生成し膨張する結果、モルタル、コンクリートを破壊す
るに至ることとなる。2CsS+6HzO-'C=FzH*+3Ca(OH)
z2C2S+4HzO-CzS2Ht+Ca(OH)z
The portlandite produced as described above reacts with M, ions, and S04 ions in seawater, resulting in gypsum (CaS).
O<), which in turn generates C, l in concrete.
It reacts with A (where A = A + zo 3) to produce ettringite (C3A.3CaSO4.3H20) and expands, resulting in the destruction of mortar and concrete.
ところで、超微粉のＳｉＯ□を多量添加した珪酸カルシ
ウム系セメントでは
Ｃａ（ＯＨ）ｚ＋５ｉｏｚ→Ｃｘ５ｙＨｚの反応によっ
て、ポルトランダイトの一部が安定な化合物として捕捉
されるため、ＣａＯによる害毒の生成がかなりな程度阻
止される。By the way, in calcium silicate cement containing a large amount of ultrafine SiO□, a part of portlandite is captured as a stable compound through the Ca(OH)z+5ioz→Cx5yHz reaction, so the generation of harmful substances caused by CaO is considerably reduced. be prevented to a certain degree.
なお、該超微粉Ｓ ｉ Ｏ宜添加旦は、珪酸カルシウム
系セメント１００重量部に対し、３０〜１２０重景部が
好重量ある。The preferred weight of the ultrafine powder SiO added is 30 to 120 parts by weight per 100 parts by weight of calcium silicate cement.
しかしながら、このようにしてもその組織は海水に対す
る充分な抵抗性を具備しない。However, even in this way, the tissue does not have sufficient resistance to seawater.
本発明者は、この点を改善すべく検討を重ねた末、珪酸
カルシウム系セメントに酸性リン酸アルミニウムを添加
、混合したところ、殊に前記超微粉Ｓ ｉ Ｏｚ添加珪
酸カルシウムｌＯＯ重量部に対し、酸性リン酸アルミニ
ウム粉末０．１〜５重量部を添加して水硬性セメント材
を調製したところ、水和硬化物は、耐海水性に優れた安
定な製品となることを見出だした。After repeated studies to improve this point, the inventor of the present invention added and mixed acidic aluminum phosphate to calcium silicate cement, and found that, especially for 10 parts by weight of calcium silicate added with ultrafine powder SiOz, When a hydraulic cement material was prepared by adding 0.1 to 5 parts by weight of acidic aluminum phosphate powder, it was found that the hydrated and cured product became a stable product with excellent seawater resistance.
ここで、本発明に使用する酸性リン酸アルミニウムはア
ルミニウムとリンを原子比（グラム−アトムの比をいう
）として、ＡＩ／Ｐ １／３〜２／３の割合で含有す
るものが好ましい。Here, the acidic aluminum phosphate used in the present invention preferably contains aluminum and phosphorus in an atomic ratio (gram-atom ratio) of AI/P 1/3 to 2/3.
酸性リン酸アルミニウムの製造方法は種々提案されてい
るが、工業的には水酸化アルミニウムとリン酸を所定の
Ａｌ／Ｐ比になるように混合し、加熱脱水して得る高粘
度の液体を熱風中にスプレーして乾燥する方法が一般に
採用されている。Various methods for producing acidic aluminum phosphate have been proposed, but industrially, aluminum hydroxide and phosphoric acid are mixed to a predetermined Al/P ratio, and a high viscosity liquid obtained by heating and dehydration is heated and heated. A method of spraying and drying is generally adopted.
本発明に使用する酸性リン酸アルミニウムは、アルミニ
ウムとリンを原子比としてＡＩ／Ｐ１／３〜２／３の割
合で含有するものであれば、その製造方法に限定される
ことなく有効に使用することができる。上記に示すよう
なリン酸と水酸化アルミニウムとの反応物をスプレー乾
燥して得る酸性リン酸アルミニウムは一般に非常に吸湿
性が大きいのでセメントに混合して保存する場合は、ビ
ニール内袋のクラフト包装袋やファイバー又はプラスチ
ックドラム等の通気性の無い包装材料を使用する必要が
ある。The acidic aluminum phosphate used in the present invention can be effectively used without being limited to its manufacturing method as long as it contains aluminum and phosphorus in an atomic ratio of AI/P 1/3 to 2/3. be able to. Acidic aluminum phosphate, which is obtained by spray-drying the reaction product of phosphoric acid and aluminum hydroxide as shown above, is generally very hygroscopic, so if it is to be mixed with cement and stored, it should be packed in a kraft plastic inner bag. Non-breathable packaging materials such as bags, fiber or plastic drums should be used.
例えば特開昭５０−１０４７９９号公報に提案されてい
るセスキリン酸アルミニウム（ＡｌＨ３（ＰＯ，）・３
ＨｔＯ）は吸湿性が小さく、セメントとの混合物も通常
のセメントの包装形態で長ＪＩＩＩ間保存できるので実
用的により好ましい酸性リン酸アルミニウムである。For example, aluminum sesquiphosphate (AlH3(PO,).3
HtO) has low hygroscopicity and can be stored in a mixture with cement for a long period of time in a normal cement packaging form, so it is a more preferred acidic aluminum phosphate for practical purposes.
液体状の酸性リン酸アルミニウムは耐火物バインダーと
して広く一般に使用されており入手しやすいものであり
、この液体状酸性リン酸アルミニウムを使用する場合は
、セメントと水を混合する際、セメントと水と同時に、
又はあらかじめ水に所定量の酸性リン酸アルミニウムを
溶解せしめた後又はセメントと水との混和後所定皿の酸
性リン酸アルミニウムを加えて、混練すれば良い。Liquid acidic aluminum phosphate is widely used as a refractory binder and is easily available. When using this liquid acidic aluminum phosphate, when mixing cement and water, at the same time,
Alternatively, a predetermined amount of acidic aluminum phosphate may be dissolved in water in advance, or after mixing cement and water, a predetermined tray of acidic aluminum phosphate may be added and kneaded.
当然のことであるが、粉末状又は固体状の酸性リン酸ア
ルミニウムも同様にモルタル、コンクリート製造時に添
加することができる。Naturally, powdered or solid acidic aluminum phosphate can also be added during the production of mortar and concrete.
これは以下の反応の進行と、生成する難水溶性のリン酸
カルシウムの働きによるものと推測される。This is presumed to be due to the progress of the following reaction and the action of poorly water-soluble calcium phosphate produced.
９−３×
Ａ ｌｘＨｔ−ａｘ（ＰＯ４）３＋ Ｃａ
（ＯＨ）ｚ３−×
一部 ｘＡ Ｉ Ｐ Ｏ４＋−Ｃａｓ（Ｐ Ｏ４）２＋
９ ３ｘＨｔＯ
本発明によれば、添加酸性リン酸アルミニウムにより、
残存Ｃａ（ＯＨＬが完全に安定的に捕捉され、海水に対
して化学的に安定なＣａ３（Ｐ Ｏ４ｈを生成するため
、本発明セメント材は結果として耐海水性の優れたもの
となるのである。9-3× A lxHt-ax(PO4)3+ Ca
(OH)z3-× Part xA I P O4+-Cas(P O4)2+
9 3xHtO According to the present invention, by adding acidic aluminum phosphate,
The cement material of the present invention has excellent seawater resistance as residual Ca (OHL) is completely and stably captured and Ca3 (PO4h) which is chemically stable against seawater is produced.
本発明において使用されるセメントとしては、素材入手
の容易性から常用のポルトランドセメントに微粉末５ｉ
Ｏｚを多量添加したものが好ましい。The cement used in the present invention is commonly used Portland cement and finely powdered 5i powder due to the ease of material availability.
Preferably, a large amount of Oz is added.
酸性リン酸アルミニウムの添加量は、セメント１００！
ｒｔｉ部に対して０．１〜５重量部が好ましい、０．１
ｆｆｉ量部より少ない添加量では効果が充分に認められ
ないし、５重量部より多い添加量では水和時のセメント
スラリーの粘度が大きく、一般に行なわれている施工法
において作業性が悪化し実用的でない。The amount of acidic aluminum phosphate added is 100% of cement!
Preferably 0.1 to 5 parts by weight based on part rti, 0.1
If the amount added is less than ffi parts, the effect will not be sufficiently recognized, and if the amount added is more than 5 parts by weight, the viscosity of the cement slurry during hydration will be high, and the workability will deteriorate in commonly used construction methods, making it impractical. Not.
また本発明の耐海水性セメント材に、常法により水、混
和材等を加えてモルタル又はコンクリートとする場合、
上記のごとく化学反応により生成するリン酸カルシウム
は微細な結晶粒子であり、その微細結晶粒子がモルタル
、コンクリート組織空孔内に充填され、密封するように
なる結果、モルタル、コンクリートは空孔率が少く、海
水浸透性のない耐海水性に優れたものとなる。Furthermore, when making mortar or concrete by adding water, admixtures, etc. to the seawater-resistant cement material of the present invention by a conventional method,
Calcium phosphate produced by the chemical reaction described above is fine crystal particles, and as a result, the fine crystal particles fill and seal the pores in the mortar and concrete structure, resulting in mortar and concrete with low porosity. It has excellent seawater resistance with no seawater permeability.
そして、前記のごとく空孔率が少く、海水浸透性のない
モルタル、コンクリートが得られる本発明の耐海水性セ
メント材を使用すれば、低温環境下において浸透水分が
凍結、膨張してモルタル、コンクリート組織を破壊する
ことがなく、よって耐スポーリング性が従来のセメント
材と比較して比常に優れたものとなる。As mentioned above, if the seawater-resistant cement material of the present invention is used, which produces mortar and concrete with low porosity and no seawater permeability, the permeated water will freeze and expand in a low-temperature environment, resulting in mortar and concrete. It does not destroy the structure, and therefore has significantly better spalling resistance than conventional cement materials.
（実施例）
珪酸カルシウム系セメント（添加超微粒Ｓ ｉ ０２４
０〜５０１ｉＪＬ％含有のポルトランドセメント）１０
０！ｉ量部に対し、酸性リン酸アルミニウム０．５重量
部、細砂４０重量部、水５０重量部を加えて混合後、養
成硬１ヒさせて、セメント硬化物を得た。(Example) Calcium silicate cement (added ultrafine particles S i 024
Portland cement containing 0-501iJL%) 10
0! After mixing, 0.5 parts by weight of acidic aluminum phosphate, 40 parts by weight of fine sand, and 50 parts by weight of water were added to i parts by weight, and the mixture was allowed to harden for 1 hour to obtain a hardened cement product.
このセメント硬化物について、海水（熱海水）に対して
８週間の浸漬試験を行ったところ、第１図に示したよう
に、本発明セメント材のセメント硬化物（ａ）は、従来
のセメント硬化物（ｃ）、（ｄ）等に比べてその長さ変
化が小さく、耐海水性に優れていることが判る。また、
残存強度比率（％）についても、第２図に示すごとく、
本発明実施例のものは第２図の（ａ）として記したグラ
フ（破線部は推定部曲線）を示すものとなり、長期に渡
って高強度が保持されることが判る。When this hardened cement material was subjected to an 8-week immersion test in seawater (hot sea water), as shown in Figure 1, the hardened cement material (a) of the cement material of the present invention was different from the conventional cement hardened material. It can be seen that the change in length is smaller than that of materials (c) and (d), and that the material has excellent seawater resistance. Also,
Regarding the residual strength ratio (%), as shown in Figure 2,
The example of the present invention shows the graph shown in FIG. 2 (a) (the broken line is the estimated curve), and it can be seen that high strength is maintained over a long period of time.
（発明の効果）
以上に述べたごとく、本発明のセメント材は、セメント
の水和、硬化時において、添加酸性リン酸アルミニウム
の作用により、残存Ｃａ（ＯＨ）２が完全に安定的に捕
捉されると同時に、海水に対して化学的に安定なＣａ５
（ＰＯ＜）ｚを生成するため、本発明セメント材は結果
として耐海水性の優れたものとなるのである。(Effects of the Invention) As described above, in the cement material of the present invention, residual Ca(OH)2 is completely and stably captured by the action of added acidic aluminum phosphate during hydration and hardening of cement. At the same time, Ca5 is chemically stable in seawater.
Since (PO<)z is generated, the cement material of the present invention has excellent seawater resistance as a result.
また本発明の耐海水性セメント材に、常法により水、混
和材等を加えてモルタル又はコンクリートとする場合、
上記のごとく化学反応により生成するリン酸カルシウム
は微細な結晶粒子であり、その微細結晶粒子がモルタル
、コンクリート組織空孔内に均等、緻密に充填される結
果、海水浸透性の非常に少ないものとなる。Furthermore, when making mortar or concrete by adding water, admixtures, etc. to the seawater-resistant cement material of the present invention by a conventional method,
Calcium phosphate produced by the chemical reaction described above is fine crystal particles, and as a result of the fine crystal particles evenly and densely filling the pores of the mortar and concrete structure, seawater permeability is extremely low.
そのため、低温環境下においても浸透水分が凍結、膨張
してモルタル、コンクリート組織を破壊する凍結融解作
用を受けることがなく、よって耐スポーリング性が従来
のセメント材使用の場合と比較して比常に優れたものと
なる。Therefore, even in low-temperature environments, penetrating water does not freeze and expand, causing freeze-thaw effects that destroy the mortar and concrete structure, resulting in significantly improved spalling resistance compared to conventional cement materials. It will be excellent.
また加えて、前記生成のリン酸カルシウムは硬度が高い
ものであるため、モルタル、コンクリ−１・構造物は耐
摩耗性の優れたものとなり、氷、氷と砂等と接触する構
造、特に極地用海洋構造物に有利に使用できる。In addition, since the calcium phosphate produced above has high hardness, mortar, concrete, and structures have excellent abrasion resistance, and are suitable for use in structures that come into contact with ice, ice and sand, etc., especially in polar regions and marine environments. Can be used advantageously for structures.
さらにまた、リン酸アルミニウムは硬化促進剤としての
作用があるため、モルタル、コンクリート未硬化物打設
後の強度発現時間が大幅に短縮される。Furthermore, since aluminum phosphate acts as a hardening accelerator, the time required to develop strength after placing uncured mortar or concrete is significantly shortened.
したがって、本発明の耐海水性セメント材を使用して得
られるコンクリートは、港湾、海岸、海洋に構築されて
海水の作用を受ける、例えば海洋プラットフォーム、護
岸構造、魚礁等の海洋コンクリート構造物のみならず、
陸上にあって波浪や温風の作用を受けるｔＦＩ造物のす
べてに適用しても劣化を受けることが少ない。Therefore, the concrete obtained using the seawater-resistant cement material of the present invention can be used only for marine concrete structures such as marine platforms, seawall structures, and fish reefs that are constructed in ports, coasts, and oceans and are subjected to the action of seawater. figure,
Even when applied to all tFI structures on land that are exposed to the effects of waves and warm winds, they are unlikely to suffer deterioration.
第１図は本発明実施例の耐海水性セメント材を使用して
得られた硬化物と池の従来セメント材を使用して得られ
た硬化物の海水浸漬による膨張率変化を示すグラフ、第
２図は、各種セメントを用いた硬化物の１０年間海水浸
漬試験における残存強度比率の推移を示すグラフである
。
（ａ）二本発明実施例セメント材便用の硬化物（い：微
粉末Ｓ ｉ Ｏｘ添加ポルトランドセメンＩ−２用の硬
化物
（Ｃ）：硫酸塩含有ポルトランドセメント使用の硬化物FIG. 1 is a graph showing the change in expansion coefficient due to seawater immersion of the cured product obtained using the seawater-resistant cement material of the example of the present invention and the cured product obtained using the conventional cement material of the pond. Figure 2 is a graph showing the transition of the residual strength ratio in a 10-year seawater immersion test of cured products using various cements. (a) Two Examples of the Present Invention Hardened product for cement material toilet (I: Hardened product for Portland cement I-2 containing fine powder SiOx (C): Hardened product using sulfate-containing Portland cement
Claims (8)
ウムを添加、混合してなることを特徴とする耐海水性セ
メント材。(1) A seawater-resistant cement material characterized by being made by adding and mixing acidic aluminum phosphate to calcium silicate cement.
トに微粉末二酸化珪素を添加、混合してなることを特徴
とする特許請求の範囲第１項記載の耐海水性セメント材
。(2) The seawater-resistant cement material according to claim 1, wherein the calcium silicate cement is made by adding and mixing finely powdered silicon dioxide to Portland cement.
ウム系セメント１００重量部に対し、０．１〜５重量部
であることを特徴とする特許請求の範囲第１項又は第２
項記載の耐海水性セメント材。(3) Claim 1 or 2, characterized in that the amount of acidic aluminum phosphate added is 0.1 to 5 parts by weight per 100 parts by weight of calcium silicate cement.
Seawater resistant cement material as described in section.
ント１００重量部に対し、３０〜１２０重量部であるこ
とを特徴とする特許請求の範囲第２項又は第３項に記載
の耐海水性セメント材。(4) The seawater-resistant cement according to claim 2 or 3, wherein the amount of finely powdered silicon dioxide added is 30 to 120 parts by weight per 100 parts by weight of Portland cement. Material.
ウムを添加、混合することを特徴とする耐海水性モルタ
ル又はコンクリートの製造方法。(5) A method for producing seawater-resistant mortar or concrete, which comprises adding and mixing acidic aluminum phosphate to calcium silicate cement.
トに微粉末二酸化珪素を添加、混合したものであること
を特徴特許請求の範囲第５項記載の耐海水性モルタル又
はコンクリートの製造方法。(6) The method for producing seawater-resistant mortar or concrete according to claim 5, wherein the calcium silicate cement is a mixture of Portland cement and finely powdered silicon dioxide.
ウム系セメント１００重量部に対し、０．１〜５重量部
であることを特徴とする特許請求の範囲第５項又は第６
項に記載の耐海水性モルタル又はコンクリートの製造方
法。(7) Claim 5 or 6, characterized in that the amount of acidic aluminum phosphate added is 0.1 to 5 parts by weight per 100 parts by weight of calcium silicate cement.
A method for manufacturing seawater-resistant mortar or concrete as described in .
ント１００重量部に対し、４０〜５０重量部であること
を特徴とする特許請求の範囲第６項又は第７項に記載の
耐海水性モルタル又はコンクリートの製造方法。(8) The seawater-resistant mortar according to claim 6 or 7, wherein the amount of finely powdered silicon dioxide added is 40 to 50 parts by weight based on 100 parts by weight of Portland cement. Or a method of manufacturing concrete.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61253225A JPH0825778B2 (en) | 1986-10-24 | 1986-10-24 | Method for producing seawater-resistant cement material and seawater-resistant mortar or concrete |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61253225A JPH0825778B2 (en) | 1986-10-24 | 1986-10-24 | Method for producing seawater-resistant cement material and seawater-resistant mortar or concrete |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63107852A true JPS63107852A (en) | 1988-05-12 |
| JPH0825778B2 JPH0825778B2 (en) | 1996-03-13 |
Family
ID=17248307
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61253225A Expired - Lifetime JPH0825778B2 (en) | 1986-10-24 | 1986-10-24 | Method for producing seawater-resistant cement material and seawater-resistant mortar or concrete |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0825778B2 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4847528A (en) * | 1971-10-20 | 1973-07-06 | ||
| JPS5921558A (en) * | 1982-07-23 | 1984-02-03 | 日本インシュレーション株式会社 | Manufacture of calcium silicate formed body |
-
1986
- 1986-10-24 JP JP61253225A patent/JPH0825778B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4847528A (en) * | 1971-10-20 | 1973-07-06 | ||
| JPS5921558A (en) * | 1982-07-23 | 1984-02-03 | 日本インシュレーション株式会社 | Manufacture of calcium silicate formed body |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0825778B2 (en) | 1996-03-13 |
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