CN101182000A - Calcium silicate hydrate, preparation method thereof, and concrete antifreeze agent containing calcium silicate hydrate - Google Patents
Calcium silicate hydrate, preparation method thereof, and concrete antifreeze agent containing calcium silicate hydrate Download PDFInfo
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Abstract
Description
技术领域technical field
本发明属于建筑材料及其制造方法的领域，具体涉及一种水化硅酸钙及其制备方法和含水化硅酸钙的混凝土防冻剂。The invention belongs to the field of building materials and manufacturing methods thereof, and in particular relates to calcium silicate hydrate, a preparation method thereof and a concrete antifreeze agent containing calcium silicate hydrate.
背景技术Background technique
混凝土是目前主要的建筑结构材料，其组成为：水泥+砂+石+矿物掺合料。此外在冬期施工中为了使水泥在负温下水化必须加入混凝土防冻剂。防冻剂的作用一方面为了在负温下产生液态水使水泥进行水化反应，另一方面是必须具有早强组分促进水泥石结构尽早形成。早期结构的形成使液态水进入孔隙降低冰点，同时结构形成后有利于水泥石结构的进一步发育。因而混凝土防冻剂必备的两个主要组分为防冻组分与早强组分，此外还有引气组分和减水组分。早强组分与防冻组分用量大且为盐类，而盐类的引入会对混凝土耐久性产生一系列影响，如引起钢筋锈蚀、碱集料反应等。这些影响直接关乎混凝土的寿命，为了提高混凝土的使用寿命，延长混凝土的服役期，目前混凝土施工业及建设主管部门均严格限制混凝土中盐的使用量。但在我国的三北地区，负温施工非常普遍。在负温施工过程中防冻剂是必要的混凝土组分。目前的防冻剂基本构成为二大系列，一是防冻型防冻剂，另一是早强型防冻剂，无论哪种防冻剂均以掺入盐类组分为主。盐类包括NaCl、Na2SO4、NaNO2、Ca(NO2)2等，这些盐类对混凝土性能尤其是长期耐久性均会产生不良影响，尤其是含氯盐的防冻剂更会给混凝土带来不利的影响，在冬期施工时因混凝土中掺氯盐而使钢筋锈蚀破坏，而目前市场上的防冻剂大多以氯盐作为早强组分，这对混凝土的寿命会产生巨大的不良作用，如何降低混凝土中盐含量特别是氯盐含量是当今混凝土防冻剂研究中的重要课题。Concrete is the main building structure material at present, and its composition is: cement + sand + stone + mineral admixture. In addition, concrete antifreeze must be added in order to hydrate the cement at negative temperatures during winter construction. On the one hand, the function of antifreeze is to produce liquid water at negative temperature to hydrate the cement, and on the other hand, it must have early strength components to promote the early formation of cement stone structure. The formation of the early structure allows liquid water to enter the pores to lower the freezing point, and at the same time, the formation of the structure is conducive to the further development of the cement stone structure. Therefore, the two main components necessary for concrete antifreeze are antifreeze components and early strength components, in addition to air-entraining components and water-reducing components. The early-strength components and antifreeze components are used in large amounts and are salts, and the introduction of salts will have a series of effects on the durability of concrete, such as causing steel bar corrosion and alkali-aggregate reaction. These effects are directly related to the life of concrete. In order to improve the service life of concrete and extend the service life of concrete, the concrete construction industry and construction authorities are currently strictly limiting the amount of salt used in concrete. However, in the three north regions of my country, negative temperature construction is very common. Antifreeze is a necessary concrete component during negative temperature construction. The current antifreeze is basically composed of two series, one is the antifreeze type antifreeze, and the other is the early strength antifreeze. No matter what kind of antifreeze is mainly mixed with salt components. Salts include NaCl, Na 2 SO 4 , NaNO 2 , Ca(NO 2 ) 2, etc. These salts will have adverse effects on the performance of concrete, especially the long-term durability, especially antifreeze agents containing chloride salts will damage concrete It will bring adverse effects. During winter construction, the steel bars will be corroded and damaged due to the addition of chlorine salts to the concrete. At present, most of the antifreeze agents on the market use chlorine salts as early strength components, which will have a huge adverse effect on the life of the concrete. How to reduce the salt content in concrete, especially the chloride salt content, is an important topic in the research of concrete antifreeze.
发明内容Contents of the invention
本发明的目的是解决因为混凝土防冻剂中盐含量大，而造成的混凝土耐久性差、钢筋锈蚀和碱集料反应的问题，提供了一种水化硅酸钙及其制备方法和含水化硅酸钙的混凝土防冻剂，本发明的防冻剂是用水化硅酸钙作为水泥水化的早强组分代替盐类早强组分，防冻剂中盐含量较目前的防冻剂中盐含量大幅下降。The purpose of the present invention is to solve the problems of poor concrete durability, steel bar corrosion and alkali-aggregate reaction caused by the high salt content in the concrete antifreeze agent, and provides a calcium silicate hydrate and its preparation method and hydrated silicic acid Calcium concrete antifreeze agent, the antifreeze agent of the present invention uses calcium silicate hydrate as the early-strength component of cement hydration to replace the salt early-strength component, and the salt content in the antifreeze agent is significantly lower than that in the current antifreeze agent.
本发明中的水化硅酸钙是由钙质材料、硅质材料和水制成，其中钙质材料与硅质材料的重量比为1.2～1.5∶1，水的重量与钙质材料和硅质材料的总重量比为3～4∶1。所述的硅质材料为硅藻土、蛋白石或矿渣，所述的钙质材料为生石灰或熟石灰。水化硅酸钙的制备方法如下：先将钙质材料与硅质材料按重量1.2～1.5∶1的比例混合均匀，然后磨细至45μ筛余3～10％的细度，再加入混合物总重量3～4倍的水调成浆状料并混匀，在1～3atm的条件下热反应2～5h，即得到水化硅酸钙。Calcium silicate hydrate among the present invention is to be made by calcareous material, siliceous material and water, wherein the weight ratio of calcareous material and siliceous material is 1.2～1.5: 1, the weight of water and calcareous material and silicon The total weight ratio of the raw materials is 3-4:1. The siliceous material is diatomite, opal or slag, and the calcareous material is quicklime or slaked lime. The preparation method of calcium silicate hydrate is as follows: first mix the calcareous material and the siliceous material in a ratio of 1.2 to 1.5:1 by weight, then grind to a fineness of 3 to 10% of the 45 μ sieve, and then add the total Mix 3-4 times the weight of water into a slurry and mix it evenly, and heat it for 2-5 hours under the condition of 1-3 atm to obtain calcium silicate hydrate.
本发明的含水化硅酸钙的混凝土防冻剂是按重量份数由40～50份的水化硅酸钙、40～50份的防冻组分、2.5～5份的减水组分、0.1份的引气组分和5～8份的粉煤灰组成，所述的防冻组分为NaNO2或Ca(NO2)2，所述的减水组分为萘磺酸甲醛聚合物、三聚氰胺缩甲醛缩合物或马来酸酐-甲基丙烯酸-稀酸磺酸盐，所述的引气组分为三萜皂甙。The concrete antifreeze agent containing hydrated calcium silicate of the present invention is composed of 40-50 parts by weight of calcium silicate hydrate, 40-50 parts of antifreeze components, 2.5-5 parts of water-reducing components, 0.1 parts The air-entraining component and 5-8 parts of fly ash, the antifreeze component is NaNO 2 or Ca(NO 2 ) 2 , the water reducing component is naphthalenesulfonic acid formaldehyde polymer, melamine condensation Formaldehyde condensate or maleic anhydride-methacrylic acid-dilute acid sulfonate, the air-entraining component is triterpene saponin.
本发明具有以下有益效果：The present invention has the following beneficial effects:
1.本发明生产过程简单易行，原材料廉价，有利于工业化生产。1. The production process of the present invention is simple and easy, and the raw materials are cheap, which is beneficial to industrialized production.
2.本发明可使混凝土中的盐含量大幅度降低，进而可使由于盐存在导致混凝土劣化的现象得到彻底解决。2. The present invention can greatly reduce the salt content in concrete, and further solve the phenomenon of concrete deterioration due to the presence of salt.
3.当本发明的水化硅酸钙的掺量为水泥量的5％时，施工3天的混凝土强度可提高20％～30％，28天强度可提高15％～20％。在使用合成的水化硅酸钙作为早强组分配制出低盐型防冻剂时，掺量为混凝土中水泥量的10％，-15℃条件下，混凝土的-7+28天强度可达到标养28天混凝土强度，产品性能可达到GB475标准要求，且混凝土中盐含量较目前常用防冻剂中盐含量降低40％。3. When the dosage of calcium silicate hydrate of the present invention is 5% of the amount of cement, the concrete strength can be increased by 20% to 30% after 3 days of construction, and by 15% to 20% after 28 days of construction. When using synthetic calcium silicate hydrate as an early strength component to prepare a low-salt antifreeze agent, the dosage is 10% of the cement in the concrete, and the strength of the concrete at -7+28 days at -15°C can reach The strength of the concrete after 28 days of standard curing, the product performance can meet the requirements of the GB475 standard, and the salt content in the concrete is 40% lower than that in the current commonly used antifreeze.
4.本发明的含水化硅酸钙的混凝土防冻剂中不含氯盐，减少了混凝土冬期施工时因掺氯盐而带来的钢筋锈蚀破坏作用。4. The concrete antifreeze agent containing calcium silicate hydrate of the present invention does not contain chloride salts, which reduces the corrosion and damage of steel bars caused by the addition of chlorine salts during concrete winter construction.
5.将本发明的含水化硅酸钙的混凝土防冻剂掺入混凝土中促进水化的原理是晶种水化，其效果会使水泥石的结构更加密实，结构更加合理，混凝土的长期性能不会衰减。5. The principle that the concrete antifreeze agent containing hydrated calcium silicate of the present invention is mixed in concrete to promote hydration is the hydration of crystal seeds, and its effect will make the structure of cement stone more compact and more reasonable, and the long-term performance of concrete is not high. will decay.
具体实施方式Detailed ways
具体实施方式一：本实施方式中的水化硅酸钙是由钙质材料、硅质材料和水制成，其中钙质材料与硅质材料的重量比为1.2～1.5∶1，水的重量与钙质材料和硅质材料的总重量比为3～4∶1，硅质材料为硅藻土、蛋白石或矿渣，钙质材料为生石灰或熟石灰。Specific embodiment one: calcium silicate hydrate in this embodiment is made of calcareous material, siliceous material and water, wherein the weight ratio of calcareous material and siliceous material is 1.2～1.5:1, the weight of water The total weight ratio of the calcareous material and the siliceous material is 3-4:1, the siliceous material is diatomite, opal or slag, and the calcareous material is quicklime or slaked lime.
具体实施方式二：本实施方式与具体实施方式一不同的是钙质材料与硅质材料的重量比为1.2～1.4∶1，其它与具体实施方式一相同。Embodiment 2: This embodiment differs from Embodiment 1 in that the weight ratio of the calcareous material to the siliceous material is 1.2-1.4:1, and the others are the same as Embodiment 1.
具体实施方式三：本实施方式与具体实施方式一不同的是钙质材料与硅质材料的重量比为1.2∶1，其它与具体实施方式一相同。Embodiment 3: This embodiment is different from Embodiment 1 in that the weight ratio of the calcareous material to the siliceous material is 1.2:1, and the others are the same as Embodiment 1.
具体实施方式四：本实施方式中水化硅酸钙制备方法的步骤如下：先将钙质材料与硅质材料按重量1.2～1.5∶1的比例混合均匀，然后磨细至45μ筛余3～10％的细度，再加入混合物总重量3～4倍的水调成浆状料并混匀，在1～3atm的条件下热反应2～5h，即得到水化硅酸钙。Embodiment 4: The steps of the method for preparing calcium silicate hydrate in this embodiment are as follows: first mix the calcareous material and the siliceous material evenly in a ratio of 1.2 to 1.5:1 by weight, and then grind to a 45 μ sieve, leaving 3 to 3 10% fineness, add water 3 to 4 times the total weight of the mixture to make a slurry and mix it evenly, and heat it for 2 to 5 hours under the condition of 1 to 3 atm to obtain calcium silicate hydrate.
具体实施方式五：本实施方式与具体实施方式四不同的是在步骤一中硅质材料与钙质材料按1.2～1.4∶1比例混合均匀。其它反应步骤与具体实施方式四相同。Embodiment 5: This embodiment differs from Embodiment 4 in that in step 1, the siliceous material and the calcareous material are uniformly mixed in a ratio of 1.2-1.4:1. Other reaction steps are the same as in Embodiment 4.
具体实施方式六：本实施方式与具体实施方式四不同的是在步骤一中硅质材料与钙质材料按1.2∶1比例混合均匀。其它反应步骤与具体实施方式四相同。Embodiment 6: The difference between this embodiment and Embodiment 4 is that in step 1, the siliceous material and the calcareous material are uniformly mixed in a ratio of 1.2:1. Other reaction steps are the same as in Embodiment 4.
具体实施方式七：本实施方式中的硅质材料为硅藻土、蛋白石或矿渣，钙质材料为生石灰或熟石灰。Embodiment 7: In this embodiment, the siliceous material is diatomite, opal or slag, and the calcareous material is quicklime or slaked lime.
具体实施方式八：本实施方式中含水化硅酸钙的混凝土防冻剂是按重量份数由40～50份的水化硅酸钙、40～50份的防冻组分、2.5～5份的减水组分、0.1份的引气组分和5～8份的粉煤灰制成，其制备是按常规的方法混合而成。Embodiment 8: The concrete antifreeze agent containing calcium silicate hydrate in this embodiment is composed of 40 to 50 parts of calcium silicate hydrate, 40 to 50 parts of antifreeze components, and 2.5 to 5 parts of antifreeze in parts by weight. It is made of water component, 0.1 part of air-entraining component and 5-8 parts of fly ash, and its preparation is mixed according to a conventional method.
本实施方式中当水化硅酸钙的掺量为水泥量的5％时，施工3天的混凝土强度可提高20％～30％，28天强度可提高15％～20％。本实施方式中含水化硅酸钙的混凝土防冻剂的掺量为混凝土中水泥量的10％时，-15℃条件下，混凝土的-7+28天强度可达到标养28天混凝土强度，产品性能可达到GB475标准要求，且混凝土中盐含量较目前常用防冻剂中盐含量降低40％，防冻效果最好。In this embodiment, when the dosage of calcium silicate hydrate is 5% of the cement amount, the strength of the concrete after 3 days of construction can be increased by 20% to 30%, and the strength after 28 days can be increased by 15% to 20%. In this embodiment, when the dosage of the concrete antifreeze agent containing calcium silicate hydrate is 10% of the amount of cement in the concrete, under the condition of -15°C, the strength of the concrete at -7+28 days can reach the strength of the standard 28-day concrete. The performance can meet the requirements of the GB475 standard, and the salt content in the concrete is 40% lower than that in the current commonly used antifreeze agent, and the antifreeze effect is the best.
具体实施方式九：本实施方式与具体实施方式八不同的是含水化硅酸钙的混凝土防冻剂是按重量份数由35～45份的水化硅酸钙、35～45份的防冻组分、3～4.5份的减水组分、0.1份的引气组分和5.5～7.5份的粉煤灰制成。其它与具体实施方式八相同。Specific embodiment nine: the difference between this embodiment and specific embodiment eight is that the concrete antifreeze agent containing hydrated calcium silicate is composed of 35 to 45 parts by weight of calcium silicate hydrate and 35 to 45 parts of antifreeze components , 3-4.5 parts of water-reducing component, 0.1 part of air-entraining component and 5.5-7.5 parts of fly ash. Others are the same as the eighth embodiment.
具体实施方式十：本实施方式与具体实施方式八不同的是含水化硅酸钙的混凝土防冻剂是按重量份数由30～40份的水化硅酸钙、30～40份的防冻组分、3.5～4份的减水组分、0.1份的引气组分和6～7份的粉煤灰制成。其它与具体实施方式八相同。Embodiment 10: This embodiment is different from Embodiment 8 in that the concrete antifreeze agent containing calcium silicate hydrate is composed of 30 to 40 parts by weight of calcium silicate hydrate and 30 to 40 parts of antifreeze components. , 3.5-4 parts of water-reducing component, 0.1 part of air-entraining component and 6-7 parts of fly ash. Others are the same as the eighth embodiment.
具体实施方式十一：本实施方式与具体实施方式八不同的是含水化硅酸钙的混凝土防冻剂是按重量份数由35份的水化硅酸钙、35份的防冻组分、3.7份的减水组分、0.1份的引气组分和6.5份的粉煤灰制成。其它与具体实施方式八相同。Embodiment 11: The difference between this embodiment and Embodiment 8 is that the concrete antifreeze agent containing calcium silicate hydrate is composed of 35 parts by weight of calcium silicate hydrate, 35 parts of antifreeze components, 3.7 parts It is made of water-reducing components, 0.1 parts of air-entraining components and 6.5 parts of fly ash. Others are the same as the eighth embodiment.
具体实施方式十二：本实施方式所述的防冻组分为NaNO2或Ca(NO2)2。其它与具体实施方式八至十一相同。Embodiment 12: The antifreeze component described in this embodiment is NaNO 2 or Ca(NO 2 ) 2 . Others are the same as the eighth to eleventh specific embodiments.
具体实施方式十三：本实施方式所述的防冻组分为Ca(NO2)2。其它与具体实施方式八至十一相同。Specific Embodiment Thirteen: The antifreeze component described in this embodiment is Ca(NO 2 ) 2 . Others are the same as the eighth to eleventh specific embodiments.
具体实施方式十四：本实施方式所述的减水组分为萘磺酸甲醛聚合物、三聚氰胺缩甲醛缩合物或马来酸酐-甲基丙烯酸-稀酸磺酸盐。其它与具体实施方式八至十一相同。Embodiment Fourteen: The water-reducing component described in this embodiment is a naphthalenesulfonic acid formaldehyde polymer, a melamine formal condensate or a maleic anhydride-methacrylic acid-dilute acid sulfonate. Others are the same as the eighth to eleventh specific embodiments.
具体实施方式十五：本实施方式所述的减水组分为三聚氰胺缩甲醛缩合物，其它与具体实施方式八至十一相同。Embodiment 15: The water-reducing component described in this embodiment is melamine formal condensate, and the others are the same as Embodiments 8 to 11.
具体实施方式十六：本实施方式所述的减水组分为马来酸酐-甲基丙烯酸-稀酸磺酸盐，其它与具体实施方式八至十一相同。Embodiment 16: The water-reducing component described in this embodiment is maleic anhydride-methacrylic acid-dilute acid sulfonate, and the others are the same as Embodiments 8 to 11.
具体实施方式十七：本实施方式所述的引气组分为三萜皂甙。其它与具体实施方式八至十一相同。Embodiment 17: The air-entraining component described in this embodiment is triterpene saponin. Others are the same as the eighth to eleventh specific embodiments.
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| CN107162010A (en) * | 2017-05-25 | 2017-09-15 | 内蒙古仁创沙漠资源利用研究院有限公司 | The hydrated calcium silicate for synthesizing the method for hydrated calcium silicate and being synthesized by this method |
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| CN101830660A (en) * | 2010-03-19 | 2010-09-15 | 华东交通大学 | High-activity crystal seed for concrete production and preparation method thereof |
| CN101830660B (en) * | 2010-03-19 | 2012-05-02 | 华东交通大学 | A kind of highly active crystal seed for concrete production and preparation method thereof |
| CN102295421A (en) * | 2011-06-14 | 2011-12-28 | 宁波大学 | Crystal seed used for improving concrete early stage strength, and application thereof |
| CN102295421B (en) * | 2011-06-14 | 2013-04-24 | 宁波大学 | Crystal seed used for improving concrete early stage strength, and application thereof |
| CN103449460A (en) * | 2012-06-05 | 2013-12-18 | 中央民族大学 | Preparation method of calcium silicate hydrate nano material |
| CN102786246A (en) * | 2012-08-31 | 2012-11-21 | 句容宁武高新技术发展有限公司 | Concrete antifreezer |
| CN104150802A (en) * | 2014-07-17 | 2014-11-19 | 华东交通大学 | Synthesis method of crystal nucleus for promoting high-belite cement hydration progress |
| CN104402009B (en) * | 2014-10-29 | 2017-02-15 | 上海建工集团股份有限公司 | Calcium silicate hydrate gel solution early strength agent and suction filtration preparation method thereof |
| CN104402009A (en) * | 2014-10-29 | 2015-03-11 | 上海建工集团股份有限公司 | Calcium silicate hydrate gel solution early strength agent and preparation method thereof |
| CN106746834A (en) * | 2016-11-28 | 2017-05-31 | 中铁十二局集团有限公司 | A kind of graphene-based nanocrystal class early strength agent and preparation method thereof |
| CN106746834B (en) * | 2016-11-28 | 2018-12-14 | 中铁十二局集团有限公司 | A kind of graphene-based nanocrystal class early strength agent and preparation method thereof |
| CN107162010A (en) * | 2017-05-25 | 2017-09-15 | 内蒙古仁创沙漠资源利用研究院有限公司 | The hydrated calcium silicate for synthesizing the method for hydrated calcium silicate and being synthesized by this method |
| CN108164179A (en) * | 2017-11-24 | 2018-06-15 | 中国铁道科学研究院铁道建筑研究所 | A kind of cement concrete antifreezer suitable for ultra-low temperature surroundings |
| CN109369051A (en) * | 2018-11-22 | 2019-02-22 | 中耕耘成建筑科技(江苏)有限公司 | A kind of preparation method of hydrated calcium silicate early strength agent and a kind of self-compacting concrete |
| CN109369055A (en) * | 2018-11-22 | 2019-02-22 | 中耕耘成建筑科技(江苏)有限公司 | A composite early strength agent and self-compacting concrete prepared by using the same |
| CN109369055B (en) * | 2018-11-22 | 2022-01-21 | 中耕耘成建筑科技(江苏)有限公司 | Composite early strength agent and self-compacting concrete prepared by utilizing same |
| CN114014580A (en) * | 2021-11-17 | 2022-02-08 | 中国铁道科学研究院集团有限公司铁道建筑研究所 | Early strength antifreezing agent and preparation method thereof |
| CN114014580B (en) * | 2021-11-17 | 2023-02-24 | 中国铁道科学研究院集团有限公司铁道建筑研究所 | A kind of early strength antifreeze and preparation method thereof |
| CN114315282A (en) * | 2022-01-17 | 2022-04-12 | 江苏中砼新材料科技有限公司 | Preparation method of early-strength anti-freezing recycled concrete |
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