JPH11246257A - Vegetable fiber cement molding and production thereof - Google Patents
Vegetable fiber cement molding and production thereofInfo
- Publication number
- JPH11246257A JPH11246257A JP5552598A JP5552598A JPH11246257A JP H11246257 A JPH11246257 A JP H11246257A JP 5552598 A JP5552598 A JP 5552598A JP 5552598 A JP5552598 A JP 5552598A JP H11246257 A JPH11246257 A JP H11246257A
- Authority
- JP
- Japan
- Prior art keywords
- cement
- nitrate
- plant fiber
- fiber cement
- weight
- 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
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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Preparation Of Clay, And Manufacture Of Mixtures Containing Clay Or Cement (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、主として建築材料
として用いられる植物繊維を補強材として使用する植物
繊維セメント成形体及びその製造方法に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded plant fiber cement using a plant fiber mainly used as a building material as a reinforcing material, and a method for producing the same.
【０００２】[0002]
【従来の技術】植物繊維セメント成形体、例えば植物繊
維セメント板は、通常木材をフレーク、木毛、木繊維等
に加工した木質系繊維または竹繊維と、各種セメント、
水とを混練し、この混練物を成形し、次いで、セメント
を養生、硬化せしめることにより製造されている。木質
系繊維の原料としては各種の針葉樹や広葉樹が広く利用
されているが、近年では木材が不足の傾向にあり、ま
た、地球環境保護の観点からも木材の節約が求められて
いる。一方、木材の代替原料として、針葉樹や広葉樹と
比較して生長速度が早く、また、強靭で弾力性に富む竹
材料が注目されてきている。しかしながら、竹材料中に
は可溶性糖類あるいは可溶性樹脂類等が含まれており、
これらはセメント硬化阻害物質としてよく知られてい
る。従って、竹材料のようにセメント硬化阻害物質含有
量が多いものを植物繊維材料の原料として実用的に使用
するには、セメントの硬化を円滑に進めることができる
ようにしなければならない。2. Description of the Related Art A plant fiber cement molded product, for example, a plant fiber cement board, is usually made of wood fiber or bamboo fiber obtained by processing wood into flakes, wool, wood fiber, etc., and various cements,
It is manufactured by kneading with water, molding the kneaded product, and then curing and hardening the cement. Various conifers and hardwoods are widely used as a raw material for wood-based fibers. However, in recent years, there has been a tendency for a shortage of wood, and there has been a demand for saving wood from the viewpoint of protecting the global environment. On the other hand, as an alternative raw material for wood, bamboo materials, which have a faster growth rate than conifers and hardwoods, and are tough and elastic, have been attracting attention. However, soluble sugars or soluble resins are contained in the bamboo material,
These are well known as cement setting inhibitors. Therefore, in order to use a material having a high cement-hardening-inhibiting substance content such as a bamboo material as a raw material for a plant fiber material, it is necessary to smoothly advance the hardening of the cement.
【０００３】従来、植物繊維材料に含まれている可溶性
糖類及び樹脂類によるセメントの硬化阻害を解消する方
策として、以下に示す方法が提案されている。例えば、
植物繊維材料中に塩化カルシウム、塩化マグネシウム、
塩化アルミニウム等の金属塩を含浸させたり、混合する
ことによってセメントの硬化を促進する方法がある(特
開昭51−26930号公報、特開昭51−151722号公報、特開
昭60−118658号公報)。更に、特公昭55−14827号公報に
は、木質原料を細片化し、セメント及び水を混合して硬
化成型せしめる方法において超速硬セメントを使用し、
これに塩化第二鉄を添加混合して、さらに９０〜１２０
℃の範囲で加熱圧締することによって硬化せしめること
を特徴とする木質セメント成型物の迅速硬化成型法が開
示されている。Conventionally, the following method has been proposed as a measure for eliminating the inhibition of cement hardening caused by soluble sugars and resins contained in plant fiber materials. For example,
Calcium chloride, magnesium chloride, in plant fiber material
There is a method of accelerating the hardening of cement by impregnating or mixing a metal salt such as aluminum chloride (JP-A-51-26930, JP-A-51-151722, JP-A-60-118658). Gazette). Further, Japanese Patent Publication No. 55-14827 discloses that ultra-rapid hardening cement is used in a method in which woody raw materials are shredded, cement and water are mixed and hardened and molded.
To this, ferric chloride was added and mixed, and further 90-120
A rapid hardening molding method of a wood cement molded product characterized by being cured by heating and pressing in the range of ° C is disclosed.
【０００４】しかし、上述のような硬化促進剤を添加す
る方法にあっては、セメントの硬化は加圧、加温条件
下、例えばホットプレス法、締結した状態でのスチーム
養生等を用いて行われているが、例えば竹繊維材料のよ
うにセメント硬化阻害物質含有量が多い植物繊維材料を
使用した系においては、常温条件下ではセメントが硬化
しにくく、仮に硬化しても、得られた成形体の強度は極
めて低い。加えて、硬化促進剤として使用される金属塩
は塩化物系が一般的であり、塩化物系の硬化促進剤を建
材に使用すると、得られた成形体の施工時に留め付け用
ネジ等の金属部位、及び成形体製造時における混練機械
や成形用鉄板等の金属部分を錆びさせる恐れ、あるいは
セメントの硬化阻害物質含有量が多い植物繊維材料を使
用した系においては、セメントの水和が著しく遅延する
ために有効にこれら硬化促進剤が作用しない恐れもあ
る。However, in the method of adding a hardening accelerator as described above, hardening of the cement is carried out under pressure and heating conditions, for example, using a hot press method, steam curing in a fastened state, or the like. However, for example, in a system using a plant fiber material having a high content of cement hardening inhibitor such as a bamboo fiber material, the cement hardly hardens under normal temperature conditions, and even if it hardens, the resulting molding is obtained. Body strength is extremely low. In addition, the metal salt used as a hardening accelerator is generally a chloride-based hardening agent. If a hardening accelerator of a chloride type is used for a building material, a metal such as a screw for fastening may be used when constructing the obtained molded body. There is a risk of rusting metal parts such as kneading machines and molding iron plates during the production of molded bodies, or in systems using plant fiber materials with a high content of hardening inhibitors in cement, the hydration of cement is significantly delayed In some cases, these curing accelerators may not work effectively.
【０００５】また、木毛セメント板用の木毛を予め河川
水、海水、薬品水中に浸漬処理して、木毛中の樹脂分を
取り除いたものを用いる方法(特開昭55−164054号公報)
がある。ここで、木毛セメント板の製造に悪影響を及ぼ
さないまで、木毛原料中の樹脂分を取り除くには、木毛
を予め１〜４５℃の範囲の冷水を主として用い、樹種に
より２〜１０時間水中浸漬する必要があるとしている。
この場合、浸漬処理に長時間が必要となり、生産性の低
下は否めない。また、安定した製品品質を得るためには
浸漬時間を長くとる必要があり、使用する樹種により製
品品質が変動する恐れがある。更に、特公昭61−4784号
公報には、木質セメント板の製造法において、予め木質
を硫酸マグネシウム、硫酸カルシウム、硫酸アルミニウ
ム及び硫酸亜鉛からなる群から選ばれた１種または２種
以上の硫酸根を有する塩、水酸化カルシウムまたは(及
び)炭酸カルシウム及びギ酸、酢酸及び蓚酸からなる群
から選ばれた１種または２種以上のカルボン酸で処理
し、しかる後セメントを混合することを特徴とする木質
セメント板の製造法が開示されている。また、特公昭61
−5422号公報には、強酸のアルミニウム塩と酢酸塩とで
木質材料をセメント硬化阻害防止処理し、このセメント
硬化阻害処理された木質材料を用いて木質セメント板を
製造することを特徴とする木質セメント板の製法が開示
されている。これらの処理においては、浸漬処理水の排
液処理コスト及びランニングコストの高騰を招く。Further, a method is used in which wood wool for a wood wool cement board is preliminarily immersed in river water, sea water, or chemical water to remove the resin content in the wood wool (Japanese Patent Laid-Open No. Sho 55-164054). )
There is. Here, in order to remove the resin component in the wood wool raw material until the wood wool cement board production is not adversely affected, the wood wool is preliminarily used with cold water in the range of 1 to 45 ° C., and depending on the tree species, 2 to 10 hours. They need to be immersed in water.
In this case, a long time is required for the immersion treatment, and a reduction in productivity cannot be denied. Further, in order to obtain stable product quality, it is necessary to increase the immersion time, and the product quality may vary depending on the type of tree used. Furthermore, Japanese Patent Publication No. 61-4784 discloses a method for producing a wood cement board, in which one or more sulfates selected from the group consisting of magnesium sulfate, calcium sulfate, aluminum sulfate and zinc sulfate in advance. Treated with one or two or more carboxylic acids selected from the group consisting of a salt having, calcium hydroxide or (and) calcium carbonate and formic acid, acetic acid and oxalic acid, and then mixing the cement. A method for producing a wood cement board is disclosed. Also, Tokiko Sho 61
Japanese Patent Application Laid-Open No. 5-5422 discloses a method in which a wood material is treated with a hard acid aluminum salt and an acetate salt to prevent cement hardening, and a wood cement board is manufactured using the cement hardening-inhibited wood material. A method of making a cement board is disclosed. In these treatments, the drainage treatment cost and the running cost of the immersion treatment water increase.
【０００６】更に、木質材料中のセメント硬化阻害物質
をパラホルムアルデヒドやホルマリン処理により不溶化
する方法がある(特開昭50−127925号公報)。しかし、該
方法に用いる薬剤は危険であり、薬品排液処理設備、現
場環境設備費等が必要となり、コストが上がる。[0006] Furthermore, there is a method of insolubilizing a cement hardening inhibitor in woody material by treatment with paraformaldehyde or formalin (Japanese Patent Laid-Open No. 50-127925). However, the chemicals used in the method are dangerous and require chemical wastewater treatment equipment, on-site environmental equipment costs, and the like, which increases costs.
【０００７】また、特公平５−65455号公報には、木質
材料、セメント及び水を混練して混合マットを成型した
後、該混合マットを圧締成型し、養生硬化して木質セメ
ント板を製造するに当たり、鉄、銅、亜鉛または鉛の硫
酸化物、塩化物または水酸化物より選ばれる１種または
２種以上の物質よりなる金属化合物を混練水中に混入
し、該金属化合物が木質材料からの抽出成分と結合して
安定度の高い錯体を形成して該抽出成分によるセメント
硬化阻害を防止することを特徴とする木質セメント板の
製造法が開示されている。[0007] Japanese Patent Publication No. 5-65555 discloses that a wood mat, a cement and water are kneaded to form a mixed mat, and then the mixed mat is pressed and cured to cure to produce a wood cement board. In doing so, a metal compound consisting of one or more substances selected from sulfates, chlorides or hydroxides of iron, copper, zinc or lead is mixed into the kneading water, and the metal compound is mixed with wood material. There is disclosed a method for producing a wood cement board characterized by forming a highly stable complex by combining with an extractive component to prevent inhibition of cement hardening due to the extractive component.
【０００８】更に、特開平８−2954号公報には、木質補
強材に水酸化カルシウムとアルカリ金属及び／またはア
ンモニアの重炭酸塩を添加混合し加熱することによっ
て、該木質補強材表面に炭酸カルシウム被覆を施すこと
を特徴とする木質補強材の処理方法が開示されている。Further, Japanese Patent Application Laid-Open No. Hei 8-2954 discloses that calcium hydroxide and a bicarbonate of an alkali metal and / or ammonia are added to a wood reinforcing material, mixed and heated, so that the surface of the wood reinforcing material is made of calcium carbonate. A method for treating a wood reinforcement characterized by applying a coating is disclosed.
【０００９】[0009]
【発明が解決しようとする課題】上記従来の技術は、原
料混合物中に補強材として配合されている植物繊維材料
からセメント硬化阻害物質(可溶性糖類及び樹脂類等)の
溶出量が比較的少ない間にゲル化を開始させ、硬化阻害
物質がセメント中へ拡散するのを防止する方法、若しく
は予め補強用の植物繊維材料を薬品で処理することで、
セメント硬化阻害物質がセメント中へ溶出するのを防止
する方法である。しかしながら、針葉樹や広葉樹のよう
な補強用の木質系繊維材料に比べて可溶性糖類及び樹脂
類を多く含有する竹繊維等を補強用の植物繊維材料とし
て使用する場合においては、セメントが硬化する前に、
可溶性糖類及び樹脂類が溶出する可能性があるため、セ
メントの硬化が阻害される恐れがある。仮に硬化が阻害
された場合に硬化促進剤を添加しても、遅延した水和反
応を通常に戻すことは難しい。また、薬品等でこれら植
物繊維材料表面を完全にコーティングするのは難しく、
また、コーティングが不十分であると前者と同様に硬化
阻害の恐れがあり、安定した高品質の製品を得ることが
困難であった。The above-mentioned prior art is based on a method in which the amount of cement hardening inhibitors (soluble saccharides and resins, etc.) eluted from a plant fiber material blended as a reinforcing material in a raw material mixture is relatively small. Initiate gelation, a method of preventing the hardening inhibitor from diffusing into the cement, or by treating the plant fiber material for reinforcement with a chemical in advance,
This is a method for preventing the cement hardening inhibitor from being eluted into the cement. However, when a bamboo fiber or the like containing a large amount of soluble saccharides and resins is used as a reinforcing plant fiber material as compared with a reinforcing wood fiber material such as softwood or hardwood, before the cement hardens. ,
Since the soluble saccharides and resins may be eluted, the setting of the cement may be inhibited. Even if a curing accelerator is added when curing is inhibited, it is difficult to return the delayed hydration reaction to normal. Also, it is difficult to completely coat the surface of these plant fiber materials with chemicals, etc.
In addition, if the coating is insufficient, there is a risk of curing inhibition as in the former case, and it has been difficult to obtain a stable and high-quality product.
【００１０】従って、本発明の目的は、高強度の植物繊
維セメント成形体及びその製造方法を提供することにあ
る。Accordingly, an object of the present invention is to provide a high-strength plant fiber cement molded article and a method for producing the same.
【００１１】[0011]
【課題を解決するための手段】即ち、本発明は、少なく
とも植物繊維材料及びセメントを含有してなる植物繊維
セメント成形体において、添加剤として硝酸塩を含有し
てなることを特徴とする植物繊維セメント成形体に係
る。That is, the present invention provides a plant fiber cement molded article comprising at least a plant fiber material and cement, wherein the molded article comprises nitrate as an additive. It relates to a molded article.
【００１２】また、本発明は、少なくとも植物繊維材
料、セメント及び水を混合し、得られた混合物を成形
し、養生硬化することからなる植物繊維セメント成形体
の製造方法において、原料を混合する際または前記混合
物を成形する際に、硝酸塩を添加することを特徴とする
植物繊維セメント成形体の製造方法に係る。[0012] The present invention also relates to a method for producing a plant fiber cement molded body comprising mixing at least a plant fiber material, cement and water, molding the resulting mixture, and curing and curing the mixture. Alternatively, the present invention relates to a method for producing a plant fiber cement molded product, wherein a nitrate is added when the mixture is molded.
【００１３】[0013]
【発明の実施の形態】本発明は、植物繊維セメント成形
体の強度発現の障害となる、植物繊維材料中のセメント
硬化阻害物質によるセメントの水和反応の遅延を、硝酸
塩を添加することにより抑制し、それによって高強度を
有する植物繊維セメント成形体及びその製造方法を提供
するものである。BEST MODE FOR CARRYING OUT THE INVENTION The present invention suppresses the delay of hydration of cement caused by a cement hardening inhibitor in a plant fiber material, which is an obstacle to the strength development of a plant fiber cement molded product, by adding nitrate. Accordingly, the present invention provides a plant fiber cement molded article having high strength and a method for producing the same.
【００１４】以下、本発明の植物繊維セメント成形体を
更に説明する。まず、本明細書に記載する植物繊維材料
とは、針葉樹及び広葉樹等で代表される木質系繊維や竹
繊維、砂糖黍繊維、椰子の木繊維等を総称するものであ
る。また、植物繊維材料は、ニードル状、チップ状、薄
片状、ストランド状、棒状、ファイバー状、フレーク状
等の形状を有する上記繊維を総称するものである。更
に、植物繊維材料は、リグノセルロースを主成分とする
麻繊維、バガス等の材料をも包含する。なお、これらの
植物繊維材料の形状は特に限定されるものではないが、
例えば平均繊維長が１０〜５０ｍｍ、平均繊維径あるい
は平均繊維厚みが０.５ｍｍ以下であるものを使用する
ことが好ましい。更に、植物繊維材料は上記繊維の２種
以上の混合物であっても良い。Hereinafter, the molded plant fiber cement of the present invention will be further described. First, the plant fiber material described in the present specification is a general term for woody fibers, bamboo fibers, sugarcane fibers, coconut tree fibers, and the like represented by conifers and hardwoods. The plant fiber material is a general term for the above fibers having a shape such as a needle shape, a chip shape, a flake shape, a strand shape, a rod shape, a fiber shape, and a flake shape. Furthermore, the plant fiber material also includes materials such as hemp fiber and bagasse containing lignocellulose as a main component. The shape of these plant fiber materials is not particularly limited,
For example, it is preferable to use one having an average fiber length of 10 to 50 mm, an average fiber diameter or an average fiber thickness of 0.5 mm or less. Further, the plant fiber material may be a mixture of two or more of the above fibers.
【００１５】本発明の植物繊維セメント成形体におい
て、上記植物繊維材料の添加割合は、１０〜３０重量
％、好ましくは２０〜３０重量％の範囲内である。ここ
で、該添加割合が１０重量％未満であると、植物繊維材
料による補強効果が低いため、得られた植物繊維セメン
ト成形体の曲げ強度が低くなるために好ましくなく、ま
た、該添加割合が３０重量％を超えると、得られた植物
繊維セメント成形体の不燃性能が著しく低下するために
好ましくない。[0015] In the plant fiber cement molded article of the present invention, the addition ratio of the plant fiber material is in the range of 10 to 30% by weight, preferably 20 to 30% by weight. Here, if the addition ratio is less than 10% by weight, the reinforcing effect of the plant fiber material is low, and thus the bending strength of the obtained plant fiber cement molded body is low, which is not preferable. If the content exceeds 30% by weight, the non-combustibility of the obtained plant fiber cement molded article is unpreferably reduced.
【００１６】本発明の植物繊維セメント成形体に使用可
能なセメントとしては、例えばポルトランドセメント、
あるいはポルトランドセメントに高炉スラグを混合した
高炉セメント、フライアッシュを混合したフライアッシ
ュセメント、火山灰、シリカフューム、白土等のシリカ
物質を混合したシリカセメント、アルミナセメント、超
速硬セメント(ジェットセメント)等を例示することがで
きる。The cement usable in the plant fiber cement molded article of the present invention includes, for example, Portland cement,
Alternatively, blast furnace cement in which blast furnace slag is mixed with Portland cement, fly ash cement in which fly ash is mixed, volcanic ash, silica fume, silica cement in which silica materials such as clay are mixed, alumina cement, ultra-rapid hardening cement (jet cement), and the like are exemplified. be able to.
【００１７】本発明の植物繊維セメント成形体におい
て、上記セメントの添加割合は、９０〜７０重量％、好
ましくは８０〜７０重量％の範囲内である。ここで、該
添加割合が７０重量％未満であると、得られた植物繊維
セメント成形体の耐水性及び長期耐久性の低下を招く恐
れがあるために好ましくなく、また、該添加割合が９０
重量％を超えると、得られた植物繊維セメント成形体の
繊維補強効果が低く、強度は低いものとなるために好ま
しくない。In the molded plant fiber cement of the present invention, the proportion of the cement added is in the range of 90 to 70% by weight, preferably 80 to 70% by weight. Here, if the addition ratio is less than 70% by weight, there is a possibility that the water resistance and long-term durability of the obtained plant fiber cement molded article may be deteriorated, so that it is not preferable.
If the amount is more than 10% by weight, the obtained plant fiber cement molded product has a low fiber reinforcing effect and is low in strength, which is not preferable.
【００１８】本発明の植物繊維セメント成形体に添加剤
として添加する硝酸塩は、植物繊維材料中に含まれるセ
メント硬化阻害物質によるセメントの水和反応の遅延を
抑制するために作用するものである。ここで、硝酸塩の
中でも、金属イオンの種類により、水和反応の回復効果
は大きく異なり、回復効果が高い順に金属イオンの種類
を列挙すると、Ｍｇ2＋、Ｆｅ3＋、Ｎｉ2＋＞Ａｌ3＋＞
Ｃａ2＋＞Ｋ＋である。従って、本発明に添加剤として
用いられる硝酸塩は、硝酸マグネシウム［Ｍｇ(Ｎ
Ｏ3)2］、硝酸第二鉄［Ｆｅ(ＮＯ3)3］、硝酸ニッケル
［Ｎｉ(ＮＯ3)3］、硝酸アルミニウム［Ａｌ(ＮＯ3)3］
等が好ましく、硝酸マグネシウム、硝酸第二鉄、硝酸ニ
ッケルが特に好ましい。これら硝酸塩の添加量は０.５
〜１０重量％、好ましくは４〜１０重量％の範囲内であ
る。The nitrate added as an additive to the plant fiber cement molded article of the present invention acts to suppress the delay of the hydration reaction of cement caused by the cement hardening inhibitor contained in the plant fiber material. Here, among nitrates, the recovery effect of the hydration reaction varies greatly depending on the type of metal ion, and the types of metal ions are listed in descending order of the recovery effect. Mg 2+ , Fe 3+ , Ni 2+ > Al 3+ >
Ca 2+ > K + . Therefore, the nitrate used as an additive in the present invention is magnesium nitrate [Mg (N
O 3 ) 2 ], ferric nitrate [Fe (NO 3 ) 3 ], nickel nitrate [Ni (NO 3 ) 3 ], aluminum nitrate [Al (NO 3 ) 3 ]
Etc. are preferred, and magnesium nitrate, ferric nitrate and nickel nitrate are particularly preferred. The amount of addition of these nitrates is 0.5
It is in the range of 10 to 10% by weight, preferably 4 to 10% by weight.
【００１９】また、上記硝酸塩以外にも、硝酸カルシウ
ム、硝酸カリウム等も使用可能であるが、これらは先に
記載した硝酸塩に比べてセメント硬化阻害物質によるセ
メントの水和反応の遅延を抑制する効果が低いため、添
加割合を増加する必要あるいは上記した抑制効果が高い
硝酸塩と組み合わせて用いる必要がある。即ち、これら
の硝酸塩を添加する場合、これら硝酸塩の添加量は０.
５〜１０重量％、好ましくは７〜１０重量％の範囲内で
ある。In addition to the above-mentioned nitrates, calcium nitrate, potassium nitrate and the like can also be used. However, these are more effective in suppressing the delay of the hydration reaction of cement due to the cement hardening inhibitor than the nitrates described above. Since it is low, it is necessary to increase the addition ratio or use it in combination with the above-mentioned nitrate having a high inhibitory effect. That is, when these nitrates are added, the added amount of these nitrates is 0.1.
It is in the range of 5 to 10% by weight, preferably 7 to 10% by weight.
【００２０】なお、硝酸塩の添加割合が０.５重量％未
満であると、セメント硬化阻害物質によるセメントの水
和反応の遅延を抑制させるには不十分であり、また、該
添加割合が１０重量％を超えると、硝酸塩の添加割合が
多くなり過ぎて植物繊維セメント成形体の長期耐久性に
悪影響を及ぼす恐れがあると共に、原料コストの上昇を
招くために好ましくない。If the addition ratio of the nitrate is less than 0.5% by weight, it is insufficient to suppress the delay of the hydration reaction of the cement by the cement hardening inhibitor, and the addition ratio is 10% by weight. %, The addition rate of the nitrate becomes too large, which may adversely affect the long-term durability of the plant fiber cement molded product, and is not preferable because it increases the raw material cost.
【００２１】更に、本発明の植物繊維セメント成形体に
は、上記必須成分に加えて、必要に応じて下記に記載す
る物質を混合材として植物繊維セメント成形体の物性に
影響を及ぼさない範囲で添加することができる： (1)マイカ等の板状結晶； (2)ワラストナイト等の針状結晶； (3)シリカフューム、珪藻土、フライアッシュ等の無機
質微粉末； (4)炭酸カルシウム、パーライト、シラスバルーン、ス
チロール等の無機質あるいは有機質増量材； (5)ベントナイト、カオリン、バーミキュライト等の粘
土鉱物； (6)パリゴルスカイト、セピオライト等の繊維状鉱物； (7)ゼオライト等の多孔質鉱物粉末； (8)有機合成繊維、ガラス繊維、パルプ繊維、金属繊維
等の補強用繊維； (9)合成樹脂エマルジョン； (10)着色剤、防水剤等の添加物。Further, the plant fiber cement molded product of the present invention may contain, in addition to the above-mentioned essential components, the substances described below as necessary as a mixture as far as the physical properties of the plant fiber cement molded product are not affected. It can be added: (1) plate-like crystals such as mica; (2) needle-like crystals such as wollastonite; (3) inorganic fine powder such as silica fume, diatomaceous earth, fly ash; (4) calcium carbonate, perlite (5) clay minerals such as bentonite, kaolin and vermiculite; (6) fibrous minerals such as palygorskite and sepiolite; (7) porous mineral powders such as zeolite; 8) Reinforcing fibers such as organic synthetic fibers, glass fibers, pulp fibers, metal fibers; (9) synthetic resin emulsions; (10) additives such as coloring agents and waterproofing agents.
【００２２】上記(1)〜(8)の成分については、それらの
合計量が水を除く混合原料全体の３５重量％以内の範囲
内で使用することができる。また、(9)の成分について
は、水を除く混合原料全体の１０重量％以内で使用する
ことが好ましい。更に、(10)の成分については、それぞ
れ水を除く混合原料全体の５重量％以内の量で添加する
ことができる。The components (1) to (8) can be used in a total amount of 35% by weight or less of the whole mixed raw material excluding water. The component (9) is preferably used within 10% by weight of the whole mixed raw material excluding water. Further, the component (10) can be added in an amount of 5% by weight or less of the whole mixed raw material excluding water.
【００２３】本発明の植物繊維セメント成形体は、少な
くとも植物繊維材料、セメント、硝酸塩及び水を混合
し、得られた混合物を成形し、養生硬化することを特徴
として製造することができる。硝酸塩は、植物繊維材
料、セメント及び水を混合する際、または植物繊維材
料、セメント及び水を含有してなる混合物を成形する際
に、添加することができる。この際、硝酸塩はそのまま
添加しても良いが、あるいは予め水に溶解した水溶液の
形態で添加することもでき、水溶液の形態で添加するこ
とが好ましい。The plant fiber cement molded article of the present invention can be produced by mixing at least a plant fiber material, cement, nitrate and water, molding the resulting mixture, and curing and curing. The nitrate can be added when mixing the plant fiber material, cement and water, or when forming a mixture containing the plant fiber material, cement and water. At this time, the nitrate may be added as it is, or may be added in the form of an aqueous solution previously dissolved in water, and is preferably added in the form of an aqueous solution.
【００２４】なお、硝酸塩の添加は、セメント並びに任
意成分である他の粉末成分と予め粉末形態で混合するこ
とによって行っても良いが、硝酸塩は水和水を含有して
いるものが多いため、予め添加する水に完全且つ均一に
溶解し、得られた水溶液を他の成分に均一に噴霧するこ
とにより添加することがより効果的である。The nitrate may be added by mixing it in advance with cement and other optional powder components in powder form. However, nitrates often contain water of hydration. It is more effective to completely and uniformly dissolve in water to be added in advance, and to uniformly add the obtained aqueous solution to other components to add the resulting aqueous solution.
【００２５】即ち、本発明の植物繊維セメント成形体
は、上述の植物繊維材料、セメント、硝酸塩及び水並び
に必要に応じて他の成分を混練し、得られた混練物をプ
レス等により成形、クランプ等により固定し、次に、セ
メントの硬化により成形体のハンドリングが可能となる
まで養生し、クランプから成形体を取り出し、更に、得
られた成形体を養生、硬化させることにより製造するこ
とができる。また、別法として、本発明の植物繊維セメ
ント成形体は、上述の植物繊維材料、セメント及び水並
びに必要に応じて他の成分を混練し、得られた混練物を
成形する前に更に硝酸塩を添加・混練した後、上記と同
様にて成形すれば良い。That is, the molded plant fiber cement of the present invention is obtained by kneading the above-mentioned plant fiber material, cement, nitrate and water and other components as necessary, molding the obtained kneaded product by pressing or the like, and clamping it. And then cured until cement can be handled by curing of the cement, taking out the molded body from the clamp, and further curing and curing the obtained molded body. . Alternatively, the plant fiber cement molded product of the present invention is obtained by kneading the above-mentioned plant fiber material, cement and water and other components as necessary, and further forming nitrate before molding the obtained kneaded product. After adding and kneading, molding may be performed in the same manner as above.
【００２６】なお、植物繊維セメント成形体を製造する
際には、上述のように所定量の水を他の原料成分と共に
添加するが、この水分量の一部または全量を植物繊維材
料に含まれている水で賄うこともできる。When producing a plant fiber cement molded product, a predetermined amount of water is added together with other raw materials as described above, and a part or all of this water content is contained in the plant fiber material. It can also be covered by the available water.
【００２７】養生方法は、使用するセメントの種類によ
っても異なるが、自然養生、スチーム養生が好適であ
る。The curing method varies depending on the type of cement used, but natural curing and steam curing are preferred.
【００２８】[0028]
【作用】植物繊維セメント成形体の製造に際して、植物
繊維材料中から原料混合物中に溶出したセメント硬化阻
害物質がセメントの水和反応を遅延させるメカニズムと
して、各種の仮説が提案されているが、セメント硬化阻
害物質がセメント中のカルシウムイオンと錯体を形成し
て錯塩となり、未水和セメント粒子表面を覆うため、水
酸化カルシウム結晶の析出が抑制され、それによってセ
メントの水和反応に遅延を来し、凝結、硬化が遅れると
言われている。そこで、前記原料混合物に硝酸塩を添加
することによって、金属イオンが水酸化物となる際に液
相に存在するセメント硬化阻害物質を共沈させ、それに
よって液相部分のセメント硬化阻害物質の濃度が低下
し、セメントに吸着していたセメント硬化阻害物質が離
脱して液相へ移動するものと考えられる。上述した理由
により、セメントに吸着していたセメント硬化阻害物質
の層を不安定化することで、セメント硬化阻害物質によ
る水和反応の遅延を抑制し、それによってセメントの硬
化阻害のない高強度の植物繊維セメント成形体を提供す
ることができるものと思料される。Various hypotheses have been proposed as a mechanism by which a cement hardening inhibitor eluted from a plant fiber material into a raw material mixture delays the hydration reaction of cement in the production of a plant fiber cement molding. The hardening inhibitor forms a complex with calcium ions in the cement to form a complex salt, which covers the surface of the unhydrated cement particles, thereby suppressing the precipitation of calcium hydroxide crystals, thereby delaying the hydration reaction of the cement. It is said that the setting and hardening are delayed. Therefore, by adding nitrate to the raw material mixture, the cement hardening inhibitor present in the liquid phase when metal ions become hydroxides is coprecipitated, whereby the concentration of the cement hardening inhibitor in the liquid phase portion is reduced. It is considered that the cement hardening inhibitor adsorbed on the cement is released and moves to the liquid phase. For the reasons described above, by destabilizing the layer of the cement hardening inhibitor adsorbed on the cement, the delay of the hydration reaction by the cement hardening inhibitor is suppressed, whereby a high-strength cement without hardening is inhibited. It is considered that a plant fiber cement molded article can be provided.
【００２９】[0029]
【実施例】以下、実施例を挙げて本発明を更に説明す
る。植物繊維の原料としては、セメント硬化阻害物質含
有量が多いことで知られている、竹材料を使用した。 実施例１〜４ 竹原料の生長方向に長さ約２００ｍｍ、幅約３０ｍｍに
切断したタイ産竹原料(PAITONG DHAM)をハンマークラッ
シャー(有限会社旭産業社製)を用いて長さ５〜６０ｍｍ
(平均繊維長：１５ｍｍ)、径０.１〜３.０ｍｍ(平均繊
維径：０.４５ｍｍ)に繊維化した。この時、得られた竹
繊維の含水率は６７重量％であった。ここで、本明細書
に記載する植物繊維材料の含水率は下記のように定義さ
れたものである。 含水率(重量％)＝(水分を含んだ植物繊維材料の重量−
絶乾状態の植物繊維材料の重量)／絶乾状態の植物繊維
材料の重量×１００The present invention will be further described below with reference to examples. As a raw material of the vegetable fiber, a bamboo material, which is known to have a high content of a cement hardening inhibitor, was used. Examples 1 to 4 A bamboo raw material (PAITONG DHAM) cut in a growth direction of a bamboo raw material of about 200 mm in length and about 30 mm in width using a hammer crusher (manufactured by Asahi Sangyo Co., Ltd.) with a length of 5 to 60 mm.
(Average fiber length: 15 mm) and a diameter of 0.1 to 3.0 mm (average fiber diameter: 0.45 mm). At this time, the water content of the obtained bamboo fiber was 67% by weight. Here, the water content of the plant fiber material described in this specification is defined as follows. Water content (% by weight) = (weight of plant fiber material containing water-
(Weight of plant fiber material in completely dried state) / weight of plant fiber material in completely dried state × 100
【００３０】次に、該竹繊維、普通ポルトランドセメン
トの割合が絶乾重量当たりで３０：７０になるように配
合し、水は絶乾状態の竹繊維重量１００重量部に対して
１３０重量部添加した。供試体の作製は含水率を１００
重量％まで噴霧器を用いて、予め水分調整した竹繊維と
普通ポルトランドセメントとを均一に混練後、残りの３
０重量部の水に硝酸マグネシウムを完全に溶解させるこ
とによって調合した硝酸マグネシウム溶液を噴霧器にて
均一に前記混練物に添加した。なお、硝酸マグネシウム
は関東化学(株)社製特級試薬硝酸マグネシウム六水和物
［Ｍｇ（ＮＯ3）2・６Ｈ2Ｏ］を使用した。得られた混
練物を鉄板上に長さ１８０ｍｍ×幅１００ｍｍの均一な
マット状とした。次いで、圧力２０ｋｇｆ／ｃｍ2でプ
レス圧縮し、クランプにて鉄板を固定した後、プレス機
から取り出し、圧縮締結したままの状態にて養生した。
養生状態については、ポリ袋中で３０℃、２４時間密封
状態にて１次養生を行った。１次養生終了後、クランプ
を取り外し、鉄板を脱板、切断後、一方を１日強度試験
に供し、もう一方については、引き続き２次養生を行っ
た。２次養生はポリ袋中に密封した状態にて３０℃で１
４日間行った。２次養生終了後、６０℃で２４時間乾燥
し、物性試験に供した。なお、硝酸マグネシウムの添加
割合は本発明品１〜４はそれぞれ２.８重量％、４.２重
量％、５.６重量％、７.０重量％である。得られた植物
繊維セメント成形体の諸特性の測定結果を表１に示す。Next, the bamboo fiber and the ordinary Portland cement were blended so that the ratio of the bamboo fiber to the absolute dry weight was 30:70. did. The specimen was prepared with a water content of 100.
Using a sprayer to uniformly knead the bamboo fiber whose moisture has been adjusted in advance and ordinary Portland cement to a weight of
A magnesium nitrate solution prepared by completely dissolving magnesium nitrate in 0 parts by weight of water was uniformly added to the kneaded material using a sprayer. The magnesium nitrate used was a special grade reagent magnesium nitrate hexahydrate [Mg (NO 3 ) 2 .6H 2 O] manufactured by Kanto Chemical Co., Ltd. The obtained kneaded material was formed into a uniform mat having a length of 180 mm and a width of 100 mm on an iron plate. Next, it was press-compressed at a pressure of 20 kgf / cm 2 , and after fixing the iron plate with a clamp, it was taken out of the press and cured under the condition of compression-fastening.
Regarding the cured state, primary curing was performed in a plastic bag in a sealed state at 30 ° C. for 24 hours. After the primary curing, the clamp was removed, the iron plate was removed and cut, and one was subjected to a one-day strength test, and the other was continuously subjected to secondary curing. Secondary curing is performed at 30 ° C in a sealed state in a plastic bag.
I went for four days. After the completion of the secondary curing, the product was dried at 60 ° C. for 24 hours and subjected to a physical property test. In addition, the addition ratio of magnesium nitrate is 2.8% by weight, 4.2% by weight, 5.6% by weight, and 7.0% by weight for the products of the present invention 1 to 4, respectively. Table 1 shows the measurement results of various properties of the obtained plant fiber cement molded product.
【００３１】比較例１ 上記実施例１に記載した方法にて作成した竹繊維と普通
ポルトランドセメントを絶乾重量比で３０：７０とし、
更に、絶乾竹繊維１００重量部に対し、１３０重量部の
水を添加して混合した以外は上記実施例１と同様の方法
により竹繊維セメント成形体を製造した。得られた植物
繊維セメント成形体の諸特性の測定結果を表１に併記す
る。Comparative Example 1 The bamboo fiber and the ordinary Portland cement prepared by the method described in the above-mentioned Example 1 were set to an absolute dry weight ratio of 30:70,
Further, a bamboo fiber cement molded body was manufactured in the same manner as in Example 1 except that water was added and mixed with 130 parts by weight with respect to 100 parts by weight of absolutely dried bamboo fiber. Table 1 also shows the measurement results of various properties of the obtained plant fiber cement molded body.
【００３２】比較例２ 上記実施例１に記載した方法で、硝酸マグネシウムの代
わりに塩化カルシウムを用いた以外は同様の方法により
竹繊維セメント成形体を製造した。得られた植物繊維セ
メント成形体の諸特性の測定結果を表１に併記する。Comparative Example 2 A bamboo fiber cement molded body was produced in the same manner as in Example 1 except that calcium chloride was used instead of magnesium nitrate. Table 1 also shows the measurement results of various properties of the obtained plant fiber cement molded body.
【００３３】比較例３ 上記実施例１に記載した方法で、硝酸マグネシウムの代
わりに硫酸アルミニウムを用いた以外は同様の方法によ
り竹繊維セメント成形体を製造した。得られた植物繊維
セメント成形体の諸特性の測定結果を表１に併記する。Comparative Example 3 A bamboo fiber cement molded body was produced in the same manner as in Example 1 except that aluminum sulfate was used instead of magnesium nitrate. Table 1 also shows the measurement results of various properties of the obtained plant fiber cement molded body.
【００３４】[0034]
【表１】 [Table 1]
【００３５】上記表１の結果から判るように、植物繊維
材料、セメント、水のみを混合し、得られた原料混合物
を成形し、養生、硬化しても、セメントの硬化阻害を生
じているため得られた植物繊維セメント成形体は強度が
極めて低く、建築材料として使用することはできない。
また、塩化カルシウム、硫酸アルミニウム等の硬化促進
剤を添加しても、竹繊維のようにセメント硬化阻害物質
を多く含有する植物繊維材料を使用する場合において
は、硬化促進剤の添加効果は得られ難い。しかし、原料
混合物に硝酸塩を添加することで、水和反応の遅延を抑
制して高強度の植物繊維セメント成形体を得ることがで
きた。As can be seen from the results shown in Table 1 above, even if only the plant fiber material, cement and water are mixed, and the resulting raw material mixture is molded, cured and cured, the curing of the cement is inhibited. The obtained plant fiber cement molded product has extremely low strength and cannot be used as a building material.
Further, even if a hardening accelerator such as calcium chloride or aluminum sulfate is added, when a plant fiber material containing a large amount of a cement hardening inhibitor such as bamboo fiber is used, the effect of adding the hardening accelerator is obtained. hard. However, by adding nitrate to the raw material mixture, it was possible to suppress the delay of the hydration reaction and obtain a high-strength plant fiber cement molded article.
【００３６】[0036]
【発明の効果】本発明によれば、添加剤として硝酸塩を
添加するという極めて簡便な手段により高強度の植物繊
維セメント成形体を安定に提供することができるという
効果を奏する。According to the present invention, it is possible to stably provide a high-strength plant fiber cement molded article by a very simple means of adding nitrate as an additive.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山本 昌彦 茨城県石岡市柏原６−１ 株式会社建材テ クノ研究所内 (72)発明者 苅部 創 千葉県佐倉市大作二丁目４番２号 秩父小 野田株式会社中央研究所内 (72)発明者 外川 祥子 千葉県佐倉市大作二丁目４番２号 秩父小 野田株式会社中央研究所内 (72)発明者 原田 宏 埼玉県熊谷市三ヶ尻5310 秩父小野田株式 会社内 ──────────────────────────────────────────────────続 き Continued on front page (72) Inventor Masahiko Yamamoto 6-1 Kashiwara, Ishioka City, Ibaraki Prefecture Inside the Building Materials Technology Laboratory (72) Inventor Sou Karibe 2-4-2 Daisaku, Sakura City, Chiba Prefecture Onoda Chichibu Central Research Institute Co., Ltd. (72) Inventor Shoko Togawa 2-4-2 Daisaku Sakura City, Chiba Prefecture Noda Chichibu Noda Co., Ltd. (72) Inventor Hiroshi Harada 5310 Mikajiri, Kumagaya City, Saitama Prefecture Chichibu Onoda Co., Ltd.
Claims (7)
含有してなる植物繊維セメント成形体において、添加剤
として硝酸塩を含有してなることを特徴とする植物繊維
セメント成形体。1. A plant fiber cement molded product comprising at least a plant fiber material and cement, wherein the molded product comprises a nitrate as an additive.
ある、請求項１記載の植物繊維セメント成形体。2. The plant fiber cement molding according to claim 1, wherein the content of nitrate is 0.5 to 10% by weight.
鉄、硝酸ニッケル及び硝酸アルミニウムからなる群から
選択された１種または２種以上である、請求項１または
２記載の植物繊維セメント成形体。3. The plant fiber cement molded product according to claim 1, wherein the nitrate is at least one member selected from the group consisting of magnesium nitrate, ferric nitrate, nickel nitrate, and aluminum nitrate.
水を混合し、得られた混合物を成形し、養生硬化するこ
とからなる植物繊維セメント成形体の製造方法におい
て、原料を混合する際または前記混合物を成形する際
に、硝酸塩を添加することを特徴とする植物繊維セメン
ト成形体の製造方法。4. A method for producing a plant fiber cement molded body, comprising mixing at least a plant fiber material, cement and water, molding the obtained mixture, and curing and curing the mixture. A method for producing a plant fiber cement molded body, wherein a nitrate is added during molding.
ある、請求項４記載の植物繊維セメント成形体の製造方
法。5. The method according to claim 4, wherein the amount of the nitrate added is 0.5 to 10% by weight.
求項４または５記載の植物繊維セメント成形体の製造方
法。6. The method according to claim 4, wherein the nitrate is added in the form of an aqueous solution.
鉄、硝酸ニッケル及び硝酸アルミニウムからなる群から
選択された１種または２種以上である、請求項４ないし
６のいずれか１項記載の植物繊維セメント成形体の製造
方法。7. The plant according to claim 4, wherein the nitrate is at least one member selected from the group consisting of magnesium nitrate, ferric nitrate, nickel nitrate and aluminum nitrate. A method for producing a fiber cement molded article.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5552598A JP4280318B2 (en) | 1998-03-06 | 1998-03-06 | Manufacturing method of plant fiber cement molding |
| PCT/JP1999/001023 WO1999044963A1 (en) | 1998-03-06 | 1999-03-03 | Cement moldings containing vegetable fiber and method for producing the same |
| US09/622,913 US6379457B1 (en) | 1998-03-06 | 1999-03-03 | Cement moldings containing vegetable fiber and method for producing the same |
| CNB998049794A CN1199906C (en) | 1998-03-06 | 1999-03-03 | Cement moldings containing vegetable fiber and method for producing the same |
| ID20001802A ID27888A (en) | 1998-03-06 | 1999-03-03 | CEMENT MOLD AGENCY FROM THE VEGETABLE FIBER AND THE PRODUCTION METHOD |
| GB0021651A GB2354235B (en) | 1998-03-06 | 1999-03-03 | Vegetable fibre cement moulded body and method of manufacturing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5552598A JP4280318B2 (en) | 1998-03-06 | 1998-03-06 | Manufacturing method of plant fiber cement molding |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11246257A true JPH11246257A (en) | 1999-09-14 |
| JP4280318B2 JP4280318B2 (en) | 2009-06-17 |
Family
ID=13001146
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5552598A Expired - Fee Related JP4280318B2 (en) | 1998-03-06 | 1998-03-06 | Manufacturing method of plant fiber cement molding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4280318B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7060211B2 (en) | 2001-09-19 | 2006-06-13 | Katsuyama Technos Ltd. | Yam and cloths made mainly from bamboo sheaths and methods for manufacturing the same |
| JP2010179196A (en) * | 2009-02-03 | 2010-08-19 | Taisei Corp | Method of stabilizing waste disposal facility early |
| WO2018116500A1 (en) * | 2016-12-22 | 2018-06-28 | 住友林業株式会社 | Cement material reinforcing fiber |
| JP2018104263A (en) * | 2016-12-22 | 2018-07-05 | 住友林業株式会社 | Fiber for reinforcing cement materials |
| JP2018118879A (en) * | 2017-01-25 | 2018-08-02 | 住友林業株式会社 | Cement material reinforcing fiber |
| JP2018134816A (en) * | 2017-02-22 | 2018-08-30 | 住友林業株式会社 | Method of producing compression molding of lignocellulose fiber |
| JP2019147736A (en) * | 2019-04-11 | 2019-09-05 | 株式会社安藤・間 | Wet curing water of concrete and cement mortar, and curing method for concrete and cement mortar using the same |
| CN115231868A (en) * | 2022-06-21 | 2022-10-25 | 宝鸡市东大洋混凝土有限公司 | Anti-cracking and anti-corrosion C30 concrete and preparation method thereof |
-
1998
- 1998-03-06 JP JP5552598A patent/JP4280318B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7060211B2 (en) | 2001-09-19 | 2006-06-13 | Katsuyama Technos Ltd. | Yam and cloths made mainly from bamboo sheaths and methods for manufacturing the same |
| JP2010179196A (en) * | 2009-02-03 | 2010-08-19 | Taisei Corp | Method of stabilizing waste disposal facility early |
| WO2018116500A1 (en) * | 2016-12-22 | 2018-06-28 | 住友林業株式会社 | Cement material reinforcing fiber |
| JP2018104263A (en) * | 2016-12-22 | 2018-07-05 | 住友林業株式会社 | Fiber for reinforcing cement materials |
| JP2018118879A (en) * | 2017-01-25 | 2018-08-02 | 住友林業株式会社 | Cement material reinforcing fiber |
| JP2018134816A (en) * | 2017-02-22 | 2018-08-30 | 住友林業株式会社 | Method of producing compression molding of lignocellulose fiber |
| JP2019147736A (en) * | 2019-04-11 | 2019-09-05 | 株式会社安藤・間 | Wet curing water of concrete and cement mortar, and curing method for concrete and cement mortar using the same |
| CN115231868A (en) * | 2022-06-21 | 2022-10-25 | 宝鸡市东大洋混凝土有限公司 | Anti-cracking and anti-corrosion C30 concrete and preparation method thereof |
| CN115231868B (en) * | 2022-06-21 | 2023-03-14 | 宝鸡市东大洋混凝土有限公司 | Anti-cracking and anti-corrosion C30 concrete and preparation method thereof |
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|---|---|
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