CN110540212A - Low modulus sodium silicate solution and preparation method thereof - Google Patents

Low modulus sodium silicate solution and preparation method thereof Download PDF

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CN110540212A
CN110540212A CN201910835164.9A CN201910835164A CN110540212A CN 110540212 A CN110540212 A CN 110540212A CN 201910835164 A CN201910835164 A CN 201910835164A CN 110540212 A CN110540212 A CN 110540212A
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sodium silicate
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叶家元
史迪
张文生
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China Building Materials Academy CBMA
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Abstract

本发明是关于一种低模数硅酸钠溶液及其制备方法。该低模数硅酸钠溶液的制备方法包括:在常温条件下,向NaOH溶液中加入纳米SiO2颗粒,进行搅拌、分散,得到设定模数的低模数硅酸钠溶液。本发明还提供了以该方法制得的低模数硅酸钠溶液作为激发剂制备的碱激发胶凝材料。本发明基于纳米SiO2颗粒在常温下的强碱溶液中快速溶解而形成单体[SiOn(OH)4‑n]n‑的原理,纳米SiO2颗粒发挥对溶液可溶性硅的快速补充作用,快速地获得具有低模数、低粘度、强稳定性特征的硅酸钠溶液。本发明制备方法制得的低模数硅酸钠溶液无论是即配即用还是长时间陈放,纳米SiO2颗粒均可发挥其效应而改善碱激发胶凝材料性能。

The invention relates to a low modulus sodium silicate solution and a preparation method thereof. The preparation method of the low-modulus sodium silicate solution comprises: adding nanometer SiO2 particles into the NaOH solution at normal temperature, stirring and dispersing to obtain the low-modulus sodium silicate solution with a set modulus. The invention also provides an alkali-activated gelling material prepared by using the low-modulus sodium silicate solution prepared by the method as an activator. The present invention is based on the principle that nano-SiO 2 particles dissolve rapidly in a strong alkali solution at normal temperature to form monomer [SiO n (OH) 4-n ] n- principle, and the nano-SiO 2 particles play a fast supplementary role to the soluble silicon in the solution, Quickly obtain sodium silicate solution with low modulus, low viscosity and strong stability. No matter the low-modulus sodium silicate solution prepared by the preparation method of the present invention is ready-to-use or stored for a long time, the nano- SiO2 particles can exert its effect to improve the performance of the alkali-activated gelling material.

Description

低模数硅酸钠溶液及其制备方法Low modulus sodium silicate solution and preparation method thereof

技术领域technical field

本发明涉及一种水玻璃技术领域,特别是涉及一种低模数硅酸钠溶液及其制备方法。The invention relates to the technical field of water glass, in particular to a low modulus sodium silicate solution and a preparation method thereof.

背景技术Background technique

碱激发剂是碱激发胶凝材料最重要组分,其使硅铝质原料颗粒溶解并释放出硅、铝单体。硅、铝单体释放过程是硅铝聚合反应的控制性过程,因此碱激发剂对胶凝材料的凝结硬化性能及微结构发育、性能发展有至关重要的影响。不同原材料对碱激发剂的特征有不同要求。对于矿渣等高钙、高硅、低铝原料,高模数(n=SiO2/Na2O)水玻璃溶液不仅可提供适当碱性环境,而且可溶性硅((聚)硅酸根离子)供给也足以保证硅铝聚合反应顺利进行。对于粉煤灰等低钙、高铝、高硅原料,必须具有足够强的碱性环境材料才能使其释放硅、铝单体,因此通常选用高浓度的NaOH溶液。但是对于粉煤灰为原料制备的胶凝材料体系,仅仅具有足够碱性环境还不足以使其在常温下快速释放硅、铝单体,即在常温下其凝结硬化异常缓慢。为了提升反应速度,通常提高养护温度以促进凝结硬化过程、促进微结构形成、提升强度。这种方法不仅能耗高,而且只适用于预制构件,因此迫切需要发展常温养护技术。The alkali activator is the most important component of the alkali-activated gelling material, which dissolves the silicon-aluminum raw material particles and releases silicon and aluminum monomers. The release process of silicon and aluminum monomers is the controlling process of the silicon-aluminum polymerization reaction, so the alkali activator has a crucial influence on the setting hardening performance, microstructure development and performance development of the gelled material. Different raw materials have different requirements for the characteristics of the alkali activator. For high-calcium, high-silicon, and low-aluminum raw materials such as slag, high modulus (n=SiO 2 /Na 2 O) water glass solution can not only provide a suitable alkaline environment, but also supply soluble silicon ((poly)silicate ions) It is sufficient to ensure the smooth progress of the silicon-aluminum polymerization reaction. For low-calcium, high-aluminum, and high-silicon raw materials such as fly ash, it is necessary to have a sufficiently strong alkaline environment material to release silicon and aluminum monomers, so a high-concentration NaOH solution is usually used. However, for the cementitious material system prepared with fly ash as raw material, only having enough alkaline environment is not enough to make it release silicon and aluminum monomers quickly at room temperature, that is, its coagulation and hardening are extremely slow at room temperature. In order to increase the reaction speed, the curing temperature is usually increased to promote the condensation hardening process, promote the formation of microstructure, and increase the strength. This method not only consumes a lot of energy, but is only suitable for prefabricated components, so it is urgent to develop normal temperature curing technology.

为了实现常温养护,在胶凝材料体系中以可溶性硅的形式额外补充硅单体不失为一种可行方法。可溶性硅的来源可以是硅酸钠溶液(水玻璃)。对粉煤灰为原料制备的胶凝材料而言,因需足够强的碱性环境,因此相适应的水玻璃溶液(在高模数水玻璃溶液中添加NaOH而制得,需陈放24小时以达到平衡)必定具有低模数(n<1.0)特征。对于低模数的水玻璃,其具有强碱及离子态可溶性硅的特征,极不稳定,放置数天后就会发生结晶、分层现象。由此可见,以低模数水玻璃作为激发剂会给材料制备及其性能调控带来诸多不确定性因素,这对工业化生产极为不利。因此,还需寻求可溶性硅供给的替代方案。In order to achieve normal temperature curing, it is a feasible method to supplement silicon monomer in the form of soluble silicon in the cementitious material system. The source of soluble silicon can be sodium silicate solution (water glass). For the cementitious material prepared from fly ash, due to the need for a sufficiently strong alkaline environment, the suitable water glass solution (made by adding NaOH to the high modulus water glass solution, needs to be aged for more than 24 hours. reach equilibrium) must have a low modulus (n<1.0) feature. For low-modulus water glass, it has the characteristics of strong alkali and ionic soluble silicon, and is extremely unstable. Crystallization and delamination will occur after a few days of storage. It can be seen that using low-modulus water glass as an activator will bring many uncertain factors to material preparation and performance regulation, which is extremely unfavorable to industrial production. Therefore, alternatives to the supply of soluble silicon need to be sought.

发明内容Contents of the invention

本发明的主要目的在于,提供一种低模数硅酸钠溶液(水玻璃)的制备方法,所要解决的技术问题是低模数硅酸钠溶液即配即用(无需长时间陈放)及其稳定性提升(可长时间储存),并使其同时具有强碱和快速提供可溶性硅的特征。The main purpose of the present invention is to provide a kind of preparation method of low-modulus sodium silicate solution (water glass), and the technical problem to be solved is that low-modulus sodium silicate solution is ready-to-use (without long-time aging) and its The stability is improved (storage for a long time), and it has the characteristics of strong alkali and fast supply of soluble silicon.

本发明的目的及解决其技术问题是采用以下技术方案来实现的。依据本发明提出的一种低模数硅酸钠溶液的制备方法,其包括:The purpose of the present invention and the solution to its technical problems are achieved by adopting the following technical solutions. According to the preparation method of a kind of low modulus sodium silicate solution proposed by the present invention, it comprises:

在常温条件下,向NaOH溶液中加入纳米SiO2颗粒,进行搅拌、分散,得到设定模数的低模数硅酸钠溶液。Under the condition of normal temperature, add nanometer SiO 2 particles into the NaOH solution, stir and disperse to obtain a low modulus sodium silicate solution with a set modulus.

本发明的目的及解决其技术问题还可采用以下技术措施进一步实现。The purpose of the present invention and its technical problems can also be further realized by adopting the following technical measures.

优选的,前述的低模数硅酸钠溶液的制备方法,其中所述纳米SiO2颗粒的添加量满足式(1):Preferably, the preparation method of aforementioned low modulus sodium silicate solution, wherein said nano-SiO The addition of particle satisfies formula (1):

m=30×c×V×n (1)m=30×c×V×n (1)

式(1)中,In formula (1),

m为NaOH溶液中纳米SiO2颗粒的添加量,单位g;m is the addition amount of nanometer SiO particles in NaOH solution, unit g;

c为NaOH溶液的浓度,单位mol/L;c is the concentration of NaOH solution, unit mol/L;

V为NaOH溶液的体积,单位L;V is the volume of NaOH solution, unit L;

n为设定模数,其中0<n<1。n is the setting modulus, where 0<n<1.

优选的,前述的低模数硅酸钠溶液的制备方法,其中所述纳米SiO2颗粒的比表面积为120~400m2/g,粒度D0.5为7~200nm。Preferably, in the aforementioned method for preparing the low-modulus sodium silicate solution, the specific surface area of the nano-SiO 2 particles is 120-400 m 2 /g, and the particle size D0.5 is 7-200 nm.

优选的,前述的低模数硅酸钠溶液的制备方法,其中所述纳米SiO2颗粒为亲水型纳米SiO2颗粒。Preferably, the aforementioned method for preparing the low modulus sodium silicate solution, wherein the nano-SiO 2 particles are hydrophilic nano-SiO 2 particles.

优选的,前述的低模数硅酸钠溶液的制备方法,其中所述搅拌为机械搅拌,所述搅拌的转速为500~900r/min,时间为10~30min;所述分散为超声分散,其在机械搅拌后随之进行,所述分散的时间为5~10min。Preferably, the aforementioned low modulus sodium silicate solution preparation method, wherein the stirring is mechanical stirring, the stirring speed is 500-900r/min, and the time is 10-30min; the dispersion is ultrasonic dispersion, which Followed by mechanical stirring, the dispersion time is 5-10 minutes.

优选的,前述的低模数硅酸钠溶液的制备方法,其中当设定模数n≥0.6时,将纳米SiO2颗粒分成质量相近的两份,并分两次加入,以避免一次加入而造成无法搅拌。Preferably, the preparation method of the aforementioned low-modulus sodium silicate solution, wherein when the modulus n≥0.6 is set, the nano- SiO2 particles are divided into two parts with similar masses, and are added in two times to avoid one-time addition and Make it impossible to stir.

本发明的目的及解决其技术问题还采用以下的技术方案来实现。依据本发明提出的一种低模数硅酸钠溶液,其由前述的任一项所述的制备方法制得。The purpose of the present invention and the solution to its technical problems are also achieved by the following technical solutions. According to the present invention, a low modulus sodium silicate solution is prepared by the preparation method described in any one of the foregoing.

优选的,前述的低模数硅酸钠溶液,其中所述低模数硅酸钠溶液的粘度为10~20mPa·s。Preferably, the aforementioned low modulus sodium silicate solution, wherein the viscosity of the low modulus sodium silicate solution is 10-20 mPa·s.

本发明的目的及解决其技术问题还采用以下的技术方案来实现。依据本发明提出的一种碱激发胶凝材料,其以前述的低模数硅酸钠溶液作为碱激发剂。The purpose of the present invention and the solution to its technical problems are also achieved by the following technical solutions. According to an alkali-activated gelling material proposed by the present invention, the aforementioned low-modulus sodium silicate solution is used as an alkali-activator.

本发明的目的及解决其技术问题还可采用以下技术措施进一步实现。The purpose of the present invention and its technical problems can also be further realized by adopting the following technical measures.

优选的,前述的碱激发胶凝材料,其中所述的低模数硅酸钠溶液为清澈溶液,机械搅拌与超声分散后不需陈放,可立即用于制备碱激发胶凝材料。Preferably, the aforementioned alkali-activated gelling material, wherein the low-modulus sodium silicate solution is a clear solution, can be used immediately to prepare the alkali-activated gelling material without aging after mechanical stirring and ultrasonic dispersion.

借由上述技术方案,本发明提出的一种低模数硅酸钠溶液及其制备方法至少具有下列优点:By means of the above-mentioned technical scheme, a kind of low modulus sodium silicate solution and preparation method thereof proposed by the present invention have at least the following advantages:

1、本发明的制备方法是在常温条件下向NaOH溶液中添加一定量的纳米SiO2颗粒,机械搅拌并超声分散后即可获得低模数的硅酸钠溶液,可即配即用,不需陈放,简单快捷。1. The preparation method of the present invention is to add a certain amount of nano-SiO particles to the NaOH solution at normal temperature, mechanically stir and ultrasonically disperse to obtain a low-modulus sodium silicate solution, which can be ready-to-use, without It needs to be aged, simple and fast.

2、本发明制备方法中对于即配即用的低模数硅酸钠溶液,纳米SiO2颗粒只有部分颗粒溶解,此时其既可发挥“提供可溶性硅”的化学作用,未溶解的颗粒还可发挥超细颗粒的物理填充作用和晶核作用,这对提升碱激发胶凝材料早期强度有明显作用;对于已长时间陈放的低模数硅酸钠溶液,纳米SiO2颗粒已完全溶解,此时其仅发挥“提供可溶性硅”的化学作用。尽管缺少了物理填充作用和晶核作用,但可溶性硅供给数量更多,即化学作用发挥得更充分,碱激发胶凝材料的强度同样会得到明显提升。因此,使用该方法制得的低模数硅酸钠溶液无论是即配即用还是长时间陈放,纳米SiO2颗粒均可发挥其效应而改善碱激发胶凝材料性能。2. For the ready-to-use low-modulus sodium silicate solution in the preparation method of the present invention, the nano- SiO2 particles only have part of the particles dissolved, and at this time it can play the chemical role of "providing soluble silicon", and the undissolved particles can also be recovered. It can play the role of physical filling and crystal nucleus of ultrafine particles, which has a significant effect on improving the early strength of alkali-activated gelling materials; for the low-modulus sodium silicate solution that has been aged for a long time, the nano-SiO 2 particles have been completely dissolved, At this time it only plays a chemical role of "providing soluble silicon". Although there is a lack of physical filling and crystal nucleation, the supply of soluble silicon is larger, that is, the chemical action is more fully exerted, and the strength of the alkali-activated gelled material will also be significantly improved. Therefore, whether the low-modulus sodium silicate solution prepared by this method is ready-to-use or stored for a long time, the nano-SiO 2 particles can exert its effect and improve the performance of the alkali-activated gelling material.

3、本发明方法中添加的纳米SiO2颗粒,具有高活性特征,可快速补充体系的高活性硅单体([SiOn(OH)4-n]n-),进而可实现高硅、高铝原料(如粉煤灰)在常温条件下制备碱激发胶凝材料,避免了加热养护,这不仅具有显著节能意义,而且还扩大了该材料的应用范围(即可用于预制构件、也可用于现浇结构)。3. The nano- SiO2 particles added in the method of the present invention have high activity characteristics, and can quickly supplement the highly active silicon monomer ([SiO n (OH) 4-n ] n- ) of the system, thereby realizing high silicon, high Aluminum raw materials (such as fly ash) are used to prepare alkali-activated cementitious materials at room temperature, avoiding heating and curing, which not only has significant energy-saving significance, but also expands the application range of the material (it can be used for prefabricated components, but also for cast-in-place structure).

4、本发明制备方法制得的低模数硅酸钠溶液,不仅具有低粘度特征,其粘度为10~20mPa·s,而且因可溶性硅的供给状态改变而可长时间储存,这显然有利于碱激发胶凝材料的工业化生产与应用。4. The low-modulus sodium silicate solution prepared by the preparation method of the present invention not only has low viscosity characteristics, its viscosity is 10-20mPa·s, and it can be stored for a long time due to the change of the supply state of soluble silicon, which is obviously beneficial to Industrial production and application of alkali-activated gelling materials.

5、本发明方法对溶液的pH值无影响。添加的纳米SiO2颗粒快速溶解并提供单体[SiOn(OH)4-n]n-,不聚合,不改变溶液特征。5. The method of the present invention has no influence on the pH value of the solution. The added nano-SiO 2 particles dissolve quickly and provide monomeric [SiO n (OH) 4-n ] n- , without aggregation and without changing the solution characteristics.

6、本发明基于纳米SiO2颗粒在常温下的强碱溶液中快速溶解而形成单体[SiOn(OH)4-n]n-的原理,纳米SiO2颗粒发挥对溶液可溶性硅的快速补充作用,快速地获得具有低模数、低粘度、强稳定性特征的硅酸钠溶液。6. The present invention is based on the principle that nano-SiO 2 particles are quickly dissolved in a strong alkali solution at room temperature to form monomer [SiO n (OH) 4-n ] n- , and nano-SiO 2 particles can quickly supplement the soluble silicon in the solution It can quickly obtain sodium silicate solution with low modulus, low viscosity and strong stability.

上述说明仅是本发明技术方案的概述,为了能够更清楚了解本发明的技术手段,并可依照说明书的内容予以实施,以下以本发明的较佳实施例并配合附图详细说明如后。The above description is only an overview of the technical solutions of the present invention. In order to understand the technical means of the present invention more clearly and implement them according to the contents of the description, the preferred embodiments of the present invention and accompanying drawings are described in detail below.

附图说明Description of drawings

图1是本发明实施例在NaOH溶液中添加纳米SiO2颗粒后溶液的放热速率曲线;Fig. 1 is the exothermic rate curve of solution after adding nanometer SiO2 particle in NaOH solution in the embodiment of the present invention;

图2是本发明实施例在NaOH溶液中添加纳米SiO2颗粒后溶液的遮光度变化曲线;Fig. 2 is that embodiment of the present invention adds nano-SiO in NaOH solution The shading degree change curve of solution after particle;

图3是本发明实施例在NaOH溶液中添加纳米SiO2颗粒后溶液的粘度变化曲线;Fig. 3 is that embodiment of the present invention adds nano-SiO in NaOH solution The viscosity change curve of solution after particle;

图4是本发明实施例在NaOH溶液中添加纳米SiO2颗粒后溶液的FTIR振动特征变化曲线;Fig. 4 is the FTIR vibration characteristic change curve of solution after adding nanometer SiO2 particle in NaOH solution in the embodiment of the present invention;

图5是本发明实施例中一种低模数硅酸钠溶液激发试样的水化放热速率曲线。Fig. 5 is the hydration heat release rate curve of a sample excited by a low modulus sodium silicate solution in an embodiment of the present invention.

具体实施方式Detailed ways

为更进一步阐述本发明为达成预定发明目的所采取的技术手段及功效,以下结合附图及较佳实施例,对依据本发明提出的低模数硅酸钠溶液及其制备方法其具体实施方式、结构、特征及其功效,详细说明如后。在下述说明中,不同的“一实施例”或“实施例”指的不一定是同一实施例。此外,一或多个实施例中的特定特征、结构或特点可由任何合适形式组合。For further elaborating the technical means and effect that the present invention takes to reach the intended invention purpose, below in conjunction with accompanying drawing and preferred embodiment, to the low modulus sodium silicate solution that proposes according to the present invention and its preparation method its specific implementation , structure, feature and effect thereof, detailed description is as follows. In the following description, different "one embodiment" or "embodiment" do not necessarily refer to the same embodiment. Furthermore, the particular features, structures or characteristics of one or more embodiments may be combined in any suitable manner.

本发明实施例提出了一种低模数硅酸钠溶液的制备方法,其包括:The embodiment of the present invention proposes a kind of preparation method of low modulus sodium silicate solution, it comprises:

在常温条件下,向NaOH溶液中加入纳米SiO2颗粒,进行搅拌、分散,得到设定模数的低模数硅酸钠溶液。Under the condition of normal temperature, add nanometer SiO 2 particles into the NaOH solution, stir and disperse to obtain a low modulus sodium silicate solution with a set modulus.

本发明实施例中,纳米SiO2颗粒的添加量根据设定模数和NaOH溶液的浓度来决定。在加入纳米SiO2颗粒前,需要事先配制满足设定水灰比和浓度的NaOH溶液,这是为了更有利于纳米SiO2颗粒分散并使其快速溶解且保持低粘度,以避免溶液中水不足而需在碱激发胶凝材料成型时补充额外水,更是为了避免溶液中水不足而可能导致溶液粘度过高甚至呈果冻状而无法使用的现象。In the embodiment of the present invention, the addition amount of nano-SiO 2 particles is determined according to the set modulus and the concentration of the NaOH solution. Before adding nano- SiO2 particles, it is necessary to prepare NaOH solution that meets the set water-cement ratio and concentration in advance. This is to facilitate the dispersion of nano- SiO2 particles and make them dissolve quickly and maintain low viscosity, so as to avoid insufficient water in the solution. Additional water needs to be added when the alkali-activated gelling material is formed, in order to avoid the phenomenon that the solution may be too viscous or even jelly-like due to insufficient water in the solution.

作为优选,所述纳米SiO2颗粒的添加量满足式(1):As preferably, described nano-SiO The addition amount of particle satisfies formula (1):

m=30×c×V×n (1)m=30×c×V×n (1)

式(1)中,In formula (1),

m为NaOH溶液中纳米SiO2颗粒的添加量,单位g;m is the addition amount of nanometer SiO particles in NaOH solution, unit g;

c为NaOH溶液的浓度,单位mol/L;c is the concentration of NaOH solution, unit mol/L;

V为NaOH溶液的体积,单位L;V is the volume of NaOH solution, unit L;

n为设定模数,其中0<n<1。n is the setting modulus, where 0<n<1.

需要重点说明的是,本发明的低模数是相对于当前常见商业产品而言的。商业产品(水玻璃溶液,即溶有硅酸钠的水溶液)的模数通常为2.0~2.4和3.0~3.4,故本发明公布的模数范围(0.0~1.0)比商业产品的模数低。It should be emphasized that the low modulus of the present invention is relative to the current common commercial products. The modulus of the commercial product (water glass solution, i.e. the aqueous solution of sodium silicate dissolved therein) is usually 2.0~2.4 and 3.0~3.4, so the modulus range (0.0~1.0) announced by the present invention is lower than the modulus of the commercial product.

本发明实施例中,在加入所述纳米SiO2颗粒前,先配制满足碱激发胶凝材料设定水灰比及其所需浓度的NaOH溶液。通常,碱激发胶凝材料砂浆实验需粉体原料450g,假设水灰比为γ,低模数硅酸钠溶液的掺量为β(%,以其Na2O含量占碱激发胶凝材料中的粉体原料的质量百分比计),则此时配制所需浓度的NaOH溶液需水量m’(单位g)满足式(2):In the embodiment of the present invention, before adding the nano-SiO 2 particles, a NaOH solution that satisfies the set water-cement ratio and the required concentration of the alkali-activated gelling material is firstly prepared. Generally, 450g of powder raw material is required for the mortar experiment of alkali-activated cementitious materials. Assuming that the water-cement ratio is γ, the dosage of low-modulus sodium silicate solution is β(%, based on the Na2O content in the alkali-activated cementitious material The mass percent of the powder raw material), then the NaOH solution water demand m' (unit g) of the preparation required concentration satisfies formula (2):

m’=450×γ (2)m'=450×γ (2)

式(2)中,In formula (2),

m’为所需浓度的NaOH溶液的需水量,单位g;m' is the water demand of the NaOH solution of required concentration, unit g;

γ为碱激发胶凝材料的设定水灰比(水的质量除以粉体原料的质量)。γ is the set water-cement ratio (the mass of water divided by the mass of powder raw materials) of the alkali-activated gelling material.

NaOH溶液的所需浓度c满足式(3):The required concentration c of NaOH solution satisfies formula (3):

c=10×β/(31×γ) (3)c=10×β/(31×γ) (3)

式(3)中,In formula (3),

c为NaOH溶液的所需浓度,单位mol/L;c is the required concentration of NaOH solution, unit mol/L;

β为低模数硅酸钠溶液的掺量,以%表示,以其Na2O含量占碱激发胶凝材料中的粉体原料的质量百分比计;β is the dosage of low modulus sodium silicate solution, expressed in %, based on the mass percentage of its Na2O content in the powder raw material in the alkali-activated gelling material;

γ为碱激发胶凝材料的设定水灰比(水的质量除以粉体原料的质量)。γ is the set water-cement ratio (the mass of water divided by the mass of powder raw materials) of the alkali-activated gelling material.

在上述需水量及浓度条件下,需配制(9×γ/20)L NaOH溶液即可满足碱激发胶凝材料的设定水灰比;需在NaOH溶液中添加(15×9×β×n/31)g纳米SiO2颗粒即可满足设定模数。Under the above water demand and concentration conditions, it is necessary to prepare (9×γ/20)L NaOH solution to meet the set water-cement ratio of the alkali-activated gelling material; it is necessary to add (15×9×β×n /31)g nano-SiO 2 particles can meet the set modulus.

本发明方法在NaOH溶液中加入纳米SiO2颗粒,可快速获得低模数的硅酸钠溶液,其具有低粘度、可长时间陈放的特点。The method of the invention adds nano- SiO2 particles into the NaOH solution, so that the sodium silicate solution with low modulus can be obtained quickly, and the solution has the characteristics of low viscosity and long-term aging.

本发明方法中对于即配即用的低模数硅酸钠溶液,纳米SiO2颗粒只有部分颗粒溶解,此时其既可发挥“提供可溶性硅”的化学作用,未溶解的颗粒还可发挥超细颗粒的物理填充作用和晶核作用,这对提升碱激发胶凝材料早期强度有明显作用;对于已长时间陈放的低模数硅酸钠溶液,纳米SiO2颗粒已完全溶解,此时其仅发挥“提供可溶性硅”的化学作用。尽管缺少了物理填充作用和晶核作用,但可溶性硅供给数量更多,即化学作用发挥得更充分,碱激发胶凝材料的强度同样会得到明显提升。因此,低模数硅酸钠溶液无论是即配即用还是长时间陈放,纳米SiO2颗粒均可发挥其效应而改善碱激发胶凝材料性能。In the method of the present invention, for the ready-to-use low-modulus sodium silicate solution, the nano- SiO2 particles only partially dissolve, and at this time it can play the chemical role of "providing soluble silicon", and the undissolved particles can also play super The physical filling effect and crystal nucleation effect of fine particles have a significant effect on improving the early strength of the alkali-activated gelled material; for the low-modulus sodium silicate solution that has been aged for a long time, the nano-SiO 2 particles have been completely dissolved, and at this time its Executes only the chemistry of "providing soluble silicon". Although there is a lack of physical filling and crystal nucleation, the supply of soluble silicon is larger, that is, the chemical action is more fully exerted, and the strength of the alkali-activated gelled material will also be significantly improved. Therefore, whether the low-modulus sodium silicate solution is ready-to-use or stored for a long time, the nano-SiO 2 particles can exert its effect and improve the performance of the alkali-activated gelling material.

本发明方法中添加的纳米SiO2颗粒,具有高活性特征,可快速补充体系的高活性硅单体([SiOn(OH)4-n]n-),进而可实现高硅、高铝原料(如粉煤灰)在常温条件下制备碱激发胶凝材料,避免了加热养护。本发明方法对溶液的pH值无影响。添加的纳米SiO2颗粒快速溶解并提供单体[SiOn(OH)4-n]n-,不聚合,不改变溶液特征。The nano- SiO2 particles added in the method of the present invention have high activity characteristics, and can quickly supplement the high-activity silicon monomer ([SiO n (OH) 4-n ] n- ) of the system, thereby realizing high-silicon and high-alumina raw materials (such as fly ash) to prepare alkali-activated gelling materials under normal temperature conditions, avoiding heating and curing. The method of the present invention has no influence on the pH value of the solution. The added nano-SiO 2 particles dissolve quickly and provide monomeric [SiO n (OH) 4-n ] n- , without aggregation and without changing the solution characteristics.

相比于现有商业产品,本发明实施例将模数小于等于0.5的硅酸钠溶液(0<n≤0.5)称为超低模数硅酸钠溶液。本发明在制备n≤0.5的超低模数的硅酸钠溶液更具有突出的优势:基于纳米SiO2颗粒在常温强碱溶液中快速溶解而形成单体[SiOn(OH)4-n]n-的原理,纳米SiO2颗粒发挥对溶液可溶性硅的快速补充作用,快速地获得具有超低模数、超低粘度、强稳定性特征的硅酸钠溶液。Compared with the existing commercial products, the embodiment of the present invention refers to the sodium silicate solution (0<n≤0.5) with a modulus less than or equal to 0.5 as an ultra-low modulus sodium silicate solution. The present invention has more prominent advantages in the preparation of ultra-low modulus sodium silicate solutions with n≤0.5: based on the rapid dissolution of nano-SiO 2 particles in strong alkali solutions at room temperature to form monomers [SiO n (OH) 4-n ] Based on the principle of n- , nano-SiO 2 particles can quickly supplement the soluble silicon in the solution, and quickly obtain a sodium silicate solution with ultra-low modulus, ultra-low viscosity, and strong stability.

作为优选,所述纳米SiO2颗粒的比表面积为120~400m2/g,粒度D0.5为7~200nm。Preferably, the specific surface area of the nano-SiO 2 particles is 120-400 m 2 /g, and the particle size D0.5 is 7-200 nm.

作为优选,所述纳米SiO2颗粒为亲水型纳米SiO2颗粒。Preferably, the nano-SiO 2 particles are hydrophilic nano-SiO 2 particles.

作为优选,所述搅拌为机械搅拌,所述搅拌的转速为500~900r/min,时间为10~30min;所述分散为超声分散,其在机械搅拌后随之进行,所述分散的时间为5~10min。Preferably, the stirring is mechanical stirring, the stirring speed is 500-900r/min, and the time is 10-30min; the dispersion is ultrasonic dispersion, which is carried out after mechanical stirring, and the dispersion time is 5~10min.

作为优选,当设定模数n≥0.6时,将纳米SiO2颗粒分成质量相近的两份,并分两次加入,以避免一次加入而造成无法搅拌。As a preference, when the modulus n≥0.6 is set, the nano-SiO 2 particles are divided into two parts with similar mass, and added in two parts, so as to avoid failure to stir due to one-time addition.

本发明实施例还提供了一种低模数硅酸钠溶液,其由前述的制备方法在常温下制得。The embodiment of the present invention also provides a low modulus sodium silicate solution, which is prepared by the aforementioned preparation method at normal temperature.

本发明实施例中,低模数硅酸钠溶液的制备方法简单快速,是在常温下进行,即配即用,无需长时间陈放使之达到平衡。In the embodiment of the present invention, the preparation method of the low-modulus sodium silicate solution is simple and fast, and it is carried out at room temperature, ready to use after mixing, and does not need to be aged for a long time to achieve equilibrium.

本发明通过采用高活性纳米SiO2的“提供补偿可溶性硅”的作用,使得到的低模数的硅酸钠溶液具有活性高、粘度低、稳定性好的特点。The present invention adopts the function of "providing compensation for soluble silicon" of highly active nano- SiO2 , so that the obtained low-modulus sodium silicate solution has the characteristics of high activity, low viscosity and good stability.

本发明的低模数硅酸钠溶液不仅具有超低粘度特征,而且因可溶性硅的供给状态改变而可长时间储存,这显然有利于碱激发胶凝材料的工业化生产与应用。The low-modulus sodium silicate solution of the present invention not only has the characteristics of ultra-low viscosity, but also can be stored for a long time due to changes in the supply state of soluble silicon, which is obviously beneficial to the industrial production and application of alkali-activated gelling materials.

作为优选,所述低模数硅酸钠溶液的粘度为10~20mPa·s。Preferably, the viscosity of the low modulus sodium silicate solution is 10-20 mPa·s.

本发明实施例还提供了一种碱激发胶凝材料,其以前述的低模数硅酸钠溶液作为碱激发剂,所述的低模数硅酸钠溶液为清澈溶液,机械搅拌与超声分散后不需陈放,可立即用于制备碱激发胶凝材料The embodiment of the present invention also provides an alkali-activated gelling material, which uses the aforementioned low-modulus sodium silicate solution as an alkali activator, and the low-modulus sodium silicate solution is a clear solution, mechanically stirred and ultrasonically dispersed It can be used immediately to prepare alkali-activated gelling materials without aging

本发明的原理如下:在常温条件下,纳米SiO2颗粒在强碱溶液中可溶解,NaOH溶液为强碱性溶液,纳米SiO2颗粒在常温条件下可快速溶于其中。采用微量热仪测定在2.2g的NaOH溶液(含有0.2g的Na2O+2.0g的水)中添加0.03g纳米SiO2颗粒的放热速率曲线,如图1所示。结果表明,在20℃的环境中溶液存在明显长时间放热过程,这说明纳米SiO2颗粒与NaOH溶液存在某种化学过程。根据其放热历程,解释如下:亲水型纳米SiO2颗粒表面被水润湿而放热,表现为第一阶段持续数十分钟的剧烈放热;亲水型纳米SiO2颗粒溶于溶液放热,释放可溶性硅并形成[SiOn(OH)4-n]n-,表现为第二阶段持续数小时的缓慢放热。上述放热行为证实了纳米SiO2颗粒可溶于NaOH溶液中。该过程虽然较长,但无论何时使用配制的低模数硅酸钠溶液,纳米SiO2颗粒均可发挥其改性效应。若即配即用,溶液中纳米SiO2颗粒只有部分溶解,此时其可同时发挥提供可溶性的化学作用和超细颗粒的物理填充作用、晶核作用;若长时间陈放后再用,溶液中纳米SiO2颗粒已完全溶解,可最大程度上发挥提供可溶性的化学作用。The principle of the present invention is as follows: under normal temperature conditions, nanometer SiO2 particles can be dissolved in strong alkali solution, and NaOH solution is a strong alkaline solution, and nanometer SiO2 particles can be rapidly dissolved therein under normal temperature conditions. The exothermic rate curve of adding 0.03 g of nanometer SiO 2 particles to 2.2 g of NaOH solution (containing 0.2 g of Na 2 O+2.0 g of water) was measured by a microcalorimeter, as shown in FIG. 1 . The results show that there is an obvious long-term exothermic process in the solution at 20 °C, which indicates that there is a certain chemical process between nano-SiO 2 particles and NaOH solution. According to its exothermic history, the explanation is as follows: the surface of hydrophilic nano-SiO 2 particles is wetted by water and exothermic, which is manifested as the first stage of intense exotherm lasting tens of minutes ; heat, releasing soluble silicon and forming [SiO n (OH) 4-n ] n- , manifested by a second stage of slow exotherm lasting several hours. The above exothermic behavior confirms that the nano- SiO2 particles are soluble in NaOH solution. Although the process is long, nano- SiO2 particles can exert their modification effect whenever the formulated low-modulus sodium silicate solution is used. If it is prepared and used immediately, the nano- SiO2 particles in the solution are only partially dissolved, and at this time it can simultaneously play the chemical role of providing solubility, the physical filling role of ultrafine particles, and the role of crystal nucleation; if it is used after a long time, the solution will The nano- SiO2 particles are fully dissolved to maximize the chemistry that provides solubility.

采用激光粒度仪,可进一步证实纳米SiO2颗粒在NaOH溶液的溶解特性。以激光粒度仪的遮光度这一参数来表征纳米SiO2颗粒的溶解特性。遮光度是指溶液中颗粒的光学浓度,当颗粒越细且分散得越好,在添加相同质量颗粒的前提下溶液的遮光度越高。纳米SiO2颗粒的尺寸很小,达到纳米级,当其添加少量至溶液中并经超声分散后,溶液遮光度将很快接近20%。若纳米SiO2一直以颗粒的形态分散于溶液中,溶液的遮光度将维持在20%左右。在NaOH溶液中添加纳米SiO2颗粒后溶液遮光度的变化曲线,如图2所示。结果表明,在数十分钟内溶液遮光度快速下降,这意味着纳米SiO2颗粒的溶解;随后遮光度缓慢变小,且这种趋势维持至数百分钟,这说明纳米SiO2颗粒逐渐溶解;当经历足够长时间(200分钟)后,遮光度已由最初的约20%降低至约1%,这说明再在此期间绝大部分纳米SiO2颗粒均已溶解。该过程持续的时长与纳米SiO2颗粒加入到NaOH溶液中的放热时长几乎一致,这再次说明纳米SiO2颗粒在NaOH溶液中的可溶性,即纳米SiO2颗粒在该溶液中确实可起到提供可溶性硅的作用。Using a laser particle size analyzer, the dissolution characteristics of nano-SiO 2 particles in NaOH solution can be further confirmed. The shading degree of the laser particle size analyzer is used to characterize the dissolution characteristics of nano-SiO 2 particles. The shading degree refers to the optical concentration of the particles in the solution. When the particles are finer and better dispersed, the shading degree of the solution is higher under the premise of adding the same mass of particles. The size of nano-SiO 2 particles is very small, reaching the nanometer level. When a small amount of it is added to the solution and dispersed by ultrasonic waves, the shading degree of the solution will soon approach 20%. If the nano-SiO 2 has been dispersed in the solution in the form of particles, the shading degree of the solution will be maintained at about 20%. The change curve of the shading degree of the solution after adding nano- SiO2 particles in the NaOH solution is shown in Figure 2. The results show that the shading of the solution decreases rapidly within tens of minutes, which means the dissolution of nano-SiO 2 particles; then the shading decreases slowly, and this trend lasts for hundreds of minutes, which means that the nano-SiO 2 particles dissolve gradually; After a sufficient time (200 minutes), the shading has been reduced from the initial 20% to about 1%, which shows that most of the nano- SiO2 particles have been dissolved during this period. The duration of this process is almost the same as the exothermic duration of adding nano- SiO2 particles into NaOH solution, which shows again the solubility of nano- SiO2 particles in NaOH solution, that is, nano- SiO2 particles can indeed play a role in providing The role of soluble silicon.

纳米SiO2颗粒的溶解过程必然伴随着溶液粘度的变化。若纳米SiO2呈颗粒状态,因其亲水特性必然使溶液粘度显著变大;若其溶解并成为溶液组分时粘度必然显著下降。在NaOH溶液中添加纳米SiO2颗粒后溶液粘度的变化曲线,如图3所示。结果表明,常温下添加纳米SiO2后溶液的粘度变化规律符合上述推测,且溶液由浑浊状态变为澄清状态,粘度接近初始溶液,这再次说明纳米SiO2颗粒的可溶特性,且对溶液粘度几乎无影响。The dissolution process of nano-SiO 2 particles is bound to be accompanied by the change of solution viscosity. If nano-SiO 2 is in a granular state, the viscosity of the solution will increase significantly because of its hydrophilic properties; if it dissolves and becomes a solution component, the viscosity will inevitably decrease significantly. The change curve of solution viscosity after adding nano- SiO2 particles in NaOH solution is shown in Fig. 3. The results show that the change of viscosity of the solution after adding nano - SiO2 at room temperature is in line with the above speculation, and the solution changes from a turbid state to a clear state, and the viscosity is close to the initial solution. Almost no effect.

基于上述所述的纳米SiO2颗粒在常温NaOH溶液中的可溶解特性,本发明设计了在NaOH溶液中添加纳米SiO2颗粒、制备低模数硅酸钠溶液的方案。该方案在常温下可快速获得低模数硅酸钠溶液,且该溶液具有高活性、低粘度、高稳定性特征。Based on the above-mentioned dissolvability of nano- SiO2 particles in NaOH solution at room temperature, the present invention designs a scheme for adding nano- SiO2 particles to NaOH solution to prepare low-modulus sodium silicate solution. This solution can quickly obtain low modulus sodium silicate solution at normal temperature, and the solution has the characteristics of high activity, low viscosity and high stability.

下面将结合具体实施例对本发明作进一步说明,但不能理解为是对本发明保护范围的限制,该领域的技术人员根据上述本发明的内容对本发明作出的一些非本质的改进和调整,仍属于本发明的保护范围。The present invention will be further described below in conjunction with specific embodiment, but can not be interpreted as the restriction to protection scope of the present invention, some non-essential improvement and adjustment that those skilled in the art make to the present invention according to the content of the above-mentioned present invention still belong to this invention. protection scope of the invention.

实施例1Example 1

在NaOH溶液中添加纳米SiO2颗粒配制模数为0.15、0.30、0.45的低模数硅酸钠溶液。Add nanometer SiO 2 particles to NaOH solution to prepare low modulus sodium silicate solutions with modulus of 0.15, 0.30, 0.45.

假定碱激发胶凝材料的水灰比为0.5,激发剂用量为6.813%(以其Na2O含量占碱激发胶凝材料中的粉体原料的质量百分比计,下同),则配制满足450g粉体原料所需的溶液各参数,见表1。Assuming that the water-cement ratio of the alkali-activated gelling material is 0.5, and the dosage of the activator is 6.813% (based on the mass percentage of the Na2O content in the powder raw material in the alkali-activated gelling material, the same below), then the preparation meets the requirement of 450g See Table 1 for the parameters of the solution required for powder raw materials.

表1配制模数为0.15、0.30、0.45的低模数硅酸钠溶液的参数Table 1 prepares the parameters of low modulus sodium silicate solution with modulus of 0.15, 0.30, 0.45

水/gwater/g 所需NaOH溶液浓度/(mol/L)Required concentration of NaOH solution/(mol/L) 所需NaOH溶液体积/LRequired volume of NaOH solution/L 纳米SiO<sub>2</sub>/gNano-SiO<sub>2</sub>/g 模数modulus 225225 4.404.40 0.2250.225 4.454.45 0.150.15 225225 4.404.40 0.2250.225 8.908.90 0.300.30 225225 4.404.40 0.2250.225 13.3513.35 0.450.45

纳米SiO2颗粒:亲水型,颗粒尺寸为7-40nm(D0.5=14nm),比表面积为400m2/g。Nano SiO 2 particles: hydrophilic type, particle size is 7-40nm (D0.5=14nm), specific surface area is 400m 2 /g.

水:225g,自来水。Water: 225g, tap water.

NaOH:39.56g,工业级片碱。NaOH: 39.56g, industrial grade caustic soda.

NaOH溶液:将片碱溶于225g水中,搅拌,密封,冷却,获得浓度为4.40mol/L的NaOH溶液。NaOH solution: dissolve caustic soda in 225g of water, stir, seal, and cool to obtain a NaOH solution with a concentration of 4.40mol/L.

常温下,分别将4.45g、8.90g、13.35g纳米SiO2颗粒加入到NaOH溶液中,在转速为500r/min的条件下机械搅拌10min,再超声分散5min,获得低模数的硅酸钠溶液,备用。At room temperature, add 4.45g, 8.90g, and 13.35g of nano- SiO2 particles into the NaOH solution, stir mechanically at a speed of 500r/min for 10min, and then ultrasonically disperse for 5min to obtain a low-modulus sodium silicate solution ,spare.

以FTIR图谱结果来说明纳米SiO2颗粒提供可溶性硅的作用。在NaOH溶液中添加纳米SiO2颗粒后FTIR振动特征的变化曲线,如图4所示。由结果可知,当纳米SiO2颗粒添加到NaOH溶液中后,其O-Si-O的特征振动谱带(1108cm-1)及Si-OH的特征振动谱带(810cm-1)消失,这说明纳米SiO2颗粒在该溶液中发生了溶解。添加有纳米SiO2颗粒的NaOH溶液,在波数为1000cm-1出现明显振动谱带,这是纳米SiO2颗粒溶解为[SiOn(OH)4-n]n-后对应的O-Si-O振动。比较模数为0.15、0.30、0.45的硅酸钠溶液,三者几乎无明显差别,这说明纳米SiO2颗粒无论掺量多少,均可溶于溶液,且提供的可溶性硅并无差异。The role of nano-SiO 2 particles in providing soluble silicon is illustrated by the results of FTIR spectra. The change curve of FTIR vibration characteristics after adding nano- SiO2 particles in NaOH solution is shown in Fig. 4. It can be seen from the results that when nano-SiO 2 particles are added to NaOH solution, the characteristic vibration band of O-Si-O (1108cm -1 ) and Si-OH characteristic vibration band (810cm -1 ) disappear, which shows that Nano-SiO 2 particles were dissolved in this solution. The NaOH solution added with nano-SiO 2 particles has an obvious vibration band at the wave number of 1000cm -1 , which is the corresponding O-Si-O after the nano-SiO 2 particles are dissolved into [SiO n (OH) 4-n ] n- vibration. Comparing the sodium silicate solutions with moduli of 0.15, 0.30, and 0.45, there is almost no significant difference among the three, which shows that no matter how much the nano- SiO2 particles are added, they can be dissolved in the solution, and there is no difference in the soluble silicon provided.

上述结果说明利用纳米SiO2颗粒“提供可溶性硅”作用而快速制备低模数硅酸钠溶液的方法切实可行。The above results show that it is feasible to rapidly prepare low-modulus sodium silicate solution by using nano-SiO 2 particles to "provide soluble silicon".

以NaOH溶液和上述硅酸钠溶液为激发剂,制备碱激发胶凝材料的砂浆试样。当NaOH溶液、硅酸钠溶液掺量为0.225L时,砂浆试样的水灰比恰好为0.5,激发剂用量恰好为6.813%。Using NaOH solution and the above-mentioned sodium silicate solution as activators, a mortar sample of alkali-activated gelling material was prepared. When the amount of NaOH solution and sodium silicate solution is 0.225L, the water-cement ratio of the mortar sample is just 0.5, and the amount of activator is just 6.813%.

以粉煤灰及矿渣粉作为原料,分别以NaOH溶液和上述硅酸钠溶液作为激发剂制备碱激发胶凝材料。胶凝材料配比为:90%粉煤灰与10%矿渣粉(比表面积405m2/kg,下同)为粉体原料。Alkali-activated gelling materials were prepared using fly ash and slag powder as raw materials, and NaOH solution and the above-mentioned sodium silicate solution as activators respectively. The ratio of the cementitious material is: 90% fly ash and 10% slag powder (specific surface area 405m 2 /kg, the same below) as powder raw materials.

按照《水泥胶砂强度检验方法(ISO法)》(GB/T 17671)制备试样、测定强度,但养护条件为常温的潮湿空气(RH=95±5%)。NaOH溶液和模数为0.15、0.30、0.45的硅酸钠溶液作为激发剂时的效果对比结果,见表2。Prepare samples and measure strength according to "Cement Mortar Strength Test Method (ISO Method)" (GB/T 17671), but the curing condition is humid air at normal temperature (RH=95±5%). See Table 2 for the comparison results of NaOH solution and sodium silicate solutions with moduli of 0.15, 0.30, and 0.45 as activators.

上述配比的胶凝材料,若以低浓度(≤3.0mol/L)NaOH溶液作为激发剂,常温下凝结异常缓慢,早期几乎无强度,且后期强度不超过10.0MPa。因此,需提升NaOH溶液的浓度和掺量。当NaOH溶液≥4.0mol/L且掺量大于5%时,常温下试样可正常凝结,其早后期均具有足够强度。For the gelling material with the above ratio, if a low concentration (≤3.0mol/L) NaOH solution is used as the activator, the coagulation is abnormally slow at room temperature, with almost no strength in the early stage, and the strength in the later stage does not exceed 10.0MPa. Therefore, it is necessary to increase the concentration and dosage of NaOH solution. When the NaOH solution is ≥ 4.0mol/L and the dosage is greater than 5%, the sample can coagulate normally at room temperature, and its early and late stages have sufficient strength.

表2 NaOH溶液和上述硅酸钠溶液作为激发剂时的效果对比Table 2 Comparison of the effects of NaOH solution and the above-mentioned sodium silicate solution as stimulators

注:模数为0即指激发剂为NaOH溶液Note: The modulus is 0 means that the activator is NaOH solution

由表2可知,以模数为0.15、0.30、0.45的硅酸钠溶液作为激发剂时的3天强度和28天强度都比以NaOH溶液作为激发剂时有所提高,而且随着模数的增大而逐渐升高。这正是由于纳米SiO2颗粒提供可溶性硅的作用,这种作用不仅促进了早期强度发展,更是对后期强度提升明显。例如,0.45模数的硅酸钠溶液作为激发剂时,28天试样的抗压强度较NaOH溶液激发试样提高了17.1MPa,提升幅度显著。It can be seen from Table 2 that when using sodium silicate solutions with modulus of 0.15, 0.30, and 0.45 as the activator, the 3-day strength and 28-day strength are all higher than when NaOH solution is used as the activator, and with the increase of the modulus increasing gradually. This is precisely due to the role of nano-SiO 2 particles in providing soluble silicon, which not only promotes the development of early strength, but also significantly improves the later strength. For example, when the sodium silicate solution with a modulus of 0.45 is used as the activator, the compressive strength of the 28-day sample is 17.1MPa higher than that of the sample excited by the NaOH solution, which is a significant increase.

实施例2Example 2

实施例1从结构特征方面证实了纳米SiO2颗粒的可溶解性,并证实了其提供可溶性硅的有效性。实施例2将扩大模数范围,进一步验证纳米SiO2颗粒对NaOH溶液的改性效果。Example 1 confirmed the solubility of nano- SiO2 particles from the aspect of structural characteristics, and confirmed its effectiveness in providing soluble silicon. Example 2 will expand the modulus range, and further verify the modification effect of nano- SiO2 particles on NaOH solution.

纳米SiO2颗粒:亲水型,颗粒尺寸为16-50nm(D0.5=30nm),比表面积290m2/g。Nano SiO 2 particles: hydrophilic type, particle size 16-50nm (D0.5=30nm), specific surface area 290m 2 /g.

水:225g,自来水。Water: 225g, tap water.

NaOH:39.56g,工业级片碱。NaOH: 39.56g, industrial grade caustic soda.

NaOH溶液:将片碱溶于225g水中,搅拌,密封,冷却,获得浓度为4.40mol/L的NaOH溶液。NaOH solution: dissolve caustic soda in 225g of water, stir, seal, and cool to obtain a NaOH solution with a concentration of 4.40mol/L.

常温下,分别将14.83g、17.80g、20.77g、23.74g、26.70g、29.67g纳米SiO2颗粒加入到0.225L上述NaOH溶液中,在转速为700r/min的条件下机械搅拌30min,再超声分散10min,获得模数为0.5、0.6、0.7、0.8、0.9、1.0的硅酸钠溶液,备用。由于纳米SiO2颗粒添加量增加,故机械搅拌适当加速,搅拌、超声时长有所延长。At room temperature, add 14.83g, 17.80g, 20.77g, 23.74g, 26.70g, 29.67g of nano- SiO2 particles into 0.225L of the above NaOH solution, mechanically stir for 30min at a speed of 700r/min, and then ultrasonically Disperse for 10 minutes to obtain sodium silicate solutions with modulus of 0.5, 0.6, 0.7, 0.8, 0.9, 1.0 and set aside. Due to the increase in the addition of nano-SiO 2 particles, the mechanical stirring was properly accelerated, and the duration of stirring and ultrasonication was prolonged.

需要指出的是,在配制模数为0.7、0.8、0.9、1.0的硅酸钠溶液时,纳米SiO2颗粒分两次加入,具体如下:It should be pointed out that when preparing sodium silicate solutions with moduli of 0.7, 0.8, 0.9, and 1.0, nano- SiO2 particles are added in two times, as follows:

模数为0.7的硅酸钠溶液:第一次加入10.77g纳米SiO2颗粒,在转速为700r/min的条件下机械搅拌30min,再超声分散10min;获得澄清溶液后立即再加入10.00g纳米SiO2颗粒,在转速为700r/min的条件下机械搅拌30min,随之超声分散10min。Sodium silicate solution with a modulus of 0.7: Add 10.77g of nano- SiO2 particles for the first time, mechanically stir at a speed of 700r/min for 30min, and then ultrasonically disperse for 10min; immediately after obtaining a clear solution, add 10.00g of nano-SiO 2 Particles were stirred mechanically for 30 minutes at a rotational speed of 700r/min, followed by ultrasonic dispersion for 10 minutes.

模数为0.8的硅酸钠溶液:第一次加入12.74g纳米SiO2颗粒,在转速为700r/min的条件下机械搅拌30min,再超声分散10min;获得澄清溶液后立即再加入11.00g纳米SiO2颗粒,在转速为700r/min的条件下机械搅拌30min,随之超声分散10min。Sodium silicate solution with a modulus of 0.8: Add 12.74g of nano- SiO2 particles for the first time, mechanically stir at a speed of 700r/min for 30min, and then ultrasonically disperse for 10min; immediately after obtaining a clear solution, add 11.00g of nano-SiO 2 Particles were stirred mechanically for 30 minutes at a rotational speed of 700r/min, followed by ultrasonic dispersion for 10 minutes.

模数为0.9的硅酸钠溶液:第一次加入13.70g纳米SiO2颗粒,在转速为700r/min的条件下机械搅拌30min,再超声分散10min;获得澄清溶液后立即再加入13.00g纳米SiO2颗粒,在转速为700r/min的条件下机械搅拌30min,随之超声分散10min。Sodium silicate solution with a modulus of 0.9: Add 13.70g of nano- SiO2 particles for the first time, mechanically stir at a speed of 700r/min for 30min, and then ultrasonically disperse for 10min; immediately after obtaining a clear solution, add 13.00g of nano-SiO 2 Particles were stirred mechanically for 30 minutes at a rotational speed of 700r/min, followed by ultrasonic dispersion for 10 minutes.

模数为1.0的硅酸钠溶液:第一次加入15.67g纳米SiO2颗粒,在转速为700r/min的条件下机械搅拌30min,再超声分散10min;获得澄清溶液后立即再加入14.00g纳米SiO2颗粒,在转速为700r/min的条件下机械搅拌30min,随之超声分散10min。Sodium silicate solution with a modulus of 1.0: Add 15.67g of nano- SiO2 particles for the first time, mechanically stir at a speed of 700r/min for 30min, and then ultrasonically disperse for 10min; immediately after obtaining a clear solution, add 14.00g of nano-SiO 2 Particles were stirred mechanically for 30 minutes at a rotational speed of 700r/min, followed by ultrasonic dispersion for 10 minutes.

当NaOH溶液和上述硅酸钠溶液掺量为0.225L时,砂浆试样的水灰比恰好为0.5,激发剂用量恰好为6.813%。When the amount of NaOH solution and the above-mentioned sodium silicate solution is 0.225L, the water-cement ratio of the mortar sample is exactly 0.5, and the dosage of the activator is just 6.813%.

以粉煤灰及矿渣粉作为原料,分别以NaOH溶液和上述硅酸钠溶液作为激发剂制备碱激发胶凝材料。胶凝材料配比为:90%粉煤灰与10%矿渣粉(比表面积405m2/kg,下同)为粉体原料。采用微量热仪观测胶凝材料的水化放热过程,结果如图5所示。根据水化放热结果可知,以NaOH溶液作为激发剂时,仅观察到了润湿、溶解对应的第一明显放热峰,而碱激发反应(硅铝聚合反应)对应的特征放热(第二放热峰)并不明显,即其水化过程缓慢,这正是试样强度偏低的主要原因。当采用低模数的硅酸钠溶液作为激发剂时,碱激发反应特征放热峰(第二放热峰)逐渐明显,这显然是纳米SiO2颗粒提供的可溶性硅对反应的促进作用。Alkali-activated gelling materials were prepared using fly ash and slag powder as raw materials, and NaOH solution and the above-mentioned sodium silicate solution as activators respectively. The ratio of the cementitious material is: 90% fly ash and 10% slag powder (specific surface area 405m 2 /kg, the same below) as powder raw materials. The exothermic process of hydration of the gelled material was observed with a microcalorimeter, and the results are shown in Figure 5. According to the exothermic results of hydration, when NaOH solution was used as the activator, only the first obvious exothermic peak corresponding to wetting and dissolution was observed, while the characteristic exothermic peak (second Exothermic peak) is not obvious, that is, its hydration process is slow, which is the main reason for the low strength of the sample. When the sodium silicate solution with low modulus is used as the activator, the characteristic exothermic peak (second exothermic peak) of the alkali excitation reaction is gradually obvious, which is obviously the promotion of the reaction by the soluble silicon provided by the nano-SiO 2 particles.

按照《水泥胶砂强度检验方法(ISO法)》(GB/T 17671)制备试样、测定强度,但养护条件为常温的潮湿空气(RH=95±5%),其结果见表3。Prepare samples and measure strength according to "Cement Mortar Strength Test Method (ISO Method)" (GB/T 17671), but the curing condition is humid air at room temperature (RH=95±5%), and the results are shown in Table 3.

表3 NaOH溶液和模数为0.5~1.0的硅酸钠溶液作为激发剂时的效果对比Table 3 Comparison of the effects of NaOH solution and sodium silicate solution with a modulus of 0.5-1.0 as activators

注:模数为0即指激发剂为NaOH溶液Note: The modulus is 0 means that the activator is NaOH solution

由表3可见,随着模数增大,试样的3天强度、28天强度都逐渐升高,说明纳米SiO2颗粒提供的可溶性硅对强度增长的作用越来越明显,这说明采用将纳米SiO2颗粒溶于NaOH溶液制备低模数硅酸钠溶液的方法是切实可行的。It can be seen from Table 3 that as the modulus increases, the 3-day strength and 28-day strength of the sample gradually increase, indicating that the soluble silicon provided by nano-SiO 2 particles has an increasingly obvious effect on the strength growth, which shows that using the It is feasible to prepare low modulus sodium silicate solution by dissolving nano SiO 2 particles in NaOH solution.

实施例3Example 3

为了进一步验证本发明方法的有效性,拟对比传统方法获得的水玻璃溶液与本发明获得硅酸钠溶液的激发效果,并比较粘度、pH值等参数。In order to further verify the effectiveness of the method of the present invention, the excitation effect of the sodium silicate solution obtained by comparing the water glass solution obtained by the traditional method with the sodium silicate solution obtained by the present invention is proposed, and parameters such as viscosity and pH value are compared.

(1)传统方法获得低模数的水玻璃溶液(1) The traditional method obtains the water glass solution of low modulus

采用添加片碱蒸煮的方式,将模数由高调低。The modulus is adjusted from high to low by adding caustic soda for cooking.

初始水玻璃溶液:模数为2.4,固含量为45.7%,pH值为12.8,粘度为345mPa·s。Initial water glass solution: the modulus is 2.4, the solid content is 45.7%, the pH value is 12.8, and the viscosity is 345mPa·s.

在100g模数为2.4的初始水玻璃溶液中,添加24.84g片碱和102.5g水,搅拌、密封、煮沸、冷却并陈放24小时。调整后水玻璃溶液的固含量为28.6%,模数为1.0。以调整后的该水玻璃溶液作为碱激发胶凝材料的激发剂时,当添加量为20%(以其固体占粉体的质量百分比计;折算为Na2O,掺量为10.16%)时,胶凝材料砂浆试样的水灰比恰好为0.5。In 100g of the initial water glass solution with a modulus of 2.4, add 24.84g of caustic soda and 102.5g of water, stir, seal, boil, cool and age for 24 hours. After adjustment, the solid content of the water glass solution is 28.6%, and the modulus is 1.0. When the adjusted water glass solution is used as the activator of the alkali-activated gelling material, when the addition amount is 20% (in terms of the mass percentage of its solids in the powder; converted to Na 2 O, the dosage is 10.16%) , the water-cement ratio of the cementitious mortar sample is exactly 0.5.

(2)本发明方法获得低模数的水玻璃溶液(2) the inventive method obtains the water glass solution of low modulus

在NaOH溶液添加纳米SiO2颗粒,将模数由零调高。Add nano- SiO2 particles in NaOH solution to increase the modulus from zero.

纳米SiO2颗粒:亲水型,颗粒尺寸为150-200nm(D0.5=185nm),比表面积120m2/g。Nano SiO 2 particles: hydrophilic type, the particle size is 150-200nm (D0.5=185nm), and the specific surface area is 120m 2 /g.

水:225g,自来水。Water: 225g, tap water.

NaOH:58.99g,工业级片碱。NaOH: 58.99g, industrial grade caustic soda.

NaOH溶液:将片碱溶于225g水中,搅拌,密封,冷却,获得浓度为6.55mol/L的NaOH溶液。NaOH solution: dissolve caustic soda in 225g of water, stir, seal, and cool to obtain a NaOH solution with a concentration of 6.55mol/L.

常温下,第一次加入22.25g纳米SiO2颗粒,在转速为900r/min的条件下机械搅拌30min,再超声分散10min;获得澄清溶液后立即再加入22.00g纳米SiO2颗粒,在转速为900r/min的条件下机械搅拌30min,随之超声分散10min。获得澄清溶液,备用。At room temperature, add 22.25g of nano- SiO2 particles for the first time, mechanically stir for 30min at a speed of 900r/min, and then ultrasonically disperse for 10min; immediately after obtaining a clear solution, add 22.00g of nano- SiO2 particles, Under the condition of 1/min, mechanically stir for 30min, followed by ultrasonic dispersion for 10min. Obtain a clear solution and set aside.

以粉煤灰及矿渣粉作为原料,分别以传统方法获得的上述水玻璃溶液和本发明方法获得的上述硅酸钠溶液作为激发剂制备碱激发胶凝材料。胶凝材料配比为:90%粉煤灰与10%矿渣粉(比表面积405m2/kg,下同)为粉体原料。450g粉体(含360g粉煤灰,90g矿粉),按照《水泥胶砂强度检验方法(ISO法)》(GB/T 17671)制备试样、测定强度,但养护条件为常温的潮湿空气(RH=95±5%)。The alkali-activated gelling material is prepared by using fly ash and slag powder as raw materials, and using the above-mentioned water glass solution obtained by the traditional method and the above-mentioned sodium silicate solution obtained by the method of the present invention as activators respectively. The ratio of the cementitious material is: 90% fly ash and 10% slag powder (specific surface area 405m 2 /kg, the same below) as powder raw materials. 450g powder (including 360g fly ash, 90g mineral powder), according to the "cement mortar strength test method (ISO method)" (GB/T 17671) to prepare samples, measure the strength, but the curing condition is humid air at normal temperature ( RH=95±5%).

当掺入314.7g由传统方法获得的模数为1.0的水玻璃溶液,带入的碱量为45.84g(以Na2O计),带入的硅量为44.26g(以SiO2计),带入的水为225g,试样的水灰比恰恰为0.5。When being mixed with 314.7g by the water glass solution that the modulus that traditional method obtains is 1.0, the alkali amount that brings is 45.84g (in Na 2 O), the silicon amount that is brought in is 44.26g (in SiO ), The water brought in was 225g, and the water-cement ratio of the sample was just 0.5.

当掺入0.225L由本发明方法获得的模数为1.0的硅酸钠溶液,带入的碱量为45.72g(以Na2O计),带入的硅量为44.25g(以SiO2计),带入的水为225g,试样的水灰比恰恰为0.5。When being mixed with 0.225L the sodium silicate solution that the modulus obtained by the inventive method is 1.0, the amount of alkali that is brought in is 45.72g (in Na 2 O), and the amount of silicon that is brought in is 44.25g (in SiO ) , the water brought in is 225g, and the water-cement ratio of the sample is just 0.5.

由此可见,这两种不同激发剂具有一致的液相环境,这为本实例的效果比较设定了可靠边界条件。It can be seen that the two different activators have a consistent liquid phase environment, which sets a reliable boundary condition for the effect comparison of this example.

NaOH溶液、模数为2.4的初始水玻璃溶液、模数为1.0蒸煮水玻璃溶液及本发明的硅酸钠溶液作为激发剂时的效果对比与溶液参数,见表4。NaOH solution, modulus is the initial water glass solution of 2.4, modulus is 1.0 cooking water glass solution and sodium silicate solution of the present invention when as activator effect contrast and solution parameter, see Table 4.

表4 NaOH溶液和上述硅酸钠溶液作为激发剂时的效果对比与溶液参数Table 4 Effect comparison and solution parameters of NaOH solution and above-mentioned sodium silicate solution as stimulator

注:“/”指OH-浓度超过pH值表征范围,呈强碱性。所有试样的水灰比均为0.5,且激发剂带入的减量保持一致,以便比较激发效果。Note: "/" means that the concentration of OH- exceeds the characteristic range of pH value, and it is strongly alkaline. The water-cement ratio of all samples is 0.5, and the reduction brought by the activator is consistent, so as to compare the activating effect.

由表4可知,相比于采取蒸煮方式获得的低模数水玻璃溶液(前者),本发明获得的低模数硅酸钠溶液(后者)具有更优异的激发效果:后者激发试样的3天、28天强度要远远高于前者激发试样的。后者的粘度更低,因为前者是由高模数调整为低模数,其所含硅部分保留了高聚合状态,而后者是纳米SiO2颗粒溶解而获得,主要以高活性单体([SiOn(OH)4-n]n-)存在。此外,后者中OH-浓度已超出pH值能表征的范围,即溶液以离子态存在,可提供更强的碱性,这显然有利于碱激发反应;而前者仍然保留有聚合态特征,故其碱性可用pH值表征,即其碱性较后者弱,相应地激发效果较后者差,试样各龄期强度偏低。除碱性强弱这一影响因素外,后者还能提供更多的高活性单体([SiOn(OH)4-n]n-),而前者因仍然保留高聚合特征而使其单体提供能力受限,这也是造成其激发试样各龄期强度偏低另一原因。As can be seen from Table 4, compared with the low modulus water glass solution (the former) that adopts cooking method to obtain, the low modulus sodium silicate solution (the latter) that the present invention obtains has more excellent excitation effect: the latter excites sample The strength of the 3-day and 28-day samples is much higher than that of the former excitation sample. The viscosity of the latter is lower, because the former is adjusted from high modulus to low modulus, and the silicon contained in it retains a high polymerization state, while the latter is obtained by dissolving nano- SiO2 particles, mainly with high activity monomer ([ SiO n (OH) 4-n ] n- ) exists. In addition, the OH - concentration in the latter has exceeded the range that can be characterized by the pH value, that is, the solution exists in an ionic state, which can provide stronger alkalinity, which is obviously beneficial to the alkali-induced reaction; while the former still retains the characteristics of the polymeric state, so Its alkalinity can be characterized by pH value, that is, its alkalinity is weaker than that of the latter, and correspondingly its excitation effect is worse than that of the latter, and the intensity of each age of the sample is on the low side. In addition to the influence factor of alkalinity, the latter can also provide more highly active monomers ([SiO n (OH) 4-n ] n- ), while the former still retains high polymerization characteristics so that its single The ability to provide body is limited, which is also another reason for the low intensity of the stimulated samples at different ages.

相比于模数为2.4的初始水玻璃溶液(前者),本发明获得的低模数硅酸钠溶液(后者),所激发试样的抗压强度虽然较前者激发试样的低,但抗折强度却更高,这正是部分未溶解纳米SiO2颗粒填充于基体而起到增韧作用的后果。由此可见,本发明方法不仅可发挥提供高活性硅这一化学作用外,物理填充作用也不可忽视。需要说明的是,前者激发试样较后者激发试样拥有更高抗压强度的原因为:尽管前者处于高聚合特征,但总体上能够提供更多的可溶性硅,毕竟其硅含量为后者的2.4倍。Compared with the initial water glass solution (the former) that the modulus is 2.4, the low modulus sodium silicate solution (the latter) that the present invention obtains, although the compressive strength of the excited sample is lower than the former excited sample, but The flexural strength is higher, which is the result of some undissolved nano-SiO 2 particles filling the matrix and playing a toughening role. It can be seen that the method of the present invention can not only play the chemical role of providing highly active silicon, but also the physical filling role can not be ignored. It should be noted that the reason why the former excited sample has higher compressive strength than the latter excited sample is that although the former is characterized by high polymerization, it can provide more soluble silicon on the whole, after all, its silicon content is lower than that of the latter 2.4 times.

相比于NaOH溶液(前者),本发明获得的低模数硅酸钠溶液(后者),不仅表现为更强的激发效果,而且诸如粘度等溶液性质相近。Compared with the NaOH solution (the former), the low modulus sodium silicate solution (the latter) obtained by the present invention not only exhibits a stronger excitation effect, but also has similar solution properties such as viscosity.

上述比较结果证实了本发明方法的可行性,且证实了本发明获得的低模数硅酸钠溶液具有高活性、低粘度、强碱性特征。The above comparison results have confirmed the feasibility of the method of the present invention, and confirmed that the low modulus sodium silicate solution obtained by the present invention has high activity, low viscosity and strong alkalinity.

实施例4Example 4

本实施例将说明陈放时间对本发明获得的低模数硅酸钠溶液激发效果、溶液特征的影响。This example will illustrate the effect of aging time on the excitation effect and solution characteristics of the low modulus sodium silicate solution obtained in the present invention.

纳米SiO2颗粒:亲水型,颗粒尺寸为40-100nm(D0.5=72nm),比表面积275m2/g。Nano SiO 2 particles: hydrophilic type, the particle size is 40-100nm (D0.5=72nm), and the specific surface area is 275m 2 /g.

水:225g,自来水。Water: 225g, tap water.

NaOH:39.56g,工业级片碱。NaOH: 39.56g, industrial grade caustic soda.

NaOH溶液:将片碱溶于225g水中,搅拌,密封,冷却,获得浓度为4.40mol/L的NaOH溶液。NaOH solution: dissolve caustic soda in 225g of water, stir, seal, and cool to obtain a NaOH solution with a concentration of 4.40mol/L.

常温下,加入14.83g纳米SiO2颗粒,在转速为500r/min的条件下机械搅拌10min,再超声分散5min,获得模数为0.5的澄清溶液,备用。At room temperature, add 14.83g of nano- SiO2 particles, mechanically stir at a speed of 500r/min for 10min, and then ultrasonically disperse for 5min to obtain a clear solution with a modulus of 0.5, which is ready for use.

当上述硅酸钠溶液掺量为0.225L时,砂浆试样的水灰比恰好为0.5,激发剂用量恰好为6.813%。When the dosage of the above-mentioned sodium silicate solution is 0.225L, the water-cement ratio of the mortar sample is just 0.5, and the dosage of the activator is just 6.813%.

溶液陈放时间分别为0min,60min,120min,240min,480min,960min,1920min,3840min,7680min,259200min。The solution aging time is 0min, 60min, 120min, 240min, 480min, 960min, 1920min, 3840min, 7680min, 259200min.

以粉煤灰及矿渣粉作为原料,以陈放了不同时间的上述硅酸钠溶液作为激发剂制备碱激发胶凝材料。胶凝材料配比为:90%粉煤灰与10%矿渣粉(比表面积405m2/kg,下同)为粉体原料。按照《水泥胶砂强度检验方法(ISO法)》(GB/T 17671)制备试样、测定强度,但养护条件为常温的潮湿空气(RH=95±5%)。模数为0.5的硅酸钠溶液陈放不同时间后的激发效果对比与溶液参数变化,见表5。Alkali-activated gelling materials were prepared using fly ash and slag powder as raw materials and the above-mentioned sodium silicate solutions aged for different times as activators. The ratio of the cementitious material is: 90% fly ash and 10% slag powder (specific surface area 405m 2 /kg, the same below) as powder raw materials. Prepare samples and measure strength according to "Cement Mortar Strength Test Method (ISO Method)" (GB/T 17671), but the curing condition is humid air at normal temperature (RH=95±5%). See Table 5 for the comparison of the excitation effect and the change of the solution parameters of the sodium silicate solution with a modulus of 0.5 aged for different periods of time.

表5陈放不同时间后的激发效果对比与溶液参数变化Table 5 Comparison of excitation effect and solution parameter changes after aging for different time

注:“/”指OH-浓度超过pH值表征范围,呈强碱性。259200min的时长为180天。Note: "/" means that the concentration of OH- exceeds the characteristic range of pH value, and it is strongly alkaline. The duration of 259200min is 180 days.

由表5可见,该溶液即使长时间陈放(7680min,约5天),未发现分层、浑浊现象,仍然为澄清溶液。将该溶液最长陈放至259200min(180天),其外观特征仍然没有改变。上述现象说明本发明获得的低模数硅酸钠溶液稳定性优异,可长时间保存。通常,水泥等胶凝材料的保质期不超过六个月。因此,本发明获得的低模数硅酸钠溶液满足建筑工业的备料周期要求。As can be seen from Table 5, even if the solution is aged for a long time (7680min, about 5 days), no stratification or turbidity is found, and it is still a clear solution. The longest aging of this solution is 259200min (180 days), and its outward appearance characteristic still does not change. The above phenomenon shows that the low modulus sodium silicate solution obtained by the present invention has excellent stability and can be stored for a long time. Typically, cementitious materials such as cement have a shelf life of no more than six months. Therefore, the low modulus sodium silicate solution obtained by the present invention meets the requirements of the material preparation period of the construction industry.

由表5结果可知,该溶液无论陈放时间多长,其激发效果及粘度等性质均没有明显变化。当短时间陈放时,虽然纳米SiO2颗粒并不能完全溶解,即并不能全部转化为可溶性硅,但未溶解的颗粒发挥超细颗粒的物理填充及晶核作用,可在一定程度上弥补化学效应未能全部发挥的不足,故试样仍然表现出与长时间陈放溶液激发试样相当的强度;当长时间陈放时,纳米SiO2颗粒几乎全部溶解,此时其提供可溶性硅的化学效应得到完全发挥,相应地试样表现为足够高强度。正是由于在短时间陈放溶液中有部分未溶解的纳米SiO2颗粒,故溶液的粘度相对于长时间陈放的要大一些。随着陈放时间的延长,纳米SiO2颗粒逐渐溶解,溶液的粘度逐渐下降并维持在相当水平。From the results in Table 5, it can be seen that no matter how long the solution is stored, the properties such as its excitation effect and viscosity do not change significantly. When stored for a short period of time, although the nano- SiO2 particles cannot be completely dissolved, that is, they cannot be completely converted into soluble silicon, but the undissolved particles play the role of physical filling and crystal nucleation of ultra-fine particles, which can compensate for the chemical effect to a certain extent. Insufficiency that failed to fully play, so the sample still shows the strength equivalent to the sample excited by the long-term aging solution; when the long-term aging, the nano- SiO2 particles are almost completely dissolved, and the chemical effect of providing soluble silicon is fully obtained. Play, correspondingly the sample shows a sufficiently high strength. Just because there are some undissolved nano- SiO2 particles in the short-term aging solution, the viscosity of the solution is larger than that of the long-term aging solution. With the prolongation of aging time, the nano-SiO 2 particles gradually dissolve, and the viscosity of the solution decreases gradually and remains at a considerable level.

上述结果表明,本发明获得的低模数硅酸钠溶液具有优异稳定性,保质期可长达6个月。The above results show that the low modulus sodium silicate solution obtained by the present invention has excellent stability, and the shelf life can be as long as 6 months.

在上述实施例中,对各个实施例的描述都各有侧重,某个实施例中没有详述的部分,可以参见其他实施例的相关描述。In the foregoing embodiments, the descriptions of each embodiment have their own emphases, and for parts not described in detail in a certain embodiment, reference may be made to relevant descriptions of other embodiments.

以上所述,仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均仍属于本发明技术方案的范围内。The above are only preferred embodiments of the present invention, and are not intended to limit the present invention in any form. Any simple modifications, equivalent changes and modifications made to the above embodiments according to the technical essence of the present invention still belong to this invention. within the scope of the technical solution of the invention.

Claims (10)

1. A method for preparing a low modulus sodium silicate solution, comprising:
And (3) adding nano SiO2 particles into the NaOH solution at normal temperature, stirring and dispersing to obtain the low-modulus sodium silicate solution with the set modulus.
2. The method for preparing a low modulus sodium silicate solution according to claim 1,
The addition amount of the nano SiO2 particles satisfies formula (1):
m=30×c×V×n (1)
In the formula (1), the reaction mixture is,
m is the addition amount of nano SiO2 particles in NaOH solution, unit g;
c is the concentration of NaOH solution, unit mol/L;
V is the volume of NaOH solution, unit L;
n is a set modulus, where 0< n <1.
3. The method for preparing a low modulus sodium silicate solution according to claim 1,
The specific surface area of the nano SiO2 particles is 120-400 m2/g, and the particle size D0.5 is 7-200 nm.
4. The method for preparing a low modulus sodium silicate solution according to claim 1,
The nano SiO2 particles are hydrophilic nano SiO2 particles.
5. the method for preparing a low modulus sodium silicate solution according to claim 1,
The stirring is mechanical stirring, the rotating speed of the stirring is 500-900 r/min, and the time is 10-30 min; the dispersion is ultrasonic dispersion, which is carried out after mechanical stirring, and the dispersion time is 5-10 min.
6. The method for preparing a low modulus sodium silicate solution according to claim 1,
When the modulus n is set to be more than or equal to 0.6, the nano SiO2 particles are divided into two parts with similar mass and added in two times, so as to avoid the problem that stirring cannot be carried out due to one-time addition.
7. A low modulus sodium silicate solution, characterized in that it is prepared by the method of any one of claims 1 to 6.
8. The low modulus sodium silicate solution according to claim 7, wherein the viscosity of said low modulus sodium silicate solution is 10 to 20 mPa-s.
9. An alkali-activated cementitious material, characterised in that it uses as alkali activator the low modulus sodium silicate solution according to claim 7 or 8.
10. The alkali-activated cementitious material of claim 9, wherein the low modulus sodium silicate solution is a clear solution that can be used immediately to prepare the alkali-activated cementitious material without the need for aging after mechanical agitation and ultrasonic dispersion.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113416025A (en) * 2021-04-29 2021-09-21 浙江天地环保科技股份有限公司 Fast-hardening high-strength fly ash geopolymer material and preparation method thereof
CN114988418A (en) * 2021-03-02 2022-09-02 香港理工大学 Method for preparing nano silicon dioxide by using waste concrete sand powder
CN118545951A (en) * 2024-05-16 2024-08-27 中国矿业大学 A method and application of nanocomposite excitation solution to enhance the mineralization of solid waste materials

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4332601A (en) * 1979-01-12 1982-06-01 Akzo N.V. Method for making silica fibers
CN102424392A (en) * 2011-09-11 2012-04-25 中国科学院过程工程研究所 Method for preparing white carbon black cogeneration nanometer calcium carbonate by integrally utilizing micro silicon powder
CN103896265A (en) * 2012-12-29 2014-07-02 苏州格瑞展泰再生能源有限公司 Method for producing activated carbon and inorganic silicon compounds from rice hulls
CN108101390A (en) * 2017-12-14 2018-06-01 中国建筑材料科学研究总院有限公司 The evaluation method of the alkali-activated carbonatite cementitious material extent of reaction
CN108249788A (en) * 2017-12-21 2018-07-06 中国建筑材料科学研究总院有限公司 Alkali-activated carbonatite cementitious material and preparation method thereof
CN109437614A (en) * 2018-12-29 2019-03-08 中国建筑材料科学研究总院有限公司 The alkali-activated carbonatite cementitious material and preparation method thereof of the low alkali soluble output of room temperature maintenance

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4332601A (en) * 1979-01-12 1982-06-01 Akzo N.V. Method for making silica fibers
CN102424392A (en) * 2011-09-11 2012-04-25 中国科学院过程工程研究所 Method for preparing white carbon black cogeneration nanometer calcium carbonate by integrally utilizing micro silicon powder
CN103896265A (en) * 2012-12-29 2014-07-02 苏州格瑞展泰再生能源有限公司 Method for producing activated carbon and inorganic silicon compounds from rice hulls
CN108101390A (en) * 2017-12-14 2018-06-01 中国建筑材料科学研究总院有限公司 The evaluation method of the alkali-activated carbonatite cementitious material extent of reaction
CN108249788A (en) * 2017-12-21 2018-07-06 中国建筑材料科学研究总院有限公司 Alkali-activated carbonatite cementitious material and preparation method thereof
CN109437614A (en) * 2018-12-29 2019-03-08 中国建筑材料科学研究总院有限公司 The alkali-activated carbonatite cementitious material and preparation method thereof of the low alkali soluble output of room temperature maintenance

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114988418A (en) * 2021-03-02 2022-09-02 香港理工大学 Method for preparing nano silicon dioxide by using waste concrete sand powder
CN113416025A (en) * 2021-04-29 2021-09-21 浙江天地环保科技股份有限公司 Fast-hardening high-strength fly ash geopolymer material and preparation method thereof
CN118545951A (en) * 2024-05-16 2024-08-27 中国矿业大学 A method and application of nanocomposite excitation solution to enhance the mineralization of solid waste materials

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