CN109903819A - A kind of analysis method of silicate cement cement composite gel material aquation kinetic parameter - Google Patents
A kind of analysis method of silicate cement cement composite gel material aquation kinetic parameter Download PDFInfo
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Abstract
The invention discloses a kind of analysis methods of silicate cement cement composite gel material aquation kinetic parameter, include the following steps: that (1) determines under experimental temperature, the hydration heat total amount and hydration rate of silicate cement cement composite gel material test specimen.And the hydration heat total amount and hydration rate of test specimen are subjected to mass normalisation processing, for calculating.(2) thermal discharge of various time points and the relationship of heat release total amount are calculated, determines the extent of reaction of different time.(3) crystal nucleation and crystal growth reaction process are calculated.(4) phase boundray reaction process (5) are calculated and calculates diffusion reaction process.The present invention can the aquations kinetic parameter such as the order of reaction, rate constant in quantitative analysis silicate cement cement composite gel material hydration process, facilitate influence of the various experimental factors to silicate cement cement composite gel material aquation power of analyzing and researching.Promotion of the model realization established to silicate cement cement composite gel material performance can be utilized.
Description
Technical field
The present invention relates to a kind of analysis methods of silicate cement cement composite gel material aquation kinetic parameter.
Background technique
The hydration process of portland cement cementitious material is usually in terms of hydration rate, degree of hydration and hydrated product three
It is studied, these three aspects can both have been characterized by aquation thermodynamics or by aquation Kinetic Characterization.However
Whether pass through aquation thermodynamics or pass through the hydration process of aquation Kinetic Characterization cementitious material, be all to find it at all
The source of aquation power, therefore be exactly to study its internal aquation power for the most effective mode of cementitious material hydration mechanism research
Knowledge topic.For dynamic angle, the aquation of cementitious material refers to its main component cement after adding the water, occurs a series of
Physicochemical change, cementitious material can release a large amount of heat in this course, this dynamic process generally uses hydration reaction
Thermal discharge and hydration reaction rate two important parameter indexes are measured.And the heat of hydration and hydration rate are by many
The influence of factor, composition, fineness, concentration, water-cement ratio, temperature, pressure, catalyst including cementitious material etc..In addition to examine
Consider the influence factor of basic cement components etc. itself, it is also contemplated that the admixture added, the brings such as additive influence.Cause
This is increasingly complex to the determination of the hydration kinetics equation of composite gelled material.
Summary of the invention
The purpose of the present invention is to provide a kind of analysis method of silicate cement cement composite gel material aquation kinetic parameter,
This method is improved based on NG-I-D hydration model and is established the aquation kinetic parameter suitable for composite gelled material
It calculates, analysis method.Involved aquation parameter during silicate cement hydration can accurately be expressed.Aquation calculated
Parameter can be used for each experimental factor of quantitative analysis to the affecting laws and degree of cementitious material hydration heat total amount and rate of heat release.
It is of the existing technology in order to solve the problems, such as, the technical solution adopted by the present invention is that:
A kind of analysis method of silicate cement cement composite gel material aquation kinetic parameter, includes the following steps:
(1) it determines under test temperature, the hydration heat total amount and aquation of silicate cement cement composite gel material test specimen
Rate.And the hydration heat total amount and hydration rate of test specimen are subjected to mass normalisation processing, for calculating.
(2) thermal discharge of various time points and the relationship of heat release total amount are calculated, determines the table of the extent of reaction of different time
It states as 1..
Q (t) --- various time points thermal discharge
QAlways--- heat release total amount.
(3) being expressed as 2. for crystal nucleation and crystal growth reaction process is calculated.
[-lg(1-α)]1/n=KIt is brilliantt ②
KIt is brilliant--- the reaction rate constant of nucleation and crystal growth
The order of reaction of n --- cementitious material
The degree of hydration of α --- cementitious material.
(4) being expressed as 3. for phase boundray reaction process is calculated.
KPhase--- in the rate constant of phase boundray reaction, KPhase=kPhase/r
R --- the radius of reaction particles in cementitious material
(5) being expressed as 4. for diffusion reaction process is calculated.
[1-(1-α)1/3]2=KExpandr-2(t-t0)=KExpandt ④
KExpand--- indicate the rate constant of diffusion reaction, KExpand=kExpand/r2
R --- the radius of reaction particles in cementitious material
In the step (4), (5) in cementitious material the radius of reaction particles not as Consideration.
To in the step (3), (4), (5), 2., 3., 4. formula two sides carry out α to the differential of t, and acquired results equation can incite somebody to action
Data measured is brought into step (2).
To in the step (3), (4), (5), 2., 3., 4. formula can be fitted solution cementitious material using double logarithmic curve
The order of reaction, nucleation and crystal growth reaction rate constant, phase boundray reaction rate constant, indicate diffusion reaction
The aquations kinetic parameter such as rate constant.
Advantage for present invention and beneficial effect are:
A kind of analysis method of silicate cement cement composite gel material aquation kinetic parameter of the present invention, is mixed by active mineral
The analysis method that material and portland cement mix the aquation kinetic parameter for the composite gelled material to be formed again is closed, is suitable for for establishing
Active mineral admixture and cement mix the aquation kinetic model for the composite gelled material to be formed again.The model established can be utilized
Realize the promotion to silicate cement cement composite gel material performance.It being capable of quantitative analysis silicate cement cement composite gel material aquation
The aquations kinetic parameter such as the order of reaction, rate constant in the process facilitates the various experimental factors of analysis and research to silicate cement
The influence of cement composite gel material aquation power.
Detailed description of the invention
The invention will be further described with reference to the accompanying drawing:
Fig. 1 is that linear fit seeks exothermic maximum spirogram；
Fig. 2 is to calculate crystal growing process aquation kinetic parameter fitted figure；
Fig. 3 is to calculate crystal-phase transformation process aquation kinetic parameter fitted figure；
Fig. 4 is to calculate intracrystalline diffusion process aquation kinetic parameter fitted figure；
Fig. 5 is the hydration reaction degree rate curve of composite gelled material fitting.
Specific embodiment
The present invention will be described in further detail combined with specific embodiments below, but protection scope of the present invention is not had
The embodiment of body is limited, and is subject to claims.In addition, with without prejudice under the premise of technical solution of the present invention, to this hair
Any modifications or changes easy to accomplish of those of ordinary skill in the art made by bright fall within claim model of the invention
Within enclosing.
A kind of analysis method of silicate cement cement composite gel material aquation kinetic parameter, includes the following steps:
(1) it determines under test temperature, the hydration heat total amount and aquation of silicate cement cement composite gel material test specimen
Rate, and the hydration heat total amount and hydration rate of test specimen are subjected to mass normalisation processing, for calculating；
(2) thermal discharge of various time points and the relationship of heat release total amount are calculated, determines the table of the extent of reaction of different time
It states as 1.:
Q (t) --- various time points thermal discharge
QAlways--- heat release total amount
(3) being expressed as 2. for crystal nucleation and crystal growth reaction process is calculated:
[-lg(1-α)]1/n=KIt is brilliantt ②
KIt is brilliant--- the reaction rate constant of nucleation and crystal growth
The order of reaction of n --- cementitious material
The degree of hydration of α --- cementitious material
(4) being expressed as 3. for phase boundray reaction process is calculated:
KPhase--- in the rate constant of phase boundray reaction, KPhase=kPhase/r
R --- the radius of reaction particles in cementitious material
(5) being expressed as 4. for diffusion reaction process is calculated:
[1-(1-α)1/3]2=KExpandr-2(t-t0)=KExpandt ④
KExpand--- indicate the rate constant of diffusion reaction, KExpand=kExpand/r2
R --- the radius of reaction particles in cementitious material
In the step (4), (5) in cementitious material the radius of reaction particles not as Consideration.
To in the step (3), (4), (5), 2., 3., 4. formula two sides carry out α to the differential of t, and acquired results equation can incite somebody to action
Data measured is brought into step (2).
To in the step (3), (4), (5), 2., 3., 4. formula is fitted using double logarithmic curve and solves cementitious material
The order of reaction, the reaction rate constant of nucleation and crystal growth, the rate constant in phase boundray reaction, the speed of expression diffusion reaction
Rate constant.
Embodiment 1:
The present embodiment with 5 DEG C, the test data of the hydration heat amount for the composite gelled material that Silica fume content is 10% be according to
According to the deduction of progress portland cement-silicon ash composite gelled material aquation kinetic model calculates hydration reaction sum of series not
With the hydration reaction rate constant in stage.
(1) function Q (t) of the thermal discharge for the silicon ash composite gelled material for being 10% in calculated yield for the time
Access time section be 600min-680min data, by Q (t) divided by test composite gelled material gross mass g=5.00 (g) into
Row normalized.And using 1/t as abscissa 1/QAlwaysThe data point that test is surveyed is brought into formula for ordinate, and scatterplot is carried out
Linear fit is as shown in Figure 1.
By the available equation of linear fit: 1/Q=1.50738 (1/t)+0.00552.When t levels off to infinity,
1/t levels off to 0, so the corresponding 1/Q in 1/t=0AlwaysAs 1/QTotal max.Therefore Q can be obtainedmaxFor 181.15942Jg-1。
The Q that will be calculatedmaxBe brought into equation 1. in, the aquation dsc data for utilizing test to obtain calculates different time
Degree of hydration α (t), then by α (t) be brought into formula 2. in, with lg (t-t0) it is abscissa, with lg [- lg (1- α)] for ordinate
It draws, and these is put and carries out linear fit, as shown in Figure 2.
Using the equation obtained after linear fit are as follows: lg [- lg (1- α)]=1.11455 × lg (t-t0) -4.43105, mark
Quasi- error sd=0.00269, correlation coefficient r=0.96939 of fitting.lg(t-t0) coefficient be hydration reaction series n, will
N is brought into n ln K 'It is brilliantIn can find out the hydration reaction rate constant of crystal growing process, so by linear fit and
It is obtained after calculating: n=1.11455, K 'It is brilliant=0.0001057693.
Choose QmaxData after calculating in hydration reaction degree and the function alpha (t) of time, with lg (t-t0) it is abscissa,
With lg [1- (1- α)1/3] it is that ordinate is drawn, while carrying out linear fit to these data points, as shown in Figure 3.
Using the equation obtained after linear fit are as follows: lg [1- (1- α)1/3]=lg (t-t0) -0.35102, standard error sd
=0.0002145 due to slope be definite value thus fitting correlation coefficient r=0.96255.The constant term of fit equation is ln
K′Phase, the hydration reaction rate constant K ' of crystal-phase transformation process can be found out by calculatingPhase=0.000010873015.
It chooses and utilizes QmaxHydration reaction degree is about the data in the function alpha (t) of time after calculating, with lg (t-t0) be
Abscissa, with 21g [1- (1- α)1/3] it is that ordinate is drawn, while carrying out linear fit to these data points, as shown in Figure 4.
Using the equation obtained after linear fit are as follows: 2lg [1- (1- α)1/3]=lg (t-t0) -0.79917, due to slope
For definite value so correlation coefficient r=0.99999 of fitting, standard error sd=0.00020317.The constant term of fit equation is
For lg K 'Expand, the hydration reaction rate constant K ' of crystal-phase transformation process can be found out by calculatingExpand=0.0006359164.
Calculated 5 DEG C above by the method for linear fit, the order of reaction of the composite gelled material of 10% silicon ash and
Hydration reaction rate constant, by n, the K ' after calculatingIt is brilliant、K′Phase、K′ExpandNumerical value be brought into formula 2., 3. and 4. in, it is brilliant to obtain characterization
The hydration reaction rate fit equation K of body growth, phase transformation and diffusion process1(a)、 K2(a)、K3(a).With hydration reaction degree α
It for abscissa, maps by ordinate of hydration rate d α/dt, the hydration reaction rate curve of actual measurement and fitting is obtained
The hydration reaction rate curve for characterizing crystal growth, phase transformation and diffusion process is drawn as shown in Figure 5 simultaneously.
The fitting for having carried out the hydration kinetics equation of silicon ash silicate composite gelled material above, calculates the order of reaction
The rate constant K ' of n and hydration reactionIt is brilliant、K′Phase、K′Expand, crystal growth-phase transformation and diffusion transformation point α1With phase transformation-diffusion transformation point
α2.The aquation kinetic model of the composite gelled material of different Silica fume contents can be calculated separately by using above method
Parameters further analyze the influence of different condition and different Silica fume contents to hydration heat rate and heat evolution velocity.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be embodied in other specific forms.
Claims (4)
1. a kind of analysis method of silicate cement cement composite gel material aquation kinetic parameter, feature include the following steps:
(1) it determines under test temperature, the hydration heat total amount and hydration rate of silicate cement cement composite gel material test specimen,
And the hydration heat total amount and hydration rate of test specimen are subjected to mass normalisation processing, for calculating；
(2) thermal discharge of various time points and the relationship of heat release total amount are calculated, determines being expressed as the extent of reaction of different time
1.:
Q (t) --- various time points thermal discharge
QAlways--- heat release total amount；
(3) being expressed as 2. for crystal nucleation and crystal growth reaction process is calculated:
[-lg(1-α)]1/n=KIt is brilliantt ②
KIt is brilliant--- the reaction rate constant of nucleation and crystal growth
The order of reaction of n --- cementitious material
The degree of hydration of α --- cementitious material；
(4) being expressed as 3. for phase boundray reaction process is calculated:
KPhase--- in the rate constant of phase boundray reaction, KPhase=kPhase/r
R --- the radius of reaction particles in cementitious material；
(5) being expressed as 4. for diffusion reaction process is calculated:
[1-(1-α)1/3]2=KExpandr-2(t-t0)=KExpandt ④
KExpand--- indicate the rate constant of diffusion reaction, KExpand=kExpand/r2
R --- the radius of reaction particles in cementitious material.
2. a kind of analysis method of silicate cement cement composite gel material aquation kinetic parameter according to claim 1,
Be characterized in that, in the step (4), (5) in cementitious material the radius of reaction particles not as Consideration.
3. a kind of analysis method of silicate cement cement composite gel material aquation kinetic parameter according to claim 1,
It is characterized in that, in the step (3), (4), (5), 2., 3., 4. formula two sides carry out α to the differential of t, and acquired results equation can incite somebody to action
Data measured is brought into step (2).
4. a kind of analysis method of silicate cement cement composite gel material aquation kinetic parameter according to claim 1,
It is characterized in that, in the step (3), (4), (5), 2., 3., 4. formula using double logarithmic curve is fitted solution cementitious material
The order of reaction, nucleation and crystal growth reaction rate constant, phase boundray reaction rate constant, indicate diffusion reaction
Rate constant.
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| CN110853107A (en) * | 2019-11-19 | 2020-02-28 | 沈阳建筑大学 | Method for calculating hydration kinetics of alkali-activated slag material based on color change numerical value |
| CN113722969A (en) * | 2021-08-12 | 2021-11-30 | 武汉理工大学 | Tricalcium silicate hydration full-process performance index determination method and computational analyzer thereof |
| CN116373103A (en) * | 2023-03-06 | 2023-07-04 | 中国长江三峡集团有限公司 | Preparation method of high-crack-resistance hydraulic concrete |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110853107A (en) * | 2019-11-19 | 2020-02-28 | 沈阳建筑大学 | Method for calculating hydration kinetics of alkali-activated slag material based on color change numerical value |
| CN110853107B (en) * | 2019-11-19 | 2023-07-21 | 沈阳建筑大学 | Method for calculating hydration kinetics of alkali-activated slag material based on color change value |
| CN113722969A (en) * | 2021-08-12 | 2021-11-30 | 武汉理工大学 | Tricalcium silicate hydration full-process performance index determination method and computational analyzer thereof |
| CN116373103A (en) * | 2023-03-06 | 2023-07-04 | 中国长江三峡集团有限公司 | Preparation method of high-crack-resistance hydraulic concrete |
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