CN105973757A - Method for obtaining chlorine ion diffusion and combination parameters in cement-based material - Google Patents

Method for obtaining chlorine ion diffusion and combination parameters in cement-based material Download PDF

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CN105973757A
CN105973757A CN201610274452.8A CN201610274452A CN105973757A CN 105973757 A CN105973757 A CN 105973757A CN 201610274452 A CN201610274452 A CN 201610274452A CN 105973757 A CN105973757 A CN 105973757A
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chloride ion
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万克树
司先军
徐自强
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Southeast University
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N13/00Investigating surface or boundary effects, e.g. wetting power; Investigating diffusion effects; Analysing materials by determining surface, boundary, or diffusion effects
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N15/00Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N17/00Investigating resistance of materials to the weather, to corrosion, or to light
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N13/00Investigating surface or boundary effects, e.g. wetting power; Investigating diffusion effects; Analysing materials by determining surface, boundary, or diffusion effects
    • G01N2013/003Diffusion; diffusivity between liquids
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N15/00Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
    • G01N2015/0042Investigating dispersion of solids
    • G01N2015/0061Investigating dispersion of solids in solids, e.g. petrography

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Abstract

The invention discloses a method for obtaining chlorine ion diffusion and combination parameters in a cement-based material. The method only needs a total chlorine ion concentration curve, and can simultaneously obtain a chlorine ion effective diffusion coefficient and adsorption isothermal curve parameters through regression calculation. The method comprises the following steps: obtaining a total chlorine ion concentration distribution curve by a non-steady state diffusion test; trying different combinations of to-be-obtained parameters, calculating to obtain a theoretical total chlorine ion concentration distribution curve; carrying out fitting regression of the theoretical curve and the experimental curve by a nonlinear least square method, to obtain a set of parameter values with the highest fitting degree; calculating the confidence interval of each parameter; and further calculating to obtain an adsorption curve, distribution curves of an apparent diffusion coefficient along with the time and space, and distribution curves of total chlorine ions, combined chlorine ions and free chlorine ions in the time and space. The method not only can obtain the diffusion parameter and the combination parameter, but also can obtain the intervals of the parameters.

Description

A kind of obtain chlorine ion binding capacity and the method for incorporating parametric in cement-based material
Technical field
The present invention relates to a kind of obtain chlorine ion binding capacity and the method for incorporating parametric in cement-based material, belong to cement matrix Material durability fields of measurement.
Background technology
The concrete reinforcement corrosion that Chloride Attack causes is an important endurance issues.In general, chloride ion Absorption can be occurred to combine with cement matrix when diffusion transport, thus chlorine ion binding capacity speed can be reduced and reduce rebar surface chlorine Ion concentration.Although controlling the mainly free chloride ion of corrosion, and combined chloride ion can being changed into freedom under certain condition Chloride ion, so the steel bar corrosion durability of research chloride binding and diffusion couple civil engineering structure is significant.
The diffusivity of chloride ion generally represents with diffusion coefficient, generally by diffusion channel process, natural diffusion method, electromigration Etc. recording corresponding diffusion coefficient.Diffusion channel process test period length and bad operation;Natural diffusion method obtains apparent diffusion coefficient, But this coefficient has included the impact combined, it it not diffusion transport parameter purely;The electromigration impact on combining is inconsiderate. Chloride binding capacity is typically described by chloride ion adsorption isotherm, and this curve is generally by counterbalanced procedure, natural diffusion method, spreading grooves The method such as method, electromigration records.Counterbalanced procedure can not reflect diffusion process;And for natural diffusion method, acid pasting can obtain relatively Total chloridion concentration accurately, but there is systematic error when recording free chloride ion by water soluble method or filter press technique;Diffusion channel process examination Test the cycle long;Electromigration can be affected by electric field.
And for consider chloride binding Life Prediction Model, generally with finite difference calculus (Mart í n-P é rez B, Zibara H, Hooton R D, et al.A study of the effect of chloride binding on Service life predictions [J] .Cement&Concrete Research, 2000,30 (8): 1215-1223.) or Analytic method (Liang M T, Huang R, Jheng H Y.Reconsideration for a study of the effect of chloride binding on service life predictions[J].Journal of Marine Science& Technology, 2011,19:531-540.) solve, but, the premise of these methods is diffusion parameter and incorporating parametric It is known.(Baroghel-Bouny V, Wang X, Thiery M, the et al.Prediction of such as Baroghel chloride binding isotherms of cementitious materials by analytical model or Numerical inverse analysis [J] .Cement&Concrete Research, 2012,42 (42): 1207- 1224.) proposing two kinds of numerical analysis methods obtaining binding curve, one is the known diffusion coefficient of requirement, and another kind is not Error solution is reasonably make use of to try to achieve diffusion coefficient in advance.The Return Law is a kind of according to data with existing and regression equation (mould Type), the method obtaining series of parameters by programming, is a kind of very universal research method.
Summary of the invention
Goal of the invention: the technical problem to be solved is to provide and a kind of obtains the expansion of chloride ion in cement-based material Dissipating and the method for incorporating parametric, the method has only to a total chloridion concentration curve, can obtain chlorine by regression Calculation simultaneously The effective diffusion cofficient of ion and adsorption isothermal curve parameter.
For solving above-mentioned technical problem, the technical solution adopted in the present invention is:
A kind of obtain chlorine ion binding capacity and the method for incorporating parametric in cement-based material, comprise the steps:
Step 1, is tested by the Unsteady Casting of chloride ion, obtains total chloridion concentration in cement-based material deep with diffusion Degree x and/or the distribution curve of t diffusion time;
Step 2, it is considered to chloride ion diffusion in cement-based material and combination, sets up following transmission equation:
Equation (1) is total chloridion Ct(x, t), free chloride ion Cf(x, t) with combined chloride ion Cb(x, t) pass of concentration Being formula, wherein, m is the parameter of free chloride ion and total chloridion unit conversion, the value of m along with each variable unit difference and Change;
Ct(x, t)=Cb(x, t)+m Cf(x, t) (1);
Equation (2) is free chloride ion Cf(x, t) with combined chloride ion Cb(x, t) functional relationship between concentration use chlorine Ionic adsorption isothermal line represents, as a example by Langmuir adsorption isotherm, wherein, α and β is incorporating parametric:
C b = αC f 1 + βC f - - - ( 2 ) ;
Equation (3) is Fick's second law and boundary condition thereof and initial condition, wherein, DaIt it is cement-based material hole solution The apparent diffusion coefficient of middle chloride ion, C0(mol/L) being the concentration of soaking solution, L is infinitely great;
∂ C f ( x , t ) ∂ t = ∂ ∂ x ( D a · ∂ C f ( x , t ) ∂ x )
Cf(x, 0)=O (3)
Cf(O, t)=c0
Cf(L, 0)=O;
Equation (4) is DaWith chloride ion effective diffusion cofficient D in cement-based material hole solutioneBetween relational expression;Wherein,It is chloride binding capacity, can be obtained by equation (2);
D a = D e 1 + 1 m · ∂ C b ( x , t ) ∂ C f ( x , t ) - - - ( 4 ) ;
Equation (5) is the analytic solutions of equation (4),;
∫ C 0 C f D a ( C f ) dC f ∫ C 0 0 D a ( C f ) dC f = e r f ( x 4 D a ( C f ) t ) - - - ( 5 ) ;
Step 3, in certain parameter area, selects any one set effective dispersion parameter DeAnd incorporating parametric, according to side Journey (2)~(5) can calculate acquisition free chloride ion Cf(x, t) concentration profile, then substitute into equation (1)~(2) can obtain always Chloride ion Ct(x, t) concentration profile i.e. have only to, in certain parameter area, go to attempt not with certain parameter step length With parameter combination calculation can obtain theoretical total chloridion concentration profile, the most again with nonlinear method of least square and The experiment total chloridion concentration profile that step 1 obtains is fitted returning, the set of parameter that final acquisition degree of fitting is the highest Value;
Step 4, it is assumed that what parameter value that degree of fitting is the highest was corresponding is real parameter value, is substituted into diffusion equation and is calculated Obtaining a theoretical curve, using theoretical curve as input curve, its highest degree of fitting will be 100%, and each degree of fitting is corresponding In set of parameter value, two degrees of fitting varied in size i.e. can determine that set of parameter scope, step 3 the highest degree of fitting obtained And the parameter area between 100% degree of fitting is the confidence interval of each parameter;
Step 5, the parameter value that the degree of fitting that step 3 obtained is the highest again substitutes into equation (1)~(5), can be calculated Adsorption isothermal curve, apparent diffusion coefficient is with diffusion time and the distribution curve of diffusion depth and total chloridion concentration, combination Chlorine ion concentration and free chloride ion concentration are with diffusion time and the distribution curve of diffusion depth.
Wherein, in step 1, described cement-based material is clean slurry, mortar or concrete.
Wherein, in step 1, the Unsteady Casting test of described chloride ion uses natural immersion method, described natural immersion method Soak including laboratory and on-the-spot immersion.
Wherein, in step 1, in described cement-based material, total chloridion concentration passes through acid pasting, electron probe, X-ray energy Spectrum or x-ray tomography imaging obtain.
Wherein, in step 2, described chloride ion suction type include linear adsorption curve, Langmuir adsorption curve, Freundlich adsorption curve, BET adsorption curve or Redlich adsorption curve.
Experimental data is returned by the inventive method by theory return model, obtains chlorine ion binding capacity parameter simultaneously Value with incorporating parametric.
The main assumption used in equation (1)~(5) is as follows: the precondition that i.e. equation is set up is:
(1) single-particle diffusion is only considered;
(2) sample is water of satisfying completely;
(3) sample is considered as uniform;
(4) Semi-infinite One-dimensional condition;
(5) chloride ion only spreads in hole solution, and the Concentraton gradient of free chloride ion is uniquely to transmit driving force;
(6) in whole diffusion process, temperature constant;
(7) the free chloride ion concentration of sample boundaries (surface) is equal to extraneous soaking concentration, and in sample, initial chloride ion is dense Degree is zero;
(8) effective dispersion parameter De, incorporating parametric, can evaporated water weDo not change with soak time and diffusion depth.
Compared with prior art, the invention have the advantages that:
First, the inventive method only with one experiment total chloridion concentration profile just can obtain simultaneously diffusion parameter and The value of incorporating parametric, it is also possible to obtain the confidence interval of every kind of parameter;
Secondly, the inventive method directly returns the concentration profile obtaining free chloride ion, it is to avoid test measure from By the problem of chlorine ion concentration, and result is more accurate, in hgher efficiency;
Finally, the inventive method serves impetus for chlorine ion binding capacity in research cement-based material with associated methods.
Accompanying drawing explanation
Fig. 1 is fitting result chart and the fitting result chart of tradition error function method of the embodiment of the present invention;
Fig. 2 is the adsorption curve figure of the embodiment of the present invention;
Fig. 3 is that the apparent diffusion coefficient of the embodiment of the present invention is with diffusion depth change curve and the table of tradition error function method See the effective diffusion cofficient that diffusion coefficient obtains with diffusion depth change curve and the inventive method;
Fig. 4 is that embodiment of the present invention apparent diffusion coefficient at diffusion depth 5mm is with soak time change curve and biography Effective diffusion that the apparent diffusion coefficient that system error function method obtains obtains with soak time change curve and the inventive method Coefficient;
Fig. 5 be the embodiment of the present invention free chloride ion concentration with diffusion depth change curve and with its experimental data Contrast;
Fig. 6 is embodiment of the present invention total chloridion at diffusion depth 5mm, free chloride ion and combined chloride ion concentration With soak time change curve.
Detailed description of the invention
Below in conjunction with the accompanying drawings and embodiment, being described in detail technical scheme, the embodiment of the present invention uses Zibara (Zibara H.Binding of external chloride by cement pastes, Ph.D.Thesis, 2001, department ofbuilding materials, University of Toronto, Canada.) data carry out Explanation.But the scope of protection of present invention is not limited to the scope that embodiment represents, therefore all according to present patent application scope The equivalence that described principle and feature are done changes or modifies, in the range of being all included in present patent application.
The present invention is that the recurrence of a kind of simple curve obtains chlorine ion binding capacity and the method for incorporating parametric in cement-based material, its tool Body comprises the steps:
Step 1, is tested by the Unsteady Casting of chloride ion, obtains total chloridion concentration in cement-based material deep with diffusion Degree x and/or the distribution curve of t diffusion time;
Determine that unit of account, diffusion depth unit are m, total chloridion Ct(x, t) with combined chloride ion Cb(x, t) concentration list Position is g chloride/g binder, free chloride ion Cf(x, t) concentration unit is mol/L, can evaporate water content weUnit is g H2O/g binder, and data in literature is carried out unit conversion;
Step 2, it is considered to chloride ion spreads in cement-based material and combines, sets up following transmission equation:
Equation (1) is the relational expression between total chloridion, free chloride ion and combined chloride ion concentration:
Ct(x, t)=Cb(x, t)+Cf(x, t) we·MCl/ρ (1);
Wherein, MClIt is the molal weight of chloride ion, equal to 35.45g/mol;ρ is the density of hole solution, approximates 1000g/ L;
Equation (2) is free chloride ion Cf(x, t) with combined chloride ion Cb(x, t) functional relationship between concentration use chlorine Ionic adsorption isothermal line represents, the chloride ion suction type used by the present embodiment is Freundlich absorption:
C b = αC f β - - - ( 2 ) ;
Equation (3) is Fick's second law and boundary condition thereof and initial condition, and wherein, Da is cement-based material hole solution In chloride ion apparent diffusion coefficient, C0 (mol/L) is the concentration of soaking solution, and L is infinitely great;
∂ C f ( x , t ) ∂ t = ∂ ∂ x ( D a · ∂ C f ( x , t ) ∂ x )
Cf(x, 0)=O (3)
Cf(O, t)=c0
Cf(L, 0)=O;
Equation (4) is DaWith the chloride ion effective diffusion cofficient D in cement-based material hole solutioneBetween relational expression:
D a = D e 1 + ραβC f β - 1 w e - M C l - - - ( 4 ) ;
Equation (5) is required analytic solutions:
∫ C 0 C f D e 1 + ραβC f β - 1 w e - M C l dC f ∫ C 0 0 D e 1 + ραβC f β - 1 w e - M C l dC f = e r f ( x 4 · D e 1 + ραβC f β - 1 w e - M C l · t ) - - - ( 5 ) ;
Step 3, setup parameter span, the span of α is: 0.001-0.025, and step-length is 0.001;The value of β Scope is: 0.1-2, and step-length is 0.01;De=0.25-11.5*10-12m2/ s, step-length is 0.25;C0=1mol/L;Carry out curve Matching, obtains the set of parameter value that degree of fitting is the highest, as shown in table 1;Calculate the contrast fitting effect of data and experimental data such as Shown in Fig. 1;
Step 4, is calculated a theoretical curve by step 3 parameters obtained value substitution diffusion equation, exports and obtained by step 3 Parameter area between the maximum degree of fitting and 100% degree of fitting that arrive, obtains the confidence interval of each parameter, as shown in table 1;
Step 5, the parameter value that the degree of fitting that step 3 obtained is the highest again substitutes into equation (1)~(5), can be calculated Adsorption isothermal curve, apparent diffusion coefficient is with diffusion time and the distribution curve of diffusion depth and total chloridion concentration, combination Chlorine ion concentration and free chloride ion concentration are with diffusion time and the distribution curve of diffusion depth, the most as shown in figures 2-6.
Table 1 parameter fitting value
Parameter Optimal value Parameter area
α 0.013 0.012-0.014
β 0.73 0.68-0.79
De(10-12m2/s) 5.71 5.43-6.29
Obviously, above-described embodiment is only for clearly demonstrating example of the present invention, and not to the present invention The restriction of embodiment.For those of ordinary skill in the field, can also be made it on the basis of the above description The change of its multi-form or variation, here without also cannot all of embodiment be given exhaustive, these changes extended out Change or variation is also among protection scope of the present invention.

Claims (5)

1. one kind obtains chlorine ion binding capacity and the method for incorporating parametric in cement-based material, it is characterised in that: comprise the steps:
Step 1, is tested by the Unsteady Casting of chloride ion, obtains in cement-based material total chloridion concentration with diffusion depth x And/or the distribution curve of t diffusion time;
Step 2, it is considered to chloride ion diffusion in cement-based material and combination, sets up following transmission equation:
Equation (1) is total chloridion Ct(x, t), free chloride ion Cf(x, t) with combined chloride ion Cb(x, t) relational expression of concentration, Wherein, m is the parameter of free chloride ion and total chloridion unit conversion;
Ct(x, t)=Cb(x, t)+m Cf(x, t) (1);
Equation (2) is free chloride ion Cf(x, t) with combined chloride ion Cb(x, t) functional relationship between concentration use chloride ion Adsorption isotherm represents, wherein, α and β is incorporating parametric:
C b = αC f 1 + βC f - - - ( 2 ) ;
Equation (3) uses Fick's second law and boundary condition thereof and initial condition, wherein, DaIt is in cement-based material hole solution The apparent diffusion coefficient of chloride ion, C0(mol/L) being the concentration of soaking solution, L is infinitely great;
∂ C f ( x , t ) ∂ t = ∂ ∂ x ( D a · ∂ C f ( x , t ) ∂ x )
Cf(x, 0)=0 (3)
Cf(0, t)=cQ
Cf(L, 0)=0;
Equation (4) is DaWith chloride ion effective diffusion cofficient D in cement-based material hole solutioneBetween relational expression;Wherein,It is chloride binding capacity, can be obtained by equation (2);
D a = D e 1 + 1 m · ∂ C b ( x , t ) ∂ C f ( x , t ) - - - ( 4 ) ;
Equation (5) is the analytic solutions of equation (4),
∫ C 0 C f D a ( C f ) dC f ∫ C 0 0 D a ( C f ) dC f = e r f ( x 4 D a ( C f ) t ) - - - ( 5 ) ;
Step 3, in certain parameter area, selects any one set effective dispersion parameter DeAnd incorporating parametric, according to equation (2) ~(5) can calculate acquisition free chloride ion Cf(x, t) concentration profile, then substitute into equation (1)~(2) can obtain total chloridion Ct(x, t) concentration profile, the experiment total chloridion concentration distribution then obtained by nonlinear method of least square and step 1 Curve is fitted returning, the set of parameter value that final acquisition degree of fitting is the highest;
Step 4, it is assumed that what parameter value that degree of fitting is the highest was corresponding is real parameter value, is substituted into diffusion equation and is calculated Article one, theoretical curve, using theoretical curve as input curve, its highest degree of fitting will be 100%, step 3 the highest plan obtained Parameter area between right and 100% degree of fitting is the confidence interval of each parameter;
Step 5, the parameter value that the degree of fitting that step 3 obtained is the highest again substitutes into equation (1)~(5), can be calculated isothermal Adsorption curve, apparent diffusion coefficient with diffusion time and the distribution curve of diffusion depth and total chloridion concentration, combined chloride from Sub-concentration and free chloride ion concentration are with diffusion time and the distribution curve of diffusion depth.
Chlorine ion binding capacity and the method for incorporating parametric in acquisition cement-based material the most according to claim 1, its feature exists In: in step 1, described cement-based material is clean slurry, mortar or concrete.
Chlorine ion binding capacity and the method for incorporating parametric in acquisition cement-based material the most according to claim 1, its feature exists In: in step 1, the Unsteady Casting test of described chloride ion uses natural immersion method, and described natural immersion method includes laboratory Soak and on-the-spot immersion.
Chlorine ion binding capacity and the method for incorporating parametric in acquisition cement-based material the most according to claim 1, its feature exists In: in step 1, in described cement-based material, total chloridion concentration is broken by acid pasting, electron probe, X-ray energy spectrum or X-ray Layer imaging obtains.
Chlorine ion binding capacity and the method for incorporating parametric in acquisition cement-based material the most according to claim 1, its feature exists In: in step 2, described chloride ion suction type includes that linear adsorption curve, Langmuir adsorption curve, Freundlich adsorb Curve, BET adsorption curve or Redlich adsorption curve.
CN201610274452.8A 2016-04-28 2016-04-28 Method for obtaining chlorine ion diffusion and combination parameters in cement-based material Pending CN105973757A (en)

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Cited By (6)

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CN106802318A (en) * 2017-01-09 2017-06-06 北京工业大学 A kind of assay method of hydrated cement paste chlorion fixed amount
CN106970207A (en) * 2017-03-02 2017-07-21 西安交通大学 A kind of method of the Chloride Ion in Concrete diffusion analysis based on meso-mechanical model
CN108827989A (en) * 2018-06-29 2018-11-16 山东大学 A kind of method that C-S-H gel adsorption combination chloride ion accounts for total binding chloride ion ratio in measurement cement paste
CN109946414A (en) * 2019-03-27 2019-06-28 东南大学 A method of amount of chloride ions is combined using cement-based material oxide content characterization
CN112557254A (en) * 2020-11-25 2021-03-26 东南大学 Method for predicting effective diffusion coefficient of chloride ions in cement slurry
CN112630129A (en) * 2020-10-28 2021-04-09 中冶建筑研究总院有限公司 Device for measuring erosion diffusion depth of FRP (fiber reinforced Plastic) material

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106802318A (en) * 2017-01-09 2017-06-06 北京工业大学 A kind of assay method of hydrated cement paste chlorion fixed amount
CN106970207A (en) * 2017-03-02 2017-07-21 西安交通大学 A kind of method of the Chloride Ion in Concrete diffusion analysis based on meso-mechanical model
CN106970207B (en) * 2017-03-02 2019-01-08 西安交通大学 A method of the Chloride Ion in Concrete diffusion analysis based on meso-mechanical model
CN108827989A (en) * 2018-06-29 2018-11-16 山东大学 A kind of method that C-S-H gel adsorption combination chloride ion accounts for total binding chloride ion ratio in measurement cement paste
CN109946414A (en) * 2019-03-27 2019-06-28 东南大学 A method of amount of chloride ions is combined using cement-based material oxide content characterization
CN109946414B (en) * 2019-03-27 2022-03-08 东南大学 Method for representing amount of combined chloride ions by using content of cement-based material oxide
CN112630129A (en) * 2020-10-28 2021-04-09 中冶建筑研究总院有限公司 Device for measuring erosion diffusion depth of FRP (fiber reinforced Plastic) material
CN112630129B (en) * 2020-10-28 2023-10-20 中冶建筑研究总院有限公司 Measuring device for erosion diffusion depth of FRP material
CN112557254A (en) * 2020-11-25 2021-03-26 东南大学 Method for predicting effective diffusion coefficient of chloride ions in cement slurry
CN112557254B (en) * 2020-11-25 2022-04-15 东南大学 Method for predicting effective diffusion coefficient of chloride ions in cement slurry

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Application publication date: 20160928