CN108875282A - The measuring method of the hydration reaction activation energy of concrete with added magnesium oxide and application - Google Patents
The measuring method of the hydration reaction activation energy of concrete with added magnesium oxide and application Download PDFInfo
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Abstract
本发明属于混凝土结构仿真技术领域，涉及外掺氧化镁混凝土的水化反应活化能的测算方法和应用。该方法包括：根据阿仑尼乌斯公式，建立氧化镁水化反应速率与温度、氧化镁水化度及水化反应活化能之间的关系；结合氧化镁水化度与混凝土膨胀量之间的关系，建立计算混凝土中氧化镁水化反应活化能的数学模型；利用所建立的数学模型，结合氧化镁混凝土自生体积变形的试验数据，计算氧化镁混凝土中的氧化镁水化反应活化能。本发明算法由数学方程推导，理论上严密，可直接借助氧化镁混凝土自生体积变形的数据求解；相比于直接采用氧化镁与水反应或者含氧化镁的水泥进行水化动力学分析，更能真实的反映氧化镁在混凝土内部的反应情况，方法简单，操作方便。
The invention belongs to the technical field of concrete structure simulation, and relates to a calculation method and application of the activation energy of hydration reaction of externally mixed magnesium oxide concrete. The method includes: according to the Arrhenius formula, establishing the relationship between the hydration reaction rate of magnesium oxide and temperature, the degree of hydration of magnesium oxide and the activation energy of hydration reaction; combining the relationship between the degree of hydration of magnesium oxide and the expansion of concrete The mathematical model for calculating the activation energy of magnesium oxide hydration reaction in concrete was established; using the established mathematical model, combined with the experimental data of magnesium oxide concrete autogenous volume deformation, the activation energy of magnesium oxide hydration reaction in magnesium oxide concrete was calculated. The algorithm of the present invention is deduced from mathematical equations, which is rigorous in theory and can be solved directly with the help of the data of autogenous volume deformation of magnesia concrete; compared with directly using magnesia and water reaction or hydration kinetics analysis of cement containing magnesia, it is more capable It truly reflects the reaction of magnesium oxide inside the concrete, and the method is simple and easy to operate.
Description
技术领域technical field
本发明属于混凝土结构仿真技术领域，具体而言，涉及一种外掺氧化镁混凝土的水化反应活化能的测算方法和应用。The invention belongs to the technical field of concrete structure simulation, and in particular relates to a method and application for measuring and calculating the activation energy of hydration reaction of externally mixed magnesium oxide concrete.
背景技术Background technique
在混凝土中掺加氧化镁，是一种非常有效的防裂技术之一：利用氧化镁水化的微膨胀性，可补偿混凝土在降温过程中产生的拉应力和体积收缩，从而到达防止结构开裂的目的。对氧化镁混凝土补偿收缩的研究，对于实际工程的研究和设计过程中，更加有效的利用氧化镁混凝土的收缩补偿功能，具有重要意义。方镁石的水化动力学是氧化镁混凝土膨胀的理论基础，对认识氧化镁的膨胀性能以及预测氧化镁的膨胀变形有重要意义，对氧化镁在水泥中的安定性评定也有指导作用。Adding magnesia to concrete is one of the very effective anti-cracking technologies: using the micro-expansion of magnesia hydration, it can compensate the tensile stress and volume shrinkage of concrete during the cooling process, so as to prevent structural cracking the goal of. The research on shrinkage compensation of magnesium oxide concrete is of great significance for more effective use of the shrinkage compensation function of magnesium oxide concrete in the process of actual engineering research and design. The hydration kinetics of periclase is the theoretical basis for the expansion of magnesia concrete. It is of great significance for understanding the expansion properties of magnesia and predicting the expansion deformation of magnesia. It also plays a guiding role in the evaluation of the stability of magnesia in cement.
方镁石的水化速度决定了氧化镁混凝土的膨胀性能，方镁石的水化速度与方镁石的生成条件(外部环境温度及湿度等)有很大关系。目前已有学者对轻烧氧化镁的水化动力学进行了研究，相关研究的结果表明轻烧氧化镁在纯水中的水化与其在水泥熟料中水化动力学方程存在明显的差异，这种差异与方镁石本身的性质和试验的方法有关。相较于直接与纯水进行反应，氧化镁在水泥混凝土中，情况要更为复杂。一些研究中采用水泥熟料内含的方镁石，这种方镁石生成温度高，水化活性低，并且会部分被水泥矿物包裹，方镁石的水化受水泥水化的影响。采用这种方法进行测试，直接反映了水泥中内含氧化镁的水化。The hydration rate of periclase determines the expansion performance of magnesia concrete, and the hydration rate of periclase has a great relationship with the formation conditions of periclase (external ambient temperature and humidity, etc.). At present, scholars have studied the hydration kinetics of light-burned magnesia. The results of related research show that there is a significant difference between the hydration kinetics of light-burned magnesia in pure water and its hydration kinetics in cement clinker. This difference is related to the nature of periclase itself and the method of testing. Compared with reacting directly with pure water, the situation of magnesium oxide in cement concrete is more complicated. In some studies, periclase contained in cement clinker is used. This kind of periclase has a high formation temperature, low hydration activity, and will be partially wrapped by cement minerals. The hydration of periclase is affected by cement hydration. Using this method to test directly reflects the hydration of magnesium oxide contained in cement.
然而，外掺轻烧氧化镁与水泥中内含氧化镁相比煅烧温度低，方镁石的活性高，同时外掺的轻烧氧化镁与水泥只是简单的混合在一起，并不存在相互包裹。因而现有研究结果得出的方镁石水化动力学与外掺氧化镁在水泥乃至于混凝土中的水化动力学是否一致还有待于进一步的研究。因此，研究外掺氧化镁在混凝土中的水化反应动力学特征具有重大意义。However, compared with the magnesia contained in cement, the calcination temperature of externally mixed light-burned magnesia is lower, and the activity of periclase is higher. At the same time, the externally mixed light-burned magnesia and cement are simply mixed together, and there is no mutual wrapping . Therefore, whether the hydration kinetics of periclase obtained from the existing research results is consistent with the hydration kinetics of magnesium oxide added in cement or even concrete needs further research. Therefore, it is of great significance to study the kinetic characteristics of the hydration reaction of external magnesium oxide in concrete.
鉴于此，特提出本发明。In view of this, the present invention is proposed.
发明内容Contents of the invention
本发明的一个目的在于提供一种外掺氧化镁混凝土的水化反应活化能的测算方法，该方法能够克服上述问题或者至少部分地解决上述技术问题，提出一种外掺氧化镁的混凝土内部水化动力学分析中的关键参数—水化反应活化能的测定与计算方法。An object of the present invention is to provide a method for measuring and calculating the activation energy of hydration reaction of externally-doped magnesia concrete, which can overcome the above-mentioned problems or at least partially solve the above-mentioned technical problems. Determination and calculation method of activation energy of hydration reaction, the key parameter in chemical kinetics analysis.
本发明的另一个目的在于提供一种所述的外掺氧化镁混凝土的水化反应活化能的测算方法在包含氧化镁的混凝土的动力学研究中的应用。Another object of the present invention is to provide an application of the method for calculating the activation energy of hydration reaction of externally added magnesia concrete in the kinetic research of concrete containing magnesia.
为实现上述目的，本发明采用的技术方案为：To achieve the above object, the technical solution adopted in the present invention is:
根据本发明的一个方面，本发明提供一种外掺氧化镁混凝土的水化反应活化能的测算方法，包括以下步骤：According to one aspect of the present invention, the present invention provides a kind of method for calculating the activation energy of hydration reaction of externally mixed magnesium oxide concrete, comprising the following steps:
根据阿仑尼乌斯公式，建立氧化镁水化反应速率与温度、氧化镁水化度及水化反应活化能之间的关系；According to the Arrhenius formula, establish the relationship between the hydration reaction rate of magnesium oxide and temperature, the degree of hydration of magnesium oxide and the activation energy of hydration reaction;
结合氧化镁水化度与混凝土膨胀量之间的关系，建立计算混凝土中氧化镁水化反应活化能的数学模型；Combining the relationship between the degree of hydration of magnesium oxide and the expansion of concrete, a mathematical model for calculating the activation energy of the hydration reaction of magnesium oxide in concrete was established;
利用所建立的数学模型，结合氧化镁混凝土自生体积变形的试验数据，计算氧化镁混凝土中的氧化镁水化反应活化能。The activation energy of hydration reaction of magnesium oxide in magnesium oxide concrete is calculated by using the established mathematical model and the experimental data of autogenous volume deformation of magnesium oxide concrete.
作为进一步优选技术方案，根据阿仑尼乌斯公式，t时刻的氧化镁水化反应速率与温度、氧化镁水化度及水化反应活化能之间的关系可表示为：As a further preferred technical solution, according to the Arrhenius formula, the relationship between the hydration reaction rate of magnesium oxide at time t and temperature, the degree of hydration of magnesium oxide and the activation energy of hydration reaction can be expressed as:
其中，ζ为氧化镁水化度；为化学反应亲和力；Em为水化反应活化能，单位kJ/mol；R为摩尔气体常数，单位kJ/mol·K；T为热力学温度，单位K。Wherein, ζ is the degree of hydration of magnesium oxide; is the chemical reaction affinity; E m is the activation energy of hydration reaction, in kJ/mol; R is the molar gas constant, in kJ/mol·K; T is the thermodynamic temperature, in K.
作为进一步优选技术方案，氧化镁水化度与混凝土膨胀量之间的关系可表示为：As a further preferred technical solution, the relationship between the degree of hydration of magnesium oxide and the expansion of concrete can be expressed as:
εau＝f(ζ)；ε au = f(ζ);
其中，εau为氧化镁混凝土的自生体积变形量；f(ζ)为混凝土内部氧化镁的水化程度的函数。Among them, ε au is the autogenous volume deformation of magnesia concrete; f(ζ) is a function of the hydration degree of magnesia inside the concrete.
作为进一步优选技术方案，混凝土中氧化镁水化反应活化能的数学模型可表示为：As a further preferred technical solution, the mathematical model of the activation energy of magnesium oxide hydration in concrete can be expressed as:
其中，Em为水化反应活化能，单位kJ/mol；R为摩尔气体常数，单位kJ/mol·K；t1和t2分别为第一龄期和第二龄期，单位day；T1和T2分别为第一热力学温度和第二热力学温度，单位K。Among them, E m is the activation energy of hydration reaction, the unit is kJ/mol; R is the molar gas constant, the unit is kJ/mol K; t 1 and t 2 are the first age and the second age respectively, the unit is day; T 1 and T 2 are the first thermodynamic temperature and the second thermodynamic temperature, unit K.
作为进一步优选技术方案，利用所建立的混凝土中氧化镁水化反应活化能的数学模型，结合氧化镁混凝土自生体积变形的试验数据，对两个不同温度条件下混凝土自生体积变形的数据进行分析，选取自生体积变形相同或相近的龄期，即可计算得出混凝土中的氧化镁水化反应活化能。As a further optimal technical solution, using the established mathematical model of the hydration reaction activation energy of magnesium oxide in concrete, combined with the experimental data of the autogenous volume deformation of magnesium oxide concrete, the data of the autogenous volume deformation of concrete under two different temperature conditions are analyzed. The activation energy of hydration reaction of magnesium oxide in concrete can be calculated by selecting the age with the same or similar autogenous volume deformation.
作为进一步优选技术方案，氧化镁混凝土自生体积变形的试验数据包括混凝土自生体积变形量、温度和龄期。As a further preferred technical solution, the experimental data of autogenous volume deformation of magnesia concrete includes concrete autogenous volume deformation, temperature and age.
作为进一步优选技术方案，所述的外掺氧化镁混凝土包括粗集料、细集料、水泥、粉煤灰、减水剂、引气剂、水以及轻烧氧化镁膨胀剂；As a further preferred technical solution, the external magnesia concrete includes coarse aggregate, fine aggregate, cement, fly ash, water reducing agent, air-entraining agent, water and light-burned magnesia expansion agent;
优选地，轻烧氧化镁膨胀剂的掺量为0.1～5.0wt％，优选为0.3～ 3.5wt％。Preferably, the dosage of the light-burned magnesium oxide expansion agent is 0.1-5.0 wt%, preferably 0.3-3.5 wt%.
作为进一步优选技术方案，所述轻烧氧化镁膨胀剂的煅烧温度为 850～1200℃，煅烧保温时间为0.5h～2h。As a further preferred technical solution, the calcination temperature of the light-burned magnesia expansion agent is 850-1200°C, and the calcination holding time is 0.5h-2h.
作为进一步优选技术方案，氧化镁来自生料中的原料含镁的方镁石、石灰石、白云石或菱镁矿中的至少一种。As a further preferred technical solution, the magnesium oxide comes from at least one of magnesium-containing periclase, limestone, dolomite or magnesite in the raw material.
根据本发明的另一个方面，本发明提供一种如上所述的外掺氧化镁混凝土的水化反应活化能的测算方法在包含氧化镁的混凝土的动力学研究中的应用。According to another aspect of the present invention, the present invention provides an application of the above-mentioned method for calculating the activation energy of hydration reaction of externally mixed magnesium oxide concrete in the kinetic research of concrete containing magnesium oxide.
与现有技术相比，本发明的有益效果在于：Compared with prior art, the beneficial effect of the present invention is:
1、本发明提供了一种新的适用于混凝土中的氧化镁水化反应动力学分析方法，尤其适用于当前研究甚少的外掺氧化镁在混凝土中的水化动力学研究，进而填补了该领域研究的空白，对于氧化镁混凝土的性能以及应用研究提供了有力的指导。1. The present invention provides a new method for analyzing the hydration reaction kinetics of magnesium oxide in concrete, especially suitable for the research on the hydration kinetics of externally mixed magnesium oxide in concrete, which is rarely studied at present, and fills the gap The research gap in this field provides a powerful guidance for the performance and application research of magnesium oxide concrete.
2、本发明的测算方法，利用阿仑尼乌斯公式、氧化镁水化度与混凝土膨胀量之间的关系、氧化镁混凝土自生体积变形的试验数据等，即可计算出氧化镁混凝土中的氧化镁水化反应活化能，即通过数学方程推导和实验数据相结合的方式，计算出氧化镁水化反应活化能，相比于直接采用水泥中内含氧化镁的水化反应活化能，本发明的方法更加严密、精准、可靠，方法简单，易于实现，具有很好的应用前景。2, the measuring and calculating method of the present invention, utilize Arrhenius formula, the relation between the degree of hydration of magnesium oxide and concrete expansion, the test data of autogenous volume deformation of magnesium oxide concrete etc., can calculate the The activation energy of magnesium oxide hydration reaction, that is, the activation energy of magnesium oxide hydration reaction is calculated through the combination of mathematical equation derivation and experimental data. Compared with the hydration reaction activation energy of magnesium oxide contained in cement, this The invented method is more rigorous, precise and reliable, simple and easy to implement, and has good application prospects.
3、本发明有利于促进氧化镁混凝土的水化动力学理论的发展，从而对外掺氧化镁的混凝土的材料设计提供一定理论依据。3. The invention is beneficial to promote the development of the hydration kinetics theory of magnesium oxide concrete, thereby providing a certain theoretical basis for the material design of concrete mixed with magnesium oxide.
4、本发明更能真实的反映氧化镁在混凝土内部的反应情况，既有明确的理论基础，又具有方法简单、灵活、易于操作，可操作性强，结果可靠性好，易于在实践中应用等特点。4. The present invention can more truly reflect the reaction of magnesia inside the concrete. It not only has a clear theoretical basis, but also has the advantages of simple, flexible, easy-to-operate methods, strong operability, good reliability of the results, and easy application in practice. Features.
附图说明Description of drawings
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to more clearly illustrate the specific implementation of the present invention or the technical solutions in the prior art, the following will briefly introduce the accompanying drawings that need to be used in the specific implementation or description of the prior art. Obviously, the accompanying drawings in the following description The drawings show some implementations of the present invention, and those skilled in the art can obtain other drawings based on these drawings without any creative work.
图1为本发明一种实施方式提供的不同温度条件下混凝土龄期与其自生体积变形之间的关系，以及本发明中t1和t2的示意图。Fig. 1 is a relationship between the age of concrete and its autogenous volume deformation under different temperature conditions provided by an embodiment of the present invention, and a schematic diagram of t 1 and t 2 in the present invention.
具体实施方式Detailed ways
下面将结合实施方式和实施例对本发明的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施方式和实施例仅用于说明本发明，而不应视为限制本发明的范围。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。未注明具体条件者，按照常规条件或制造商建议的条件进行。The embodiments of the present invention will be described in detail below in conjunction with the embodiments and examples, but those skilled in the art will understand that the following embodiments and examples are only for illustrating the present invention, and should not be regarded as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention. If the specific conditions are not specified, follow the general conditions or the conditions suggested by the manufacturer.
第一方面，在至少一个实施例中提供一种外掺氧化镁混凝土的水化反应活化能的测算方法，包括以下步骤：In the first aspect, in at least one embodiment, a method for calculating the activation energy of hydration reaction of externally mixed magnesium oxide concrete is provided, comprising the following steps:
根据阿仑尼乌斯公式，建立氧化镁水化反应速率与温度、氧化镁水化度及水化反应活化能之间的关系；According to the Arrhenius formula, establish the relationship between the hydration reaction rate of magnesium oxide and temperature, the degree of hydration of magnesium oxide and the activation energy of hydration reaction;
结合氧化镁水化度与混凝土膨胀量之间的关系，建立计算混凝土中氧化镁水化反应活化能的数学模型；Combining the relationship between the degree of hydration of magnesium oxide and the expansion of concrete, a mathematical model for calculating the activation energy of the hydration reaction of magnesium oxide in concrete was established;
利用所建立的数学模型，结合氧化镁混凝土自生体积变形的试验数据，计算氧化镁混凝土中的氧化镁水化反应活化能。The activation energy of hydration reaction of magnesium oxide in magnesium oxide concrete is calculated by using the established mathematical model and the experimental data of autogenous volume deformation of magnesium oxide concrete.
本发明提供了一种外掺氧化镁的混凝土内部水化动力学分析中的关键参数—水化反应活化能的测定与计算方法。该方法是采用常规的自生体积变形测试配合理论推导的方法：在求解氧化镁的水化反应活化能过程中，采用阿伦尼乌斯公式描述氧化镁的水化反应速率与温度之间的关系，结合氧化镁水化反应程度与混凝土膨胀量之间的关系，建立计算氧化镁在混凝土中的水化反应活化能的数学模型；最后，结合常规的自生体积变形的试验结果，即可求出氧化镁在混凝土中的水化反应活化能。The invention provides a method for measuring and calculating the activation energy of hydration reaction, which is a key parameter in the internal hydration kinetic analysis of concrete doped with magnesium oxide. This method adopts conventional autogenous volume deformation test and theoretical derivation method: in the process of solving the activation energy of hydration reaction of magnesium oxide, the relationship between the hydration reaction rate and temperature of magnesium oxide is described by the Arrhenius formula , combined with the relationship between the degree of hydration reaction of magnesium oxide and the amount of concrete expansion, a mathematical model for calculating the activation energy of hydration reaction of magnesium oxide in concrete is established; finally, combined with the test results of conventional self-generated volume deformation, it can be obtained Activation energy of hydration reaction of magnesium oxide in concrete.
本发明的方法填补了外掺氧化镁在混凝土中的水化动力学研究方面的空白，对于氧化镁混凝土的性能以及应用研究提供了有力的指导。相比于直接采用水泥中内含氧化镁的水化反应活化能，本发明的方法更加严密、精准、可靠，方法简单，易于实现，具有很好的应用前景。The method of the invention fills up the gap in the research on the hydration kinetics of the externally mixed magnesia in concrete, and provides powerful guidance for the performance and application research of the magnesia concrete. Compared with directly using the activation energy of hydration reaction of magnesia contained in cement, the method of the present invention is more rigorous, accurate and reliable, simple and easy to implement, and has a good application prospect.
本发明有利于促进氧化镁混凝土的水化动力学理论的发展，从而对外掺氧化镁的混凝土的材料设计提供一定理论依据。本发明更能真实的反映氧化镁在混凝土内部的反应情况，既有明确的理论基础，又具有方法简单、灵活、易于操作，可操作性强，结果可靠性好，易于在实践中应用等特点。The invention is beneficial to promote the development of the hydration dynamics theory of magnesium oxide concrete, thereby providing a certain theoretical basis for the material design of the concrete mixed with magnesium oxide. The present invention can more truly reflect the reaction of magnesium oxide inside the concrete, not only has a clear theoretical basis, but also has the characteristics of simple, flexible, easy-to-operate, strong operability, good reliability of results, and easy application in practice. .
在一种优选的实施方式中，所述方法包括以下步骤：In a preferred embodiment, the method comprises the following steps:
(a)氧化镁混凝土膨胀速率：(a) Expansion rate of magnesium oxide concrete:
根据阿仑尼乌斯公式，建立氧化镁水化反应速率与温度、氧化镁水化度及水化反应活化能之间的关系。According to the Arrhenius formula, the relationship between the hydration reaction rate of magnesium oxide and temperature, the degree of hydration of magnesium oxide and the activation energy of hydration reaction was established.
氧化镁混凝土的膨胀本质上是氧化镁水化生成氢氧化镁的过程。因此，该过程也同样遵循化学反应的一般规律，温度和浓度是主要影响因素，温度越高反应越快，氧化镁水化速率越快，相应膨胀增量也越大；同时，膨胀速率与参与反应的氧化镁的含量(可以理解为液态化学反应中的浓度)成正比，符合化学反应动力学方程—阿仑尼乌斯方程(Arrhenius方程)。The expansion of magnesium oxide concrete is essentially the process of hydration of magnesium oxide to generate magnesium hydroxide. Therefore, this process also follows the general law of chemical reactions, and temperature and concentration are the main influencing factors. The higher the temperature, the faster the reaction, the faster the hydration rate of magnesium oxide, and the larger the corresponding expansion increment; at the same time, the expansion rate and participation The content of the reacted magnesium oxide (which can be understood as the concentration in the liquid chemical reaction) is proportional to the kinetic equation of the chemical reaction—the Arrhenius equation (Arrhenius equation).
因而，t时刻的氧化镁水化反应速率可表示为该时刻的化学反应亲和力和温度、水化反应活性能的函数，即为式(1)：Therefore, the magnesium oxide hydration reaction rate at time t can be expressed as a function of chemical reaction affinity, temperature, and hydration reaction activity energy at this time, which is formula (1):
其中，ζ为氧化镁水化度；为化学反应亲和力；Em为水化反应活化能，单位kJ/mol；R为摩尔气体常数，单位kJ/mol·K；T为热力学温度，单位K。Wherein, ζ is the degree of hydration of magnesium oxide; is the chemical reaction affinity; E m is the activation energy of hydration reaction, in kJ/mol; R is the molar gas constant, in kJ/mol·K; T is the thermodynamic temperature, in K.
(b)氧化镁混凝土自生体积变形：(b) Autogenous volume deformation of magnesium oxide concrete:
氧化镁混凝土的自生体积变形主要由氧化镁的水化造成，因此，将氧化镁混凝土自身体积变形可采用其水化程度的函数来模拟。即，氧化镁水化度与混凝土膨胀量之间的关系可表示为式(2)：The autogenous volume deformation of magnesium oxide concrete is mainly caused by the hydration of magnesium oxide. Therefore, the volume deformation of magnesium oxide concrete itself can be simulated by the function of its hydration degree. That is, the relationship between the degree of hydration of magnesium oxide and the expansion of concrete can be expressed as formula (2):
εau＝f(ζ) (2)ε au = f(ζ) (2)
其中，εau为氧化镁混凝土的自生体积变形量；f(ζ)为混凝土内部氧化镁的水化程度的函数。Among them, ε au is the autogenous volume deformation of magnesia concrete; f(ζ) is a function of the hydration degree of magnesia inside the concrete.
对于成分完全相同的混凝土试件，可以认为在混凝土的自生体积变形相同时，其内部氧化镁的水化程度也相同。For concrete specimens with exactly the same composition, it can be considered that when the autogenous volume deformation of the concrete is the same, the hydration degree of the internal magnesium oxide is also the same.
(c)氧化镁水化反应活化能：(c) activation energy of magnesium oxide hydration reaction:
结合氧化镁水化度与混凝土膨胀量之间的关系，建立计算混凝土中氧化镁水化反应活化能的数学模型；Combining the relationship between the degree of hydration of magnesium oxide and the expansion of concrete, a mathematical model for calculating the activation energy of the hydration reaction of magnesium oxide in concrete was established;
依据式(1)，对任意的氧化镁水化程度(ζ)，混凝土的膨胀速率仅与温度相关。因此，在两种不同的恒定的混凝土养护温度条件下，水化反应速率(膨胀速率)之比是温度的函数：According to formula (1), for any degree of hydration of magnesium oxide (ζ), the expansion rate of concrete is only related to temperature. Therefore, under two different constant concrete curing temperature conditions, the ratio of the hydration reaction rate (expansion rate) is a function of temperature:
因此，到达相同的水化程度所需的时间也同样与混凝土的温度相关。式(1)可改写为：Therefore, the time required to reach the same degree of hydration is also related to the temperature of the concrete. Formula (1) can be rewritten as:
对式(5)两边同时积分，可得：Integrating both sides of equation (5) at the same time, we can get:
从而，在不同温度条件下到达某一固定的水化程度所需的时间可以表示为：Thus, the time required to reach a fixed degree of hydration at different temperatures can be expressed as:
进而，结合上述公式，混凝土中氧化镁水化反应活化能Em的数学模型可表示为：Furthermore, combined with the above formula, the mathematical model of the activation energy E m of the hydration reaction of magnesium oxide in concrete can be expressed as:
其中，Em为水化反应活化能，单位kJ/mol；R为摩尔气体常数，单位kJ/mol·K；t1和t2分别为第一龄期和第二龄期，单位day；T1和T2分别为第一热力学温度和第二热力学温度，单位K。Among them, E m is the activation energy of hydration reaction, the unit is kJ/mol; R is the molar gas constant, the unit is kJ/mol K; t 1 and t 2 are the first age and the second age respectively, the unit is day; T 1 and T 2 are the first thermodynamic temperature and the second thermodynamic temperature, unit K.
根据上述方程(11)，结合氧化镁混凝土的自生体积变形实验数据，只需对两个不同温度条件下混凝土自生体积变形的数据进行分析，选取自生体积变形相同或相近的龄期，即可由该方程推求氧化镁的水化反应活化能。According to the above equation (11), combined with the experimental data of autogenous volume deformation of magnesia concrete, it is only necessary to analyze the data of autogenous volume deformation of concrete under two different temperature conditions, and select the age with the same or similar autogenous volume deformation, then the Calculate the activation energy of hydration reaction of magnesium oxide from the equation.
通过以上分析可知，氧化镁在混凝土中的水化反应活化能可以通过测试其自生体积变形间接求出。From the above analysis, it can be seen that the activation energy of hydration reaction of magnesium oxide in concrete can be obtained indirectly by testing its autogenous volume deformation.
本发明给出了外掺氧化镁混凝土的水化反应活化能的测算方法的具体求解方法，操作简单，易于实现。The invention provides a specific solution method for the calculation method of the hydration reaction activation energy of the externally mixed magnesium oxide concrete, which is simple in operation and easy to realize.
在一种优选的实施方式中，所述的外掺氧化镁混凝土包括粗集料、细集料、水泥、粉煤灰、减水剂、引气剂、水以及轻烧氧化镁膨胀剂；In a preferred embodiment, the external magnesia concrete includes coarse aggregate, fine aggregate, cement, fly ash, water reducing agent, air-entraining agent, water and light-burned magnesia expansion agent;
优选地，轻烧氧化镁膨胀剂的掺量为0.1～5.0wt％，优选为0.3～ 3.5wt％；Preferably, the dosage of the light-burned magnesium oxide expansion agent is 0.1-5.0 wt%, preferably 0.3-3.5 wt%;
优选地，外掺氧化镁混凝土的水胶比为0.45～0.65，优选为 0.56～0.59。Preferably, the water-binder ratio of the externally mixed magnesium oxide concrete is 0.45-0.65, preferably 0.56-0.59.
可以理解的是，本发明对于氧化镁混凝土的具体组成成分不作特殊限制，对于各原料的用量也不作特殊限制，根据实际的设计、应用需求，采用本领域中常用的或熟知的混凝土原料以及配比进行配制，并外掺一定量的氧化镁即可。该方法具有适应性好，实用性强等特点。It can be understood that the present invention does not make special restrictions on the specific composition of magnesium oxide concrete, nor does it make special restrictions on the amount of each raw material. According to actual design and application requirements, commonly used or well-known concrete raw materials and ingredients in this field are used. It can be prepared by mixing with a certain amount of magnesium oxide. This method has the characteristics of good adaptability and strong practicability.
在一种优选的实施方式中，所述轻烧氧化镁膨胀剂的煅烧温度为 850～1200℃，煅烧保温时间为0.5h～2h。In a preferred embodiment, the calcination temperature of the light-burned magnesia expansion agent is 850-1200°C, and the calcination holding time is 0.5h-2h.
在一种优选的实施方式中，氧化镁来自生料中的原料含镁的方镁石、石灰石、白云石或菱镁矿中的至少一种。In a preferred embodiment, the magnesium oxide comes from at least one of magnesium-containing periclase, limestone, dolomite or magnesite in the raw material.
应当理解的是，本发明对于氧化镁的来源，其煅烧温度等处理方式和条件也不作特殊限制，可根据实际情况，选择本领域常用的或适宜的氧化镁原料，并进行处理后掺加到混凝土中即可。It should be understood that the present invention does not impose special restrictions on the source of magnesium oxide, its calcination temperature and other treatment methods and conditions, and can select commonly used or suitable magnesium oxide raw materials in this field according to actual conditions, and mix them into in concrete.
第二方面，在至少一个实施例中提供一种所述的外掺氧化镁混凝土的水化反应活化能的测算方法在包含氧化镁的混凝土的动力学研究中的应用。In the second aspect, at least one embodiment provides an application of the method for calculating the activation energy of hydration reaction of externally mixed magnesium oxide concrete in the kinetic research of concrete containing magnesium oxide.
下面结合具体实施例和附图，对本发明作进一步说明。The present invention will be further described below in combination with specific embodiments and accompanying drawings.
实施例Example
图1显示了本发明一种实施方式提供的不同温度条件下混凝土龄期与其自生体积变形之间的关系，以及本发明中t1和t2的示意图；参照图1所示，一种外掺氧化镁混凝土的水化反应活化能的测算方法，采用理论推导实现：在求解氧化镁混凝土中的氧化镁水化反应活化能过程中，首先，依据化学反应速率所服从的阿伦尼乌斯公式，推求出化学反应活化能与龄期及温度之间的关系；然后，通过选择两个不同的固定温度T1和T2，求出达到相同水化度所需的时间的比值与温度之间的关系，建立计算混凝土中的氧化镁水化反应活化能求解的数学模型。Fig. 1 shows the relationship between concrete age and its autogenous volume deformation under different temperature conditions provided by an embodiment of the present invention, and the schematic diagram of t1 and t2 among the present invention; With reference to shown in Fig. 1, a kind of external mixing The calculation method of the activation energy of hydration reaction of magnesium oxide concrete is realized by theoretical derivation: in the process of solving the activation energy of magnesium oxide hydration reaction in magnesium oxide concrete, first, according to the Arrhenius formula obeyed by the chemical reaction rate , deduce the relationship between chemical reaction activation energy and age and temperature; then, by choosing two different fixed temperatures T 1 and T 2 , find the ratio of the time required to reach the same degree of hydration and the temperature Establish the mathematical model for calculating the activation energy of hydration reaction of magnesium oxide in concrete.
然后，只需依据本发明给出的混凝土中氧化镁水化反应活化能的数学模型，结合混凝土的自生体积变形试验数据，选取相同的自生体积变形量(水化程度)对应的龄期，即可进行求解。Then, only need to select the age corresponding to the same autogenous volume deformation (hydration degree) according to the mathematical model of the activation energy of magnesium oxide hydration reaction in concrete provided by the present invention, in conjunction with the autogenous volume deformation test data of concrete, namely can be solved.
现以某采用外掺氧化镁混凝土作为大坝填筑材料的水电工程为例，说明本发明的应用。The application of the present invention will now be described by taking a hydropower project that uses externally mixed magnesium oxide concrete as a dam filling material as an example.
某水电站工程位于云贵高原西部峡谷区，水库大坝采用外掺氧化镁混凝土作为填筑材料以达到减少温控措施，缩短工期，节约投资的目的。结合设计要求，经过一系列的试验，确定了大坝混凝土的配合比，见表1：A hydropower project is located in the western canyon area of the Yunnan-Guizhou Plateau. The dam of the reservoir uses concrete mixed with magnesium oxide as the filling material to achieve the purpose of reducing temperature control measures, shortening the construction period, and saving investment. Combined with the design requirements, after a series of tests, the mix ratio of the dam concrete was determined, as shown in Table 1:
表1大坝混凝土各组分表Table 1 Components of dam concrete
混凝土在不同温度条件下各个龄期的自生体积变形数据，如表2 所示。The autogenous volume deformation data of concrete at different ages under different temperature conditions are shown in Table 2.
表2不同水胶比的氧化镁混凝土在不同温度条件下各个龄期的自生体积变形Table 2 Autogenous volume deformation of MgO concrete with different water-binder ratios at different ages at different temperatures
应用本发明的外掺氧化镁混凝土的水化反应活化能的测算方法，分别对两种水胶比的外掺氧化镁混凝土的水化反应活化能进行计算。Applying the method for measuring and calculating the activation energy of hydration reaction of externally-mixed magnesium oxide concrete of the present invention, the hydration reaction activation energy of externally-mixed magnesium oxide concrete with two water-binder ratios is calculated respectively.
(1)w/b＝0.56的氧化镁混凝土(1) Magnesia concrete with w/b=0.56
选取自生体积变形最为接近的两个值：53.422(30℃，28d龄期)、 51.544(40℃，14d龄期)，应用公式(11)，可得：Select the two values closest to autogenous volume deformation: 53.422 (30°C, 28d age) and 51.544 (40°C, 14d age), and apply formula (11), we can get:
其中，R为摩尔气体常数，8.314kJ/mol·K，进而可求得氧化镁水化反应活化能Em为54.7kJ/mol。Among them, R is the molar gas constant, 8.314kJ/mol·K, and then the activation energy E m of magnesium oxide hydration reaction can be obtained as 54.7kJ/mol.
(2)w/b＝0.59的氧化镁混凝土(2) Magnesia concrete with w/b=0.59
选取自生体积变形最为接近的两个值：13.378(20℃，7d龄期)、 11.826(40℃，3d龄期)，应用公式(11)，可得：Select the two values closest to autogenous volume deformation: 13.378 (20°C, 7d age) and 11.826 (40°C, 3d age), and apply formula (11), we can get:
其中，R为摩尔气体常数，8.314kJ/mol·K，进而可求得氧化镁水化反应活化能Em为32.5kJ/mol。Among them, R is the molar gas constant, 8.314kJ/mol·K, and then the activation energy E m of magnesium oxide hydration reaction can be obtained as 32.5kJ/mol.
从以上的算例可以看出，不同混凝土内部的氧化镁的水化反应活化能并不相同。From the above calculation example, it can be seen that the activation energy of hydration reaction of magnesium oxide in different concretes is not the same.
另外，本领域技术人员可以理解的是，在实践过程中，可通过增加测量次数以加密数据点，以寻找出多组自生体积变形值相同的数据点进行计算，并通过多组平均的方法提高计算的精度。当然，这里指出的是该方法在实践应用过程中的注意事项，但并不影响该方法理论上的严密性。In addition, those skilled in the art can understand that, in practice, the data points can be encrypted by increasing the number of measurements to find multiple sets of data points with the same autogenous volume deformation value for calculation, and improve the The precision of the calculation. Of course, what is pointed out here is the precautions in the practical application of the method, but it does not affect the theoretical rigor of the method.
本发明的算法由数学方程推导，理论上严密、可靠，并且可直接借助氧化镁混凝土自生体积变形的数据求解；相比于直接采用氧化镁与水反应或者含氧化镁的水泥进行水化动力学分析，这种间接求解方法不仅比较便利，而且更能真实的反映氧化镁在混凝土内部的反应情况。此外，本发明结合实际工程实践，给出了该方法的具体算例，该方法易于在实践中应用。The algorithm of the present invention is deduced from mathematical equations, which is rigorous and reliable in theory, and can be solved directly with the help of the data of autogenous volume deformation of magnesia concrete; compared with directly using magnesia and water reaction or hydration kinetics of cement containing magnesia Analysis, this indirect solution method is not only more convenient, but also can more truly reflect the reaction of magnesium oxide inside the concrete. In addition, the present invention provides specific calculation examples of the method in combination with actual engineering practice, and the method is easy to be applied in practice.
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present invention, rather than limiting them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: It is still possible to modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the various embodiments of the present invention. scope.
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| CN113030742A (en) * | 2019-12-24 | 2021-06-25 | 比亚迪股份有限公司 | Method, device and equipment for estimating battery capacity |
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