CN108827989A - A kind of method that C-S-H gel adsorption combination chloride ion accounts for total binding chloride ion ratio in measurement cement paste - Google Patents
A kind of method that C-S-H gel adsorption combination chloride ion accounts for total binding chloride ion ratio in measurement cement paste Download PDFInfo
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 154
- 239000004568 cement Substances 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 33
- 238000005259 measurement Methods 0.000 title claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 26
- 239000004567 concrete Substances 0.000 claims abstract description 25
- 238000012360 testing method Methods 0.000 claims description 31
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000004458 analytical method Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 239000011780 sodium chloride Substances 0.000 claims description 10
- 238000012423 maintenance Methods 0.000 claims description 8
- 238000005520 cutting process Methods 0.000 claims description 7
- 238000005516 engineering process Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 230000007774 longterm Effects 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000004364 calculation method Methods 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000010998 test method Methods 0.000 claims description 4
- 239000010881 fly ash Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 101100008047 Caenorhabditis elegans cut-3 gene Proteins 0.000 claims 1
- 239000000523 sample Substances 0.000 abstract description 58
- 238000003763 carbonization Methods 0.000 abstract description 19
- 239000002002 slurry Substances 0.000 abstract description 14
- 230000009467 reduction Effects 0.000 abstract description 8
- 230000008275 binding mechanism Effects 0.000 abstract description 3
- 239000004035 construction material Substances 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
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- Crystallography & Structural Chemistry (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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- Pathology (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The present invention provides a kind of C-S-H gel adsorption combination chloride ion method that accounts for total binding chloride ion ratio in measurement cement paste, belongs to construction material determination techniques field.This method is based on Friedel ' s salt and C-S-H gel content greatest differences in cement slurry, Friedel ' s salt and C-S-H gel are decomposed using carbonization mode, obtain the reduction amount that chloride ion reduction amount and corresponding C-S-H gel are combined after Friedel ' s salt is not present, to obtain the content of unit C-S-H gel adsorption chloride ion, and then obtains chloride binding and reach the amount of C-S-H gel adsorption combination chloride ion in balance after-hardening cement slurry and account for the ratio of total binding chloride ion content.This method is ingenious in design, and method is simple, further to probe into chloride binding mechanism and its influence to cement base gel rubber system and concrete structure durability lays the foundation.
Description
Technical field
The invention belongs to construction material determination techniques fields, and in particular to C-S-H gel is inhaled in a kind of measurement cement paste
The method that attached combination chloride ion accounts for total binding chloride ion ratio.
Background technique
The steel bar corrosion that chloride ion induces under marine environment or deicing salt environment is to cause the durability of concrete structure bad
One of the main reason for change.It is well known that being that free chloride ion causes steel bar corrosion in the presence of oxygen and moisture.
And in cement-based material in conjunction with chloride ion formation can correspondingly reduce free chloride ion content (total chloridion be equal to free chlorine
The sum of ion and combination chloride ion, if the amount of total chloridion is constant, increases in conjunction with chloride ion and inevitably result in free chloride ion
Reduce), to reduce the risk that reinforcing bar corrodes.Therefore, the chloride binding capacity of matrix is durable for concrete structure
Property have great influence.
There are two types of the mechanism of chloride binding:Physical bond and chemical bonding [Andrej I, V, Roman G,
et al. Chloride binding into hydrated blended cements: The influence of
limestone and alkalinity[J]. Cement and Concrete Research, 2013, 48: 74-85.
].Physical bond refers to that chloride ion is adsorbed on hydrolysis product of cement, predominantly C-S-H gel, because it compares table with biggish
Area and adsorbing chloride ions;Chemical bonding refers to that (AFm is single sulfur type aquation sulphur to chloride ion with AFm phase compound in hydrated product
Abbreviation [Mickael S, V é ronique B, the Fabien B. Chloride binding in sound of calcium aluminate family
and carbonated cementitious materials with various types of binder[J].
Construction and Building Materials, 2014, 68:82-91.]) chemical reaction generation chloride containing occurs
Close object, such as Friedel ' s salt.Total combination chloride ion be mainly exactly by C-S-H gel adsorption chloride ion and
The chloride ion composition that Friedel ' s salt combines.After cement slurry and chloride ion contact, the combination chloride ion of both forms is same
When formed and existed, and test sum that the combination chloride ion content that measures both is at present, be not easy exclusion and test one independent of one another
Class combination chloride ion.Along with the formation for combining chloride ion is an extremely complex process, and affected by many factors, institute
To be difficult to determine C-S-H gel or Friedel ' s salt are capable of forming how many chloride ion respectively, in other words every kind of form combined chloride from
Son accounts for the ratio of summary and chloride ion, it is therefore necessary to the content ratio of single form combination chloride ion in hardened cement paste
Measuring method is studied.
Summary of the invention
In view of the above shortcomings of the prior art, inventor provides a kind of indirect determination through long-term technology and practical exploration
The method that C-S-H gel adsorption combination chloride ion accounts for total binding chloride ion ratio in cement paste.This method is based on cement slurry
Middle Friedel ' s salt and C-S-H gel content greatest differences, decompose Friedel ' s salt and C-S-H gel using carbonization mode,
The reduction amount that chloride ion reduction amount and corresponding C-S-H gel are combined after Friedel ' s salt is not present is obtained, to obtain list
The content of position C-S-H gel adsorption chloride ion, and then acquisition chloride binding reaches C-S-H in balance after-hardening cement slurry and coagulates
Glue absorption accounts for the ratio of total binding chloride ion content in conjunction with the amount of chloride ion.This method is ingenious in design, and method is simple, is further
It probes into chloride binding mechanism and its influence to cement base gel rubber system and concrete structure durability lays the foundation.
Specifically, the present invention adopts the following technical scheme that:
A kind of method that C-S-H gel adsorption combination chloride ion accounts for total binding chloride ion ratio in measurement cement paste, institute
The method of stating includes:
1) sample cement plus water is stirred into cement paste processed, will be conserved after the molding of cement paste reverse mould, demoulding;
2) three pieces of samples are taken out from test specimen and marks S0, S1, S2 respectively;By sample S0 in no CO2After being dried under environment
Measure its sample free chloride ion content cf,0, total chloridion content ct,0, can be calculated in sample and combine chloride ion cb,0,
Quantitative XRD material phase analysis is carried out simultaneously obtains C-S-H gel content csh0;
3) sample S1, S2 is respectively placed in CO2Until Friedel ' s salt is carbonized completely in S1, S2 sample in atmosphere;Take out sample
In no CO after product S12Its sample free chloride ion content c is measured after being dried under environmentf,1With total chloridion content ct,1, i.e.,
It can be calculated in sample and combine chloride ion cb,1, while carrying out quantitative XRD material phase analysis and obtaining C-S-H gel content csh1;
4) in CO after certain interval of time2Sample S2 is taken out in atmosphere, then in no CO2It is surveyed after being dried under environment
Fixed its sample free chloride ion content cf,2With total chloridion content ct,2, can be calculated in sample and combine chloride ion cb,2, together
Shi Jinhang quantifies XRD material phase analysis and obtains C-S-H gel content csh2;
5) pass through the amount of the combination chloride ion of formula (1) unit of account C-S-H gel adsorption;And then carbon is not carried out known
C-S-H gel content csh in the sample S0 of change0And its combine the amount c of chloride iontotal,CSHIn the case of to get hardened cement paste
The amount of middle C-S-H gel adsorption combination chloride ion accounts for the ratio P of total binding chloride ion contentCSH;
Preferably, in the step 1),
Any one cement that sample cement can be known in the art, such as reference cement and other existing cement
Type is also possible to the compounding cement doped with other components, such as doped with flyash or the cement of miberal powder;
Water-cement ratio is not particularly limited in the present invention, as long as with certain flowing when can guarantee cement paste stirring
Property, it can form in a mold, specifically, water-cement ratio is 0.3~0.7, further preferably 0.4;
Certain density chlorate is added in the present invention into mixing water, to guarantee that the amount of chloride ion can make in slurry
The combination of hydrated product and chloride ion reaches saturation, specifically, the chlorate is NaCl, it is preferred that mixing water is concentration
3.0%~10.0% NaCl solution;The further preferably NaCl solution of concentration 3.5%;
Reverse mould forms concrete technology:It is the close of 85~95% (preferably 90%) that cement paste reverse mould, which is placed on humidity,
20~28h (preferably for 24 hours) is stood in seal apparatus;
Conserving concrete technology is:It is 85~95% (preferably 90%) that hardened paste test specimen after demoulding, which is placed in humidity,
Maintenance is stood in sealing device, to avoid test specimen from directly contacting with water or solution in maintenance processes;Curing time control 28~
112d (preferably 56d), to guarantee that hydrated product and chloride binding reach balance in curing time entoplasm body;
Preferably, in the step 2),
Three pieces of sample specification sizes are identical, for convenient for follow-up test step, specifically, three pieces of sample collection methods
For:3 thin slices (preferably 1.0mm) with a thickness of 1.0~3.0mm are cut from position among test specimen using precision gas cutting machine, into
One step is preferred, and lamina dimensions are 40mm × 40mm × 1mm;Guarantee the complete identity property of three pieces of samples;
Sample S0 is in no CO2Actual conditions, which are dried, under environment is:40~50 DEG C of drying temperature (preferably 45 DEG C) is done
The dry time is 7~14d;
Preferably, in the step 3),
CO is used to sample S1, S22The actual conditions being carbonized are:Temperature is 23 ± 1 DEG C, humidity 70 ± 2%, CO2It is dense
Degree is 10~100% (preferably 20%);
Sample S1 is in no CO2Actual conditions, which are dried, under environment is:40~50 DEG C of drying temperature (preferably 45 DEG C) is done
The dry time is 7~14d;
Preferably, in the step 4),
Interval time is 1~60d;It can be 1d, 14d, 28d, 56d (preferably 28d);
Sample S2 is in no CO2Actual conditions, which are dried, under environment is:40~50 DEG C of drying temperature (preferably 45 DEG C) is done
The dry time is 7~14d;
Preferably, the step 2), 3) and 4) in,
The measurement of free chloride ion and total chloridion can be according to《Marine traffic engineering concrete test specification (JTJ270-98)》Or
《Standard for test methods of longterm performance and durability of ordinary concrete standard (GB/T50082-2009)》It carries out, and quantitative XRD object phase
Analysis then can be according to document [Chang H.Chloride binding capacity of pastes influenced by
carbonation under three conditions[J].Cement&Concrete Composites,2017,84:1-
9.] tested.
Preferably, in the step 5), the amount of the combination chloride ion of C-S-H gel adsorption in the sample S0 that is not carbonized
The amount c of the combination chloride ion of total C-S-H gel adsorption when as initialtotal,CSH, shown in calculation formula such as formula (2):
CToral, CSH=cUiit, CSH×csh0 (2)
And then the ratio of total binding chloride ion content is accounted for by the amount that formula (3) obtain C-S-H gel adsorption combination chloride ion
Example PCSH
Beneficial effects of the present invention:
The present invention provides C-S-H gel adsorption combination chloride ion in a kind of indirect determination cement paste for the first time and accounts for total binding chlorine
The method of ion ratio.It is described to be based on Friedel ' s salt and C-S-H gel content greatest differences in cement slurry, using carbonization
Mode decomposes Friedel ' s salt and C-S-H gel, obtains that there is no chloride ion reduction amount and right is combined after Friedel ' s salt
The reduction amount for the C-S-H gel answered to obtain the content of unit C-S-H gel adsorption chloride ion, and then obtains chloride ion knot
It closes and reaches the ratio that the amount for balancing C-S-H gel adsorption combination chloride ion in after-hardening cement slurry accounts for total binding chloride ion content
Example.
This method is ingenious in design, and method is simple, further to probe into chloride binding mechanism and its to cement base gelinite
The influence of system and concrete structure durability lays the foundation.
Detailed description of the invention
Fig. 1 is the total chloridion and free chloride ion content schematic diagram in embodiment 1 after different carbonization times in sample;
Fig. 2 is each object phase constituent content schematic diagram in sample after different carbonization times.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
As previously mentioned, although there are two types of the mechanism of chloride binding:Physical bond and chemical bonding.And when cement slurry with
After chloride ion contact, the combination chloride ion of both forms is formed simultaneously and exists, but tests the combination chloride ion measured at present
Content is the sum of the two, is not easy to exclude test one kind independent of one another and combines chloride ion.
In view of this, in a kind of specific embodiment of the invention, C-S-H gel in a kind of measurement cement paste is provided and is inhaled
The method that attached combination chloride ion accounts for total binding chloride ion ratio, the method includes:
1) sample cement plus water is stirred into cement paste processed, will be conserved after the molding of cement paste reverse mould, demoulding;
2) three pieces of samples are taken out from test specimen and marks S0, S1, S2 respectively;By sample S0 in no CO2After being dried under environment
Measure its sample free chloride ion content cf,0, total chloridion content ct,0, can be calculated in sample and combine chloride ion cb,0,
Quantitative XRD material phase analysis is carried out simultaneously obtains C-S-H gel content csh0;
3) sample S1, S2 is respectively placed in CO2Until Friedel ' s salt is carbonized completely in S1, S2 sample in atmosphere;Take out sample
In no CO after product S12Its sample free chloride ion content c is measured after being dried under environmentf,1With total chloridion content ct,1, i.e.,
It can be calculated in sample and combine chloride ion cb,1, while carrying out quantitative XRD material phase analysis and obtaining C-S-H gel content csh1;
4) in CO after certain interval of time2Sample S2 is taken out in atmosphere, then in no CO2It is surveyed after being dried under environment
Fixed its sample free chloride ion content cf,2With total chloridion content ct,2, can be calculated in sample and combine chloride ion cb,2, together
Shi Jinhang quantifies XRD material phase analysis and obtains C-S-H gel content csh2;
5) pass through the amount of the combination chloride ion of formula (1) unit of account C-S-H gel adsorption;And then carbon is not carried out known
C-S-H gel content csh in the sample S0 of change0And its combine the amount c of chloride iontotal,CSHIn the case of to get hardened cement paste
The amount of middle C-S-H gel adsorption combination chloride ion accounts for the ratio P of total binding chloride ion contentCSH;
When the amount of the combination chloride ion of C-S-H gel adsorption is initial in the sample S0 wherein, not being carbonized always
The amount c of the combination chloride ion of C-S-H gel adsorptiontotal,CSH, shown in calculation formula such as formula (2):
cToral, CSH=cUnit, CSH×csh0 (2)
And then the ratio of total binding chloride ion content is accounted for by the amount that formula (3) obtain C-S-H gel adsorption combination chloride ion
Example PCSH
In still another embodiment of the invention, in the step 1),
Any one cement that sample cement can be known in the art, such as reference cement and other existing cement
Type is also possible to the compounding cement doped with other components, such as doped with flyash or the cement of miberal powder;
Water-cement ratio is not particularly limited in the present invention, as long as with certain flowing when can guarantee cement paste stirring
Property, it can form in a mold, specifically, water-cement ratio is 0.3~0.7, further preferably 0.4;
Certain density chlorate is added in the present invention into mixing water, to guarantee that the amount of chloride ion can make in slurry
The combination of hydrated product and chloride ion reaches saturation, specifically, the chlorate is NaCl, it is preferred that mixing water is concentration
3.0%~10.0% NaCl solution;The further preferably NaCl solution of concentration 3.5%;
Reverse mould forms concrete technology:It is the close of 85~95% (preferably 90%) that cement paste reverse mould, which is placed on humidity,
20~28h (preferably for 24 hours) is stood in seal apparatus;
Conserving concrete technology is:It is 85~95% (preferably 90%) that hardened paste test specimen after demoulding, which is placed in humidity,
Maintenance is stood in sealing device, to avoid test specimen from directly contacting with water or solution in maintenance processes;Curing time control 28~
112d (preferably 56d), to guarantee that hydrated product and chloride binding reach balance in curing time entoplasm body;
In still another embodiment of the invention, in the step 2),
Three pieces of sample specification sizes are identical, for convenient for follow-up test step, specifically, three pieces of sample collection methods
For:3 thin slices (preferably 1.0mm) with a thickness of 1.0~3.0mm are cut from position among test specimen using precision gas cutting machine, into
One step, lamina dimensions are 40mm × 40mm × 1mm;;
Sample S0 is in no CO2Actual conditions, which are dried, under environment is:40~50 DEG C of drying temperature (preferably 45 DEG C) is done
The dry time is 7~14d;
In still another embodiment of the invention, in the step 3),
CO is used to sample S1, S22The actual conditions being carbonized are:Temperature is 23 ± 1 DEG C, humidity 70 ± 2%, CO2It is dense
Degree is 10~100% (preferably 20%);
Sample S1 is in no CO2Actual conditions, which are dried, under environment is:40~50 DEG C of drying temperature (preferably 45 DEG C) is done
The dry time is 7~14d;
In still another embodiment of the invention, in the step 4),
Interval time is 1~60d;It can be 1d, 14d, 28d, 56d
In still another embodiment of the invention, interval time 28d;
Sample S2 is in no CO2Actual conditions, which are dried, under environment is:40~50 DEG C of drying temperature (preferably 45 DEG C) is done
The dry time is 7~14d;
In still another embodiment of the invention, the step 2), 3) and 4) in,
The measurement of free chloride ion and total chloridion can be according to《Marine traffic engineering concrete test specification (JTJ270-98)》Or
《Standard for test methods of longterm performance and durability of ordinary concrete standard (GB/T50082-2009)》It carries out, and quantitative XRD object phase
Analysis then can be according to document [Chang H.Chloride binding capacity of pastes influenced by
carbonation under three conditions[J].Cement&Concrete Composites,2017,84:1-
9.] tested.
In conjunction with specific example, the present invention is further illustrated, and following instance is not right merely to the explanation present invention
Its content is defined.If the experiment actual conditions being not specified in embodiment, usually according to normal condition, or it is public according to sale
Take charge of recommended condition;It is not particularly limited in the present invention, can be commercially available by commercial sources.
Embodiment 1
Using reference cement, water-cement ratio 0.40, mixing water is the NaCl solution that concentration is 3.5%.In net slurry agitated kettle
After the completion of stirring, slurry is poured into 40mm × 40mm × 160mm mold.Then by mold be put into humidity be about 90% it is close
It is stood for 24 hours in joint sealing.It takes out demoulding afterwards for 24 hours, and the slurry test specimen of hardening is continued to be put into the seal box that humidity is about 90%
Conserve 56d.Test specimen is avoided directly to contact with water or solution in maintenance processes.
Test specimen is taken out after the completion of maintenance, cutting 3 thickness from position among test specimen using precision gas cutting machine is about 1.0mm's
Thin slice, lamina dimensions are about 40mm × 40mm × 1mm, and are respectively labeled as S0, S1, S2.Cutting process will avoid contacting with water,
Test specimen and cutting tool are cooled down using dehydrated alcohol.S0 is put into 45 DEG C of vacuum ovens first, dry 7~14d is most
Amount makes S0 in no CO2In the environment of it is dry.Then S1, S2 are put into temperature is 23 ± 1 DEG C, humidity 70 ± 2%, CO2Concentration is about
20%, be carbonized in case 28d, the 56d of being successively carbonized.
It is S0 after drying is broken and levigate extremely can then weigh three parts of 2g samples, Yi Fenyong all by 80 μm of sieves
Free chloride ion in test sample, portion are used for the total chloridion of test sample, and portion is for doing quantitative XRD object phase point
Analysis.The test of free chloride ion and total chloridion can be according to《Marine traffic engineering concrete test specification (JTJ270-98)》Or《Commonly
Concrete long-term behaviour and endurance quality test method standard (GB/T 50082-2009)》It carries out, and quantitative XRD material phase analysis
It then can be according to document [Chang H.Chloride binding capacity of pastes influenced by
carbonation under three conditions[J].Cement&Concrete Composites,2017,84:1-
9.] tested.It is the same with S0 after sample S1 and S2 successively reach carbonization time, vacuum oven drying is put it into first,
Then powder is made and distinguishes the free chloride ion content in test sample, total chloridion content according to the method described above and quantifies
XRD material phase analysis.
Free chloride ion and the total chloridion content of S0, S1, S2 as shown in Figure 1, the object phase constituent quantitative result of three such as
Shown in Fig. 2.Since total chloridion is free chloride ion and the sum for combining chloride ion, the total chloridion content shown in Fig. 1
It is greater than free chloride ion, thus the combination chloride ion content in S0, S1, S2 can be calculated according to formula (1), and successively remember
For cb,0、cb,1、cb,2.In addition, it can also be seen that the difference of counter sample total chloridion content and free chloride ion content from Fig. 1
It is being gradually reduced, i.e., is increasing to 56d from 0d with three sample S0, S1, S2 carbonization times, free chloride ion content is gradually increasing
Add, this is because carbonization by combined chloride ion dissociation and can be converted into free chloride ion [Goni S, Guerrero
A.Accelerated carbonation of Friedel’s salt in calcium aluminate cement paste
[J].Cement and Concrete Research,2003,33(1):21-26.], so cb,0、cb,1、cb,2When with carbonization
Between increase be sequentially reduced.
cb=cr-cj (1)
It should be noted that the chemical bonding chloride ion and C-S-H that are mainly combined by Friedel ' s salt in conjunction with chloride ion
The physical bond chloride ion of gel adsorption forms, and being carbonized causes the reason of combining chloride ion content to reduce to be exactly to pass through decomposition
[the Chang H.Chloride binding capacity of pastes that Friedel ' s salt and C-S-H gel are realized
influenced by carbonation under three conditions[J].Cement&Concrete
Composites,2017,84:1-9.].Therefore from Fig. 2 it will be clear that when carbonization 0d, containing a large amount of in S0
Friedel ' s salt and C-S-H gel;When carbonization 28d, Friedel ' s salt has not been observed in S1, C-S-H gel is also significant
It reduces, illustrates that Friedel ' s salt has almost been carbonized at this time and decompose completely;When carbonization 56d, S2 does not observe still
Friedel ' s salt, and C-S-H gel is also further reduced and (Friedel ' s salt is just not present in sample when carbonization 28d and 56d
It is because C-S-H gel is the main product after hydrated cementitious, content can achieve total yield there are still C-S-H gel
The 60~70% of object, and Friedel ' s is a kind of novel substance formed after hydrated product is contacted with chloride ion, content compared to
CSH gel is many less, therefore during carbonization, Friedel ' s can be first completely broken down).
Described above, when being carbonized 0d, the combination chloride ion in sample is still by the combination chloride ion in Friedel ' s salt
With the combination chloride ion composition in C-S-H gel;But it after carbonization 28d, in the case where no longer there is Friedel ' s salt, connects down
The decomposition for continuing to reduce entirely from C-S-H gel of chloride ion is combined in sample out of carbonization 29d to 56d.Cause
This, the case where obtaining the reduction amount of the reduction amount and corresponding C-S-H gel that combine chloride ion in carbonization 29d~56d
Under, so that it may unit C-S-H gel is calculated can be with the content of adsorbing chloride ions.And then the C- in sample in known carbonization 0d
In the case where S-H gel content and combination chloride ion content, available chloride binding reaches balance after-hardening cement slurry
The amount of middle C-S-H gel adsorption combination chloride ion accounts for the ratio of total binding chloride ion content.Specific calculating process such as table 1 and formula
(2), (3), (4) are shown.
Combination chloride ion content and C-S-H gel content after the different carbonization times of table 1 in sample
cTotal, CSH=cUnit, CSH×csh0 (3)
In formula,
cUnit, CSHFor the amount of the combination chloride ion of unit C-S-H gel adsorption;
cTotal, CSHThe amount of the combination chloride ion of total C-S-H gel adsorption when being initial;
PCSHThe ratio of total binding chloride ion is accounted for for the combination chloride ion of C-S-H gel adsorption.
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, for the skill of this field
For art personnel, various changes and changes are possible in this application.Within the spirit and principles of this application, made any to repair
Change, equivalent replacement, improvement etc., should be included within the scope of protection of this application.
Claims (10)
1. a kind of method that C-S-H gel adsorption combination chloride ion accounts for total binding chloride ion ratio in measurement cement paste, special
Sign is, the method includes:
1) sample cement plus water is stirred into cement paste processed, will be conserved after the molding of cement paste reverse mould, demoulding;
2) three pieces of samples are taken out from test specimen and marks S0, S1, S2 respectively;By sample S0 in no CO2It is measured after being dried under environment
Sample free chloride ion content cf,0, total chloridion content ct,0, can be calculated in sample and combine chloride ion cb,0, while into
The quantitative XRD material phase analysis of row obtains C-S-H gel content csh0;
3) sample S1, S2 is respectively placed in CO2Until Friedel ' s salt is carbonized completely in S1, S2 sample in atmosphere;Take out sample S1
Afterwards in no CO2Its sample free chloride ion content c is measured after being dried under environmentf,1With total chloridion content ct,1, Ji Keji
Calculation obtains combining chloride ion c in sampleb,1, while carrying out quantitative XRD material phase analysis and obtaining C-S-H gel content csh1;
4) in CO after certain interval of time2Sample S2 is taken out in atmosphere, then in no CO2It is measured after being dried under environment
Sample free chloride ion content cf,2With total chloridion content ct,2, can be calculated in sample and combine chloride ion cb,2, while into
The quantitative XRD material phase analysis of row obtains C-S-H gel content csh2;
5) pass through the amount of the combination chloride ion of formula (1) unit of account C-S-H gel adsorption;And then it is not carbonized known
C-S-H gel content csh in sample S00And its combine the amount c of chloride iontotal,CSHIn the case of to get C- in hardened cement paste
The amount of S-H gel adsorption combination chloride ion accounts for the ratio P of total binding chloride ion contentCSH;
2. a kind of measuring method as described in claim 1, which is characterized in that in the step 1),
Sample cement is benchmark cement or compounding cement, and the compounding cement is the cement doped with flyash or miberal powder.
3. a kind of measuring method as described in claim 1, which is characterized in that in the step 1),
Water-cement ratio is 0.3~0.7, preferably 0.4.
4. a kind of measuring method as described in claim 1, which is characterized in that in the step 1),
Chlorate is added into mixing water,
Preferably, the chlorate is NaCl;
It is further preferred that mixing water is the NaCl solution that concentration is 3.0%~10.0%;Most preferably concentration 3.5%
NaCl solution.
5. a kind of measuring method as described in claim 1, which is characterized in that in the step 1), reverse mould forms concrete technology
For:Cement paste reverse mould is placed in the sealing device that humidity is 85~95% (preferably 90%) and stands 20~28h (preferably
For for 24 hours);
Conserving concrete technology is:Hardened paste test specimen after demoulding is placed in the sealing that humidity is 85~95% (preferably 90%)
Maintenance is stood in device, avoids test specimen from directly contacting with water or solution in maintenance processes;Curing time control is (excellent in 28~112d
It is selected as 56d).
6. a kind of measuring method as described in claim 1, which is characterized in that in the step 2),
Three pieces of sample specification sizes are identical;
Preferably, three pieces of sample collection methods are:Using precision gas cutting machine among the test specimen position cut 3 with a thickness of 1.0~
The thin slice (preferably 1.0mm) of 3.0mm;
It is further preferred that lamina dimensions are 40mm × 40mm × 1mm;
Sample S0 is in no CO2Actual conditions, which are dried, under environment is:40~50 DEG C of drying temperature (preferably 45 DEG C), when dry
Between be 7~14d.
7. a kind of measuring method as described in claim 1, which is characterized in that in the step 3),
CO is used to sample S1, S22The actual conditions being carbonized are:Temperature is 23 ± 1 DEG C, humidity 70 ± 2%, CO2Concentration is
10~100% (preferably 20%);
Sample S1 is in no CO2Actual conditions, which are dried, under environment is:40~50 DEG C of drying temperature (preferably 45 DEG C), when dry
Between be 7~14d.
8. a kind of measuring method as described in claim 1, which is characterized in that in the step 4),
Interval time is 1~60d;It can be 1d, 14d, 28d, 56d (preferably 28d);
Sample S2 is in no CO2Actual conditions, which are dried, under environment is:40~50 DEG C of drying temperature (preferably 45 DEG C), when dry
Between be 7~14d.
9. a kind of measuring method as described in claim 1, which is characterized in that the step 2), 3) and 4) in,
The measurement of free chloride ion and total chloridion according to《Marine traffic engineering concrete test specification (JTJ270-98)》Or《Commonly
Concrete long-term behaviour and endurance quality test method standard (GB/T 50082-2009)》It carries out.
10. a kind of measuring method as described in claim 1, which is characterized in that in the step 5), the sample that is not carbonized
The amount of the combination chloride ion of total C-S-H gel adsorption when the amount of the combination chloride ion of C-S-H gel adsorption is initial in S0
ctotal,CSH, shown in calculation formula such as formula (2):
cTotal, CSH=cUnit, CSH×csh0 (2)
And then the ratio P of total binding chloride ion content is accounted for by the amount that formula (3) obtain C-S-H gel adsorption combination chloride ionCSH
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