effectoftipaonchlorideimmobilizationincement-fly...

Research ArticleEffect of TIPA on Chloride Immobilization in Cement-FlyAsh Paste

Baoguo Ma Ting Zhang Hongbo Tan Xiaohai Liu Junpeng Mei Wenbin JiangHuahui Qi and Benqing Gu

State Key Laboratory of Silicate Materials for Architectures Wuhan University of Technology Wuhan 430070 China

Correspondence should be addressed to Hongbo Tan thbwhutwhuteducn

Received 27 January 2018 Accepted 26 April 2018 Published 16 July 2018

Academic Editor Cristina Leonelli

Copyright copy 2018 Baoguo Ma et al is is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

Utilization of sea sands and coral aggregate for concrete in ocean construction is increasingly attracting the attention all over theworld However the potential risk of steel corrosion resulting from chloride in these raw materials was one of the most concernedproblems To take this risk into account chloride transporting to the surface of steel should be hinderede formation of Friedelrsquossalt in hydration process is widely accepted as an effective manner for this hindrance In this study an attempt to hasten theformation of Friedelrsquos salt by adding triisopropanolamine (TIPA) was done in the cement-fly ash system with intention tochemical bind chloride and the chloride-binding capacity at 60 d age was examined e results show that TIPA can enhance thechloride-binding capacity of cement-fly ash paste at 60 d age and the reason is that the formation of Friedelrsquos salt can beaccelerated with addition of TIPA e mechanism behind is revealed as follows on the one hand the accelerated cementhydration provides more amount of calcium hydroxide to induce the pozzolanic reaction of fly ash which can hasten thedissolution of aluminum into liquid phase on the other hand TIPA can directly hasten the dissolution of aluminum in fly ashoffering more amounts of aluminum in liquid phase In this case the aluminumsulfate (AlS) ratio was obviously increasedbenefiting the formation of Friedelrsquos salt in hydration products Such results would expect to provide useful experience to promotethe chloride-binding capacity of cement-fly ash system

1 Introduction

In recent years marine exploitation is increasingly attractingthe attention all over the world In ocean construction thedurability of concrete is of great importance [1 2] Howeverattempt to utilize the sea sands and coral aggregate as rawmaterials of concrete has been done and the potential risk ofsteel corrosion is one of the most concerned problems interms of durability In fact this risk depends on whether thechloride could transport to the surface of the steel or noterefore binding the chloride to hinder its transport wouldbe of great importance to the durability of reinforcedconcrete [3ndash5]

ere are two forms of chloride ions in ocean aggregatesOne is free chloride which means that this kind ofchloride can transport around in concrete and the other isbound chloride e former would lead to the corrosion of

reinforcing steel if the chloride is transported to the surface ofsteel while the latter has almost no risk of steel corrosionerefore binding free chloride would significantly reduce therisk of steel corrosion with great benefit to the durability ofconcrete structures According to the binding mechanismchemical reactions and physical absorption can be found in theliteratures [6ndash8] e former means that chloride ions canparticipate in the hydration reaction to form the hydrationproducts such as Friedelrsquos salt (FS 3CaOmiddotAl2O3middotCaCl2middot10H2O)and Kuzelrsquos salt (KS 3CaOmiddotAl2O3middot05CaCl2middot05CaSO4middot10H2O)[9 10] e latter is that chloride ions are mainly absorbed bycalcium silicate hydrate (C-S-H) gel [11ndash13] By contrast theformer is more effective and plays the dominant role Fur-thermore binding chloride by formation of FS and KS de-pends on the reaction of aluminum ions sulfate ions chlorideions and calcium ions [14] Generally more amounts of thealuminum phase in the cement system can lead to more

HindawiAdvances in Materials Science and EngineeringVolume 2018 Article ID 4179421 11 pageshttpsdoiorg10115520184179421

amounts of formation of FS Taking C3A for example cementwith higher content of C3A can obviously increase the contentof FS in hydration products [15ndash17] Addition of supple-mentary cementitious materials such as shyy ash (FA) can alsohasten the formation of FS because aluminum can be dissolvedin the process of pozzolanic reaction [18ndash20]

In the cement-FA system chemicals can also hasten thepozzolanic reaction of FA and dissolution of aluminum Payaet al showed that grinding shyy ash to ner particles can ob-viously hasten the hydration of shyy ash but this method willlead to energy consumption [21] Dakhane et al reported thatpH-neutral alkali sulfates could activate shyy ash resulting in70 reduction of clinker factor [22] Sodium sulfate can alsoactivate the pozzolanic reaction of shyy ash but this kind ofchemical has negative eect on long-term performance ofcement-based materials [23] By contrast TIPA can exert higheciency to hasten the dissolution of FA and cement minerals[24ndash27] On the one hand the accelerated hydration of cementcan form more calcium hydroxide (CH) to hasten the poz-zolanic reaction of FA on the other hand TIPA can alsoinduce the dissolution of FA to releasemore amounts of silicateand aluminum into solution to participate in the hydration Inthis case with addition of TIPA in the cement-FA systempozzolanic reaction of FA and dissolution of aluminum wouldbe accelerated and the amount of FS would be expected toincrease with great contribution to chloride-binding capacity

In this study the chloride-binding capacity of thecement-FA system with addition of TIPA was systemicallystudied e free chloride was induced with addition ofsodium chloride (NaCl) and the chloride-binding capacityof the paste cured for 60 d was examined Hydration processof the system was investigated with analysis of hydrationheat and the hydration products were characterized withscanning electron microscope (SEM) thermogravimetricanalysis (TGA) and X-ray diraction (XRD) e reactiondegree of cement and FA was evaluated with solid-statenuclear magnetic resonance (NMR) e dissolution of FAwas analyzed with SEM and inductively coupled plasma(ICP) emission spectrometer e mechanism behind wasinvestigated in terms of hydration heat hydration productsand dissolution of FA Such results were expected to provideuseful experience to promote the chloride-binding capacityof the cement-FA system

2 Materials and Test Methods

21 Materials

211 Cement and Fly Ash Portland cement (PI 425Wuhan Yadong Cement Co Ltd) in accordance with therequirements of GB175-2007 (Chinese Standard) and classF-II FA in accordance with the requirements of GBT1596-2005 (Chinese Standard) were used in this study

e chemical compositions of cement and FA were ana-lyzed by XRF and the results are given in Table 1

212 TIPA A reagent-grade triisopropanolamine (TIPAanhydrous white solid ge95 purity made by Aladdin Bio-chemical Technology Co Ltd Shanghai China) was usedAdditionally the added dosage of TIPA was recorded as thesolid amount e chemical structure of TIPA is show inFigure 1

213 Preparation of Specimens Cement-FA paste (30 FAand 70 cement) with addition of NaCl (111 of cement-FAbinder) and TIPA (0 003 006 and 010 of cement-FA binder) was prepared with a waterbinder ratio of 038TIPA and NaCl were dissolved in water in advance e freshpastes were cast in 40mmtimes 40mmtimes 40mm cubic metallicmoulds cured in a gt90 RH and 20plusmn 1degC chamber for 24 hand then demoulded and further cured with the same con-dition At the age of 60 days compressive strength wasmeasurede samples were also broken into small pieces andimmediately immersed into ethanol in order to stop hydra-tion e pieces were dried in a vacuum drier at 60degC esamples were prepared for the measurement of chloride-binding capacity Additionally these specimens were alsopowdered by hand and the powder which could pass througha 63 μm sieve was prepared for the phase analysis(ie hydration products)

22 Test Methods

221 Chloride-Binding Capacity e sample (about 20 g)was dried in a vacuum drier at a temperature of 60plusmn 5 degC for

Table 1 Chemical compositions of cement and FA

Loss SiO2 Al2O3 Fe2O3 SO3 CaO MgO K2O Na2OCement (wt) 382 2408 472 246 231 5824 195 102 027FA (wt) 597 4833 3169 414 137 412 050 134 037

HO CH

H2C

CH3 H2C

HCOH

CH3

CH2

CH

HO CH3

N

Figure 1 Schematic diagram of molecular structure of TIPA

2 Advances in Materials Science and Engineering

2 hours and then powdered by hand e powder whichcould pass through a 15 μm sieve was prepared for themeasurement e sample (10 g) was put into a triangularflask and distilled water (100 g) was added and then it wasoscillated violently for 1-2min e sample was soaked for24 hours and then filtered e filtrate (20 g) was put intotriangular flask Two drops of phenolphthalein wereadded as a pH indicator and then it was neutralized withdilute sulfuric acid to be colorless After that 10 drops ofpotassium chromate indicator with a concentration of 5were added and silver nitrate (002molL) was addedcontinuously until brick red precipitate appears At thistime the added volume of silver nitrate solution wasmarked [28]

e amount of free chloride ion can be calculated asfollows

P CV3 times 003545

G times V2V1( 1113857times 100 (1)

where P is the content of free chloride ions in paste C isthe concentration of AgNO3 molL G is the weight of thepaste sample g V1 is the volume of water used to soak thesample mL V2 is the volume of filtrate used for mea-surement mL and V3 is the volume of consumption of silvernitrate solution mL

e initial content of chloride ions (P0) in the samplecould be calculated by the added amount of NaCl and thechloride-binding rate (CBR) was calculated as follows

CBR P0 minusP( 1113857

P0times 100 (2)

222 Compressive Strength ree specimens of eachmixture were tested in accordance with GBT50081-2002and the average was the result of compressive strength

223 Ions Dissolution of FA Firstly pore solution withdifferent concentrations of TIPA (0ndash20 gL) was prepared withKOH and NaOH (K+Na+ 1 1 pH 13) One gram of FAwas added into these solutions (20 g) respectively and thenmixed e suspension was sealed in a plastic container andcured at a temperature of 20plusmn 1degC For each 12h the containerswere shocked in order to make the suspension to be even

At the age of 60 d the suspension was centrifuged at3600 rmin for 10 minutes in a centrifuge and the content ofAl Fe and Si in supernatant solution was tested with in-ductively coupled plasma (ICP Optima 4300DV made byPerkin Elmer Ltd USA) emission spectrometer Based onthese results the effect of TIPA on the dissolution of FA wasinvestigated

In addition the solid was dried in a vacuum drier withthe temperature of 60plusmn 5degC and then the surficial mor-phology of the FA was characterized with field emissionscanning electron microscope (SEM)

224 Hydration Heat TIPA (0ndash010wt of cement-FAbinder) and NaCl (111wt of cement-FA binder) were

added into water in advance and then the solution andcement-FA (30 FA and 70 cement) were mixed togetherwith a waterbinder ratio of 05 Hydration heat was ob-tained with an isothermal calorimetry (TAM AIR C80SETARAM France)

225 Phase Analysis e effect of TIPA on hydrationproducts was investigated with scanning electron microscope(SEM) thermogravimetric analysis (TGA) solid-state nuclearmagnetic resonance (NMR) and X-ray diffraction (XRD)

(1) XRD XRD data were collected with an X-ray diffrac-tometer (XRD DMax-RB) (Cu Kα radiation) at roomtemperature (2θ 5ndash70deg step 003deg with 3 spoint)

(2) SEM Field emission scanning electron microscope (FE-SEM QUANTA FEG 450 FEI Co USA) was used for SEMmicrostructural characterization

(3) TG-DTG TGA was conducted with the comprehensivethermal analyzer (German-resistant STA449F3) e heat-ing rate was 10degCmin using nitrogen as purging gas andthe temperature ranged from the room temperature to 1000degCCH was decomposed at the temperature ranging from 400 to500degC and calcium carbonate resulting from the carbonationof CH in the process of preparing the samples was decomposedat 500ndash750degC as shown in the following equation [23]

Ca(OH)2⟶ CaO + H2O

CaCO3⟶ CaO + CO2(3)

e total content of CH in hydration products can becalculated as follow

MCa(OH)274 times MH2O

18+74 times MCO2

44 (4)

where MCa(OH)2 the mass of calcium hydroxide MH2O at

400ndash500degC the weight loss resulting fromwater andMCO2 at

500ndash750degC the weight loss resulting from carbon dioxideAdditionally the weight loss at the temperature range

from 50 to 200degC due to evaporation of free water de-hydration of C-S-H gel decomposition of ettringite (AFt)and dehydration of FS is of great interest To be moreprecise the first peak at the low temperature is related to theevaporation of free water and dehydration of C-S-H gel andthe second peak with higher temperature is involved inevaporation of free water dehydration of C-S-H gel anddecomposition of AFt the third one is about dehydration ofFS [29] Such results can provide supplementary evidence toillustrate the effect of TIPA on the formation of FS

(4) NMR To further verify the effect of TIPA on hydration ofcement-FA paste the hydration products were characterizedwith 29Si MAS NMR As reported in the literatures [30] sixpeaks can be found in NMR spectrum of hydrated cement-FA paste Q1 (chain-end groups) Q2 (middle-chain groups)and Q2 (1Al) (middle-chain groups where one of the ad-jacent tetrahedral sites is occupied by Al3+) represent theSi-O tetrahedron in hydration products and Q0 represents

Advances in Materials Science and Engineering 3

the Si-O tetrahedron in unhydrated cement minerals andQ3 and Q4 represent the Si-O tetrahedron in FA Due todierent chemical surroundings of Si sites in cementitiousmaterials the polymerization degree of Si-O tetrahedronand AlSi ratios in C-S-H can be evaluated

29Si-NMR (solid-state nuclear magnetic resonance) wasconducted with a Bruker Advance III400 spectrometeroperating at 795MHz e rotation frequency was 5 kHzand the delay time was 10 s Tetramethylsilane was used asa standard for 29Sie data were processed with commercialsolid-state NMR software package It was rstly tted andthen the phasing and baseline were corrected followed bysubsequently iterative tting During the deconvolution of29Si-NMR spectra the peak shapes were constrained with theGaussian function e main chain length (MCL) of C-S-Hgel and the ratio of Si in C-S-H substituted by Al were cal-culated as follows [31]

MCL 2I Q1( ) + 2I Q2( ) + 3I Q2(Al)[ ]

Q1

AlSi

05I Q2(Al)[ ]I Q1( ) + I Q2( ) + I Q2(Al)[ ]

(5)

Reaction degree of FA and cement was also calculated asfollows

AFA() 1minus I Q3 + Q4( )I0 Q3 + Q4( )

AC() 1minus I Q0( )I0 Q0( )

(6)

where I(Q0) I(Q1) I(Q2) and I[Q2(Al)] represent theintegrated intensities of signals Q0 Q1 Q2 and Q2(Al) inhydrated cement-FA paste respectively I0(Q0) I0(Q3) andI0(Q4) represent the integrated intensities of signals Q0 Q3and Q4 in unhydrated cement-FA mixture

3 Results and Discussion

31Chloride Solidication e eect of TIPA on the CBR ofcement-FA paste cured for 60 days was examined and theresults are shown in Figure 2 As can be seen from the gurein comparison with the reference (ie without TIPA) CBRat the age of 60 days is increased with addition of TIPA withthe dosage of 006 CBR reaches 4840 with an increaseof 111 when the dosage is further increased to 010 CBRincreases to 5347 with an increase of 228

e binding of chlorine ions in the cement-FA systemcan be divided into chemical binding and physical ad-sorption It can be inferred that addition of TIPA probablyhastens the hydration of cement-FA system On the onehand the addition of TIPA can accelerate the dissolution ofthe ferric phase in cement minerals which in most casesexists on the surface of the mineral particles due to the lowermelting point Accordingly the dissolution of other phasecan also be hastened resulting in formation of more amount

of CH which can induce the pozzolanic reaction of FA [32]On the other hand the addition of TIPA can also hasten thedissolution of FA and in this case the more amounts ofaluminum would exist in the liquid phase and participate inhydration Most likely more amounts of FS or KS could beformed [33]

Additionally physical adsorption of chloride resultingfrom C-S-H gel can also contribute to chloride immobili-zation With addition of TIPA formation of C-S-H gel canbe promoted and more amount of C-S-H gel can exertstronger ability to adsorb and wrap chloride ions

Based on discussion above the improvement in CBR ofthe cement-FA system with addition of TIPA at 60 d age isclosely related to the hydration of the system and the for-mation of FS and KS which would be further illustrated inthe following text

32 Analysis of Hydration Products To verify the contri-bution of FS or KS to CBR the hydration products werecharacterized with XRD TG and SEM

321 XRD Cement-FA paste hydrated for 60 days withaddition of TIPA (006) was discussed with XRD and theresults are shown in Figure 3 As can be seen from the gurethe peaks of CH AFm AFt and FS can be observed ob-viously By contrast the addition of TIPA increases the peakintensity of AFt and FS and reduces the intensity of AFmis result indicates that TIPA can hasten the formation ofAFt and FS at 60 d age

322 TG-DTG e mass loss curve of the sample is shownin Figure 4(a) As it can be seen from the TGA curve themass loss at the temperature range from 0 to 400degC isrelated to the loss of free water decomposition of C-S-Hgel hydrated calcium sulphoaluminate and FS that for400ndash500degC is involved in the decomposition of CH andthat for 500ndash750degC is due to the decomposition of carbon

000

100

1088 1111

1228

003 006 01030

35

40

45

50

55

60

TIPA content (wt)

Chlo

ride-

bind

ing

rate

()

Figure 2 Eect of TIPA on the chloride-binding rate of 60 d


dioxide which was formed in the process of preparing forthe samples [34]

e weight loss at the temperature from 50 to 200degCmainly resulting from evaporation of free water and the de-composition of hydrate (C-S-H gel AFt and FS) shows greatinterest As reported in the literatures [35] FS would bedecomposed at the temperature range of about 160degC It isnoticed that in Figure 4(b) the absorption peak resulting fromdecomposition of FS is obviously increased with addition ofTIPA (006) indicating more amount of FS is resultprovides supplementary evidence to prove that TIPA canfacilitate formation of FS in agreement with the XRD results

However the amount of CH in hydration productsattracts more interest As shown in Table 2 for 60 d age theamount of CH in blank (without TIPA) is greater than thatwith addition of TIPA is result indicates that TIPA can

10 7050 60402θ (degree)

Blank

006 TIPA

3020

Δ

Friedelrsquos saltCa(OH)2AFt

Δ

(a)

90 1151101052θ (degree)

10095

AFtAFm

Friedelrsquos salt

C-FAC-FA + 006 TIPA

(b)

Figure 3 XRD patterns of cement-FA paste hydrated at 60 days

Table 2 Calcium hydroxide content in the cement-FA system(wt)

Temperature range (degC) Blank 006 TIPA400ndash500degC 266 255500ndash750degC 414 429CH content 1789 1769

0 200 400 600 800 1000Temperature (degC)

75

80

85

90

95

100

C-FAC-FA + 006 TIPA

Mas

s los

s (

)

(a)

C-FAC-FA + 006 TIPA


ndash10

ndash08

ndash06

ndash04

ndash02

00

02

DTG

(m

in)

Free water + C-S-H

Free water + C-S-H + AFt

FS

(b)Figure 4 TG-DTG curve of the paste hydrated for 60 d (a) TG (b) DTG


reduce the amount of CH in hydration products at 60 d agee amount of CH depends on the cement hydration andpozzolanic reaction of FA Greater degree of cement hy-dration would generate more amount of CH and greaterdegree of pozzolanic reaction of FA would consume moreamount of CH In comparison with the blank the pre-dominant aspect would determine the relative amount ofCH Obviously the acceleration of the FA namely con-sumption of CH should be predominated is implies thatTIPA can signicantly hasten the pozzolanic reaction of FA

Based on discussion above pozzolanic reaction of FAand formation of FS can be hastened with addition of TIPAand the improvement in CBR is mainly because of theaccelerated formation of FS in hydrates which would beclosely related to the hydration process

33 Hydration Process

331 Compressive Strength To further verify the eect ofTIPA on hydration of cement-FA paste the compressivestrength was examined and the results are shown in Figure 5As can be seen from the gure the compressive strength at theage of 60 days increases with the increasing dosage of TIPACompared with the sample without TIPA 003 TIPA in-creases the strength by 155 with the dosage of 010 thestrength reaches 778MPa with an increase by 344 e in-creased strength implies that TIPA can also accelerate the hy-dration of the cement-FA system

332 Hydration Heat As reported in the literatures thehydration of cement-FA includes the initial reaction

000 003 006 010TIPA content (wt)

Stre

ngth

(MPa

)

50

60

70

80

90

100

1283

1155

1344

Figure 5 Eect of TIPA on compressive strength of 60 d

30

25

20

15

10

05

000

Hea

t flo

w (m

Wg

)

1681441209672Time (h)

4824

C-FAC-FA + 006 TIPAC-FA + 010 TIPA

(a)

300

250

200

150

100

50

00

Hyd

ratio

n he

at (J

g)

1681441209672Time (h)

4824


(b)

Figure 6 Hydration heat of cement-FA paste with TIPA (a) Heat shyow (b) hydration heat


a period of slow reaction an acceleration period anda deceleration period as described by Taylor [36] As shownin Figure 6(a) the addition of TIPA cannot change thesefour steps but can accelerate the release of hydration heatindicating that TIPA can hasten the hydration of thecement-FA systemis can also be conrmed in Figure 6(b)that the cumulated heat is increased with addition of TIPA

Furthermore it is noticed that the extra peak at about30 h can be seen clearly with addition of TIPA As reportedthe eect of TIPA on cement hydration can be divided intothree phases (1) adsorb on the surface of cement particlesand slightly delay the hydration (2) hasten the dissolution ofions especially the ferric ion to accelerate the formation ofAFt and (3) facilitate the conversion of AFt to AFm [37 38]It can be inferred that the extra peak should be related to thatconversion e reason can be revealed that at the verybeginning of the hydration AFt should be formed because ofthe much faster dissolution speed of gypsum to provideenough sulfates with lower AlS ratio While with timegoing on more amount of aluminum can increase the AlSratio resulting in conversion of AFt to AFm In cement-FA

paste with TIPA the dissolution of aluminum in FA wouldbe hastened and the AlS ratio would be much higher thanthat without TIPA In this case the conversion of AFt toAFm can be facilitated

3CaO middot Al2O3 middot CaSO4 middot 12H2O(AFm) + 2Clminus ⟶

3CaO middot Al2O3 middot CaCl2 middot 10H2O(Fs) + SO 2minus4 + 2H2O

(7)

According to results in the literatures [14 39] AFm cancombine with chloride ions to form FS and in cement-FApaste with TIPA the conversion of AFt to AFm can befacilitated which can further hasten the formation of FS

333 29Si-NMR e deconvoluted 29Si MAS NMR spectraof the samples obtained from the tting are plotted inFigure 7 reaction ratio MCL and AlSi ratio were calcu-lated and the results are shown in Table 3 As shown inFigure 7Q0Q1Q2 (1Al)Q2Q3 andQ4 can be seen clearlyIn comparison with the unhydrated C-FA (as shown inFigure 7(a)) the increase in peak intensity of Q1 Q2 (1Al)

Q4Q3

Q0

Observed

Generated

ndash120 ndash110 ndash100 ndash90 ndash80 ndash70 ndash60 ndash50ppm

(a)

Observed

Generated

ndash120 ndash110 ndash100 ndash90ppm

ndash80 ndash70 ndash60 ndash50

Q4Q3

Q2(1A1)Q2

Q1 Q0

(b)


Observed

Generated

Q4

Q3

Q2 Q2(1A1)Q1

Q0

(c)

Figure 7 29Si-NMR spectrum of cement-FA paste (a) Unhydrated C-FA (b) C-FA hydrated for 60d (c) C-FAwith 006 TIPA hydrated for 60d


and Q2 can be found and the decline in Q0 Q3 and Q4 canalso be observed ese results illustrate the hydration ofcement and the pozzolanic reaction of FA More details canbe found in Table 3 in comparison with the blank sample006 TIPA obviously reduces the amount ofQ0 and slightlydeclines the amount ofQ3＋Q4 this result demonstrates thatTIPA can promote the cement hydration as well as thepozzolanic reaction of FA by contrast this promoting effecton cement hydration is much stronger than that of FAFurthermore C-FA has a MCL of 504 while that for C-FA-TIPA (006) it was 653 which indicates that the additionof TIPA can increase the degree of silicate polymerizationthis can also show that a higher degree of hydration hasoccurred Moreover the AlSi ratio is also increased with006 TIPA in comparison with blank paste (C-FA) isincrease definitely confirms that the incorporation of TIPAinto the cement-FA system induces the substitution of Si byAl (Al [4]) into C-S-H resulting in an increase in the lengthof silicate chain of C-S-H in agreement with the results ofMCL Additionally the reaction degree of cement withoutTIPA is 6811 while that for addition of TIPA (006) it is7431 which indicates the accelerated hydration of cementby TIPA e same results can also be found in FA thereaction degree of FA is increased from 3618 to 4198with 006 TIPA

According to the analysis of NMR the addition of TIPAnot only hastens the hydration of cement but also acceleratesthe pozzolanic reaction of FA and it also increases thedegree of silicate polymerization the length of C-S-H andsubstitution of Si by Al with contribution to the mechanicalperformance is also hastens the dissolution of aluminumof FA into liquid phase

334 SEM Figure 8 shows the SEM images of the pastehydrated for 60 d in the presence and absence of TIPA

As shown in Figure 8 more serious erosion can be seenclearly in Figure 8(b) than that in Figure 8(a) which impliesthat the addition of TIPA can hasten pozzolanic reaction of FA

Based on the discussion of hydration heat NMR SEMand compressive strength it is concluded that TIPA canaccelerate the pozzolanic reaction of FA and hydration ofcement minerals at the age of 60 d

34 Dissolution of Fly Ash

341 Ions Dissolution e accelerated hydration of FA byTIPA has been confirmed above and the mechanism behindthis is closely related to the dissolution of ions from FA intoliquid Accordingly the reaction of FA in pore solution withvarious dosages of TIPA was investigated to further revealthe reason for the accelerated hydration of FA by TIPA

e effect of TIPA on dissolution of FA in pore solutionis shown in Figure 9 As shown in the figure the dissolutionof aluminum ions ferric ions and silicon ions was increasedwith the increasing dosage of TIPA indicating that TIPA inpore solution can significantly hasten the dissolution of FATIPA (20 gL) can make the aluminum ions about 25 timesand silicate ions about 2 times of the blank (without TIPA) atthe age of 60 days Furthermore as shown in Figure 9(b)very little amount of Fe can be found without TIPA whichimplies that ferric in FA is not that easy to be dissolved intopore solution in hydration process However with additionof TIPA surprisingly the dissolution of ferric ions wasconsiderably hastened in agreement with the results in theliteratures [40 41]

e morphology of FA was observed with SEM asa supplementary evidence to prove the dissolution of ions ofFA in pore solution As shown in Figure 10(a) at the age of60 d the erosion of FA in the pore solution can be seenclearly and the amount of flocculent reaction products on

Figure 8 SEM images of the paste hydrated for 60 d

Table 3 Deconvolution results of the sample

Q0 Q1 Q2 (1Al) Q2 Q3＋Q4 MCL AlSi Reaction ratioof cement ()

Reaction ratioof fly ash ()

Unhydrated C-FA 6227 mdash mdash mdash 3773 mdash mdash mdash mdashC-FA 1986 2420 986 2200 2408 504 00879 6811 3618C-FA with 06 TIPA 1600 2177 1800 2234 2189 653 01449 7431 4198


the surface can also be found By contrast as shown inFigure 10(b) with TIPA solution (20 gL) the erosion of thesurface is more seriously indicating that dissolution of FAcan be hastened at the age of 60 d in agreement with theresults of ions dissolution

Based on the discussion above the promoted ions dis-solution of FA into the liquid phase by addition of TIPA can

be concluded and this can benet the improvement in CBRof the cement-FA system e details for the reason can besummarized as follow

On the one hand the promotion of TIPA on cementhydration has been conrmed which can generate moreamount of CH to activate the pozzolanic reaction of FA whichmeans that the dissolution of FA can be hastened On the other

0 5 10 15 200

200

400

600

800

1000

1200

1400

TIPA content (gL)

Con

cent

ratio

n (m

gL)

(a)

0 5 10 15 200

50

100

150

200

250

300

350

TIPA content (gL)

Con

cent

ratio

n (m

gL)

(b)

0 5 10 15 200

200

400

600

800

1000

1200

1400

1600

1800

TIPA content (gL)

Con

cent

ratio

n (m

gL)

(c)

Figure 9 Ions dissolution of FA in the pore solution with TIPA at the age of 60 days (a) Al (b) Fe (c) Si

Figure 10 Morphology of FA immersed in pore solution for 60 days


hand the addition of TIPA can also accelerate dissolution of Alinto the pore solution As a result the addition of TIPA cansignificantly accelerate the dissolution of FA into the liquidphase especially the dissolution of aluminum Furthermorethe aluminum dissolved from FA can participate in the for-mation of C-S-H gel as C-A-S-H gel and also increase the AlSratio to induce the formation of AFm fromAFt AFm can reactwith chloride to formFS Additionally the excessive can also bedirectly reacted with calcium and chloride to generate FSConsequently the formation of FS can be hastened and theCBR of the cement-FA system can be improved

4 Conclusion

(1) Addition of TIPA in the cement-FA system can notonly hasten the hydration of cement minerals butalso accelerate the pozzolanic reaction of FA withcontribution to the mechanical performance

(2) e FS can also be accelerated with addition of TIPAat the age of 60 d which is responsible for the im-proved chloride-binding capacity of the system

(3) Dissolution of aluminum silicate and ferric in FAcan be hastened with addition of TIPA which at-tributes to the increased amount of FS and C-A-S-Hgel in hydration products

Data Availability

e data used to support the findings of this study areavailable from the corresponding author upon request

Conflicts of Interest

e authors declare that there are no conflicts of interestregarding the publication of this paper

Acknowledgments

Financial support from the National Key RampD Program ofChina (2016YFC0701003-5) is gratefully acknowledged

References

[1] X Y Lu C L Li and H Zhang ldquoRelationship between thefree and total chloride diffusivity in concreterdquo Cement andConcrete Research vol 30 no 2 pp 323ndash326 2002

[2] W Li B Dong Z Yang et al ldquoRecent advances in intrinsicself-healing cementitious materialsrdquo Advanced Materialsvol 30 no 17 2018

[3] X Shi N Xie K Fortune and J Gong ldquoDurability of steelreinforced concrete in chloride environments an overviewrdquoConstruction and Building Materials vol 30 pp 125ndash1382012

[4] B Martın-Pereza H Zibarab R D Hootonb andM D Aomas ldquoA study of the effect of chloride binding onservice life predictionsrdquo Cement and Concrete Researchvol 30 no 8 pp 1215ndash1223 2000

[5] J Xiao C Qiang A Nanni and K Zhang ldquoUse of sea-sandand seawater in concrete construction current status andfuture opportunitiesrdquo Construction and Building Materialsvol 155 pp 1101ndash1111 2017

[6] F Zou H Tan Y Guo B Ma X He and Y Zhou ldquoEffect ofsodium gluconate on dispersion of polycarboxylate super-plasticizer with different grafting density in side chainrdquoJournal of Industrial and Engineering Chemistry vol 55pp 91ndash100 2017

[7] H Tan B Gu Y Guo et al ldquoImprovement in compatibility ofpolycarboxylate superplasticizer with poor-quality aggregatecontainingmontmorillonite by incorporating polymeric ferricsulfaterdquo Construction and Building Materials vol 162pp 566ndash575 2018

[8] B Ma Y Peng H Tan et al ldquoEffect of hydroxypropyl-methylcellulose ether on rheology of cement paste plasticized bypolycarboxylate superplasticizerrdquo Construction and BuildingMaterials vol 160 pp 341ndash350 2018

[9] F P Glasser A Kindness and S A Stronach ldquoStability andsolubility relationships in AFm phasesrdquo Cement and ConcreteResearch vol 29 no 6 pp 861ndash866 1999

[10] S Yoon J Ha S R Chae et al ldquoPhase changes of mono-sulfoaluminate in NaCl aqueous solutionrdquo Materials vol 9no 5 p 401 2016

[11] E P Nielsen D Herfort and M R Geiker ldquoBinding ofchloride and alkalis in Portland cement systemsrdquo Cement andConcrete Research vol 35 no 1 pp 117ndash123 2005

[12] M Marinescu and J Brouwers ldquoChloride binding related tohydration products part I ordinary Portland cementrdquo Ad-vances in Modeling Concrete Service Life vol 3 pp 125ndash1312012

[13] D M Burgos A Guzman N Torres and S DelvastoldquoChloride ion resistance of self-compacting concretes in-corporating volcanic materialsrdquo Construction and BuildingMaterials vol 156 pp 565ndash573 2017

[14] J Geng D Easterbrook L Y Li and L W Mo ldquoe stabilityof bound chlorides in cement paste with sulfate attackrdquoCement and Concrete Research vol 68 pp 211ndash222 2015

[15] C Alonsoa C Andradea M Castellotea and P CastrobldquoChloride threshold values to depassivate reinforcing barsembedded in a standardized OPC mortarrdquo Cement andConcrete Research vol 30 no 7 pp 1047ndash1055 2000

[16] H Justnes ldquoA review of chloride binding in cementitioussystemsrdquo Nordic Concrete Research vol 21 pp 1ndash6 1998

[17] Y Guo B Ma Z Zhi et al ldquoEffect of polyacrylic acidemulsion on fluidity of cement pasterdquo Colloids and Surfaces APhysicochemical and Engineering Aspects vol 535 pp 139ndash148 2017

[18] R K Dhir M A K El-Mohr and T D Dyer ldquoDevelopingchloride resisting concrete using PFArdquo Cement and ConcreteResearch vol 17 no 11 pp 1633ndash1639 1997

[19] H Zibara R D Hooton M D A omas and K StanishldquoInfluence of the CS and CA ratios of hydration products onthe chloride ion binding capacity of lime-SF and lime-MKmixturesrdquo Cement and Concrete Research vol 38 no 3pp 422ndash426 2008

[20] X Gong Y Wang and T Kuang ldquoZIF-8-based membranesfor carbon dioxide capture and separationrdquo ACS SustainableChemistry and Engineering vol 5 no 12 pp 11204ndash112142017

[21] J Paya J Monzo M V Borrachero and E Peris-MoraldquoMechanical treatment of fly ashes Part I physico-chemicalcharacterization of ground fly ashesrdquo Cement and ConcreteResearch vol 25 no 7 pp 1469ndash1479 1995

[22] A Dakhane S Tweedley S Kailas RMarzke andN NeithalathldquoMechanical and microstructural characterization of alkali sul-fate activated high volume fly ash bindersrdquoMaterials and Designvol 122 pp 236ndash246 2017


[23] J Mei H Tan H Li et al ldquoEffect of sodium sulfate and nano-SiO2 on hydration and microstructure of cementitious ma-terials containing high volume fly ash under steam curingrdquoConstruction and Building Materials vol 163 pp 812ndash8252018

[24] E Gartner and D Myers ldquoInfluence of tertiary alkanolamineson Portland cement hydrationrdquo Journal of the AmericanCeramic Society vol 76 no 6 pp 1521ndash1530 1993

[25] Z Xu W Li J Sun et al ldquoResearch on cement hydration andhardening with different alkanolaminesrdquo Construction andBuilding Materials vol 141 pp 296ndash306 2017

[26] H Huang X-R Li and X-D Shen ldquoHydration of ternarycement in the presence of triisopropanolaminerdquo Constructionand Building Materials vol 111 pp 513ndash521 2016

[27] B Zhang H Tan B Ma et al ldquoPreparation and application offine-grinded cement in cement-based materialrdquo Constructionand Building Materials vol 157 pp 34ndash41 2017

[28] JGJT 322-2013 Technical Specification for Test of Chloride IonContent in Concrete China Architecture and Building PressBeijing China 2013 in Chinese

[29] U A Birnin-Yauri and F P Glasser ldquoFriedelrsquos salt Ca2Al(OH)6(ClOH)middot2H2O its solid solutions and their role inchloride bindingrdquo Cement and Concrete Research vol 28no 12 pp 1713ndash1723 1998

[30] C A Love I G Richardson and A R Brough ldquoCompositionand structure of CndashSndashH in white Portland cementndash20metakaolin pastes hydrated at 25degCrdquo Cement and ConcreteResearch vol 37 no 2 pp 109ndash117 2007

[31] L Wang and Z He ldquoQuantitative of fly ash-cement hydrationby 29Si MAS NMRrdquo Journal of the Chinese Ceramic Societyvol 38 no 11 pp 2212ndash2216 2010

[32] Z Wang J Wu P Zhao et al ldquoImproving cracking resistanceof cement mortar by thermo-sensitive poly N-isopropyl ac-rylamide (PNIPAM) gelsrdquo Journal of Cleaner Productionvol 176 pp 1292ndash1303 2018

[33] M D A omas R D Hooton A Scott and H Zibara ldquoeeffect of supplementary cementitious materials on chloridebinding in hardened cement pasterdquo Cement and ConcreteResearch vol 42 no 1 pp 1ndash7 2012

[34] Z Shi M R Geiker B Lothenbach et al ldquoFriedelrsquos saltprofiles from thermogravimetric analysis and thermodynamicmodelling of Portland cement-based mortars exposed tosodium chloride solutionrdquo Cement and Concrete Compositesvol 78 pp 73ndash83 2017

[35] J-P Rapina G Renaudinb E Elkaimc and M FrancoisaldquoStructural transition of Friedelrsquos salt 3CaOmiddotAl2O3middotCaCl2middot10H2Ostudied by synchrotron powder diffractionrdquo Cement and Con-crete Research vol 32 pp 513ndash519 2002

[36] H Taylor Cement Chemistryomas Telford London UK1997

[37] Z Shi C Shi H Liu and P Li ldquoEffects of triisopropanolamine sodium chloride and limestone on the compressivestrength and hydration of Portland cementrdquoConstruction andBuilding Materials vol 125 pp 210ndash218 2016

[38] Y Wang and X Gong ldquoSpecial oleophobic and hydrophilicsurfaces approaches mechanisms and applicationsrdquo Journalof Materials Chemistry A vol 5 no 8 pp 3759ndash3773 2017

[39] A Ipavec T Vuk R Gabrovsek and V Kaucic ldquoChloridebinding into hydrated blended cements the influence oflimestone and alkalinityrdquo Cement and Concrete Researchvol 48 pp 74ndash85 2013

[40] H Huang X Shen and J Zheng ldquoModeling analysis ofinteraction effects of several chemical additives on the

strength development of silicate cementrdquo Construction andBuilding Materials vol 24 no 10 pp 1937ndash1943 2010

[41] S Ma W Li S Zhang Y Hu and X Shen ldquoStudy on thehydration and microstructure of Portland cement containingdiethanol-isopropanolaminerdquoCement and Concrete Researchvol 67 pp 122ndash130 2015


CorrosionInternational Journal of

Hindawiwwwhindawicom Volume 2018

Advances in

Materials Science and EngineeringHindawiwwwhindawicom Volume 2018


Journal of

Chemistry

Analytical ChemistryInternational Journal of


ScienticaHindawiwwwhindawicom Volume 2018

Polymer ScienceInternational Journal of



Advances in Condensed Matter Physics


International Journal of

BiomaterialsHindawiwwwhindawicom

Journal ofEngineeringVolume 2018

Applied ChemistryJournal of


NanotechnologyHindawiwwwhindawicom Volume 2018

Journal of


High Energy PhysicsAdvances in

Hindawi Publishing Corporation httpwwwhindawicom Volume 2013Hindawiwwwhindawicom

The Scientific World Journal

Volume 2018

TribologyAdvances in



ChemistryAdvances in


Advances inPhysical Chemistry


BioMed Research InternationalMaterials

Journal of


Na

nom

ate

ria

ls


Journal ofNanomaterials

Submit your manuscripts atwwwhindawicom

amounts of formation of FS Taking C3A for example cementwith higher content of C3A can obviously increase the contentof FS in hydration products [15ndash17] Addition of supple-mentary cementitious materials such as shyy ash (FA) can alsohasten the formation of FS because aluminum can be dissolvedin the process of pozzolanic reaction [18ndash20]

In the cement-FA system chemicals can also hasten thepozzolanic reaction of FA and dissolution of aluminum Payaet al showed that grinding shyy ash to ner particles can ob-viously hasten the hydration of shyy ash but this method willlead to energy consumption [21] Dakhane et al reported thatpH-neutral alkali sulfates could activate shyy ash resulting in70 reduction of clinker factor [22] Sodium sulfate can alsoactivate the pozzolanic reaction of shyy ash but this kind ofchemical has negative eect on long-term performance ofcement-based materials [23] By contrast TIPA can exert higheciency to hasten the dissolution of FA and cement minerals[24ndash27] On the one hand the accelerated hydration of cementcan form more calcium hydroxide (CH) to hasten the poz-zolanic reaction of FA on the other hand TIPA can alsoinduce the dissolution of FA to releasemore amounts of silicateand aluminum into solution to participate in the hydration Inthis case with addition of TIPA in the cement-FA systempozzolanic reaction of FA and dissolution of aluminum wouldbe accelerated and the amount of FS would be expected toincrease with great contribution to chloride-binding capacity

In this study the chloride-binding capacity of thecement-FA system with addition of TIPA was systemicallystudied e free chloride was induced with addition ofsodium chloride (NaCl) and the chloride-binding capacityof the paste cured for 60 d was examined Hydration processof the system was investigated with analysis of hydrationheat and the hydration products were characterized withscanning electron microscope (SEM) thermogravimetricanalysis (TGA) and X-ray diraction (XRD) e reactiondegree of cement and FA was evaluated with solid-statenuclear magnetic resonance (NMR) e dissolution of FAwas analyzed with SEM and inductively coupled plasma(ICP) emission spectrometer e mechanism behind wasinvestigated in terms of hydration heat hydration productsand dissolution of FA Such results were expected to provideuseful experience to promote the chloride-binding capacityof the cement-FA system

2 Materials and Test Methods

21 Materials

211 Cement and Fly Ash Portland cement (PI 425Wuhan Yadong Cement Co Ltd) in accordance with therequirements of GB175-2007 (Chinese Standard) and classF-II FA in accordance with the requirements of GBT1596-2005 (Chinese Standard) were used in this study

e chemical compositions of cement and FA were ana-lyzed by XRF and the results are given in Table 1

212 TIPA A reagent-grade triisopropanolamine (TIPAanhydrous white solid ge95 purity made by Aladdin Bio-chemical Technology Co Ltd Shanghai China) was usedAdditionally the added dosage of TIPA was recorded as thesolid amount e chemical structure of TIPA is show inFigure 1

213 Preparation of Specimens Cement-FA paste (30 FAand 70 cement) with addition of NaCl (111 of cement-FAbinder) and TIPA (0 003 006 and 010 of cement-FA binder) was prepared with a waterbinder ratio of 038TIPA and NaCl were dissolved in water in advance e freshpastes were cast in 40mmtimes 40mmtimes 40mm cubic metallicmoulds cured in a gt90 RH and 20plusmn 1degC chamber for 24 hand then demoulded and further cured with the same con-dition At the age of 60 days compressive strength wasmeasurede samples were also broken into small pieces andimmediately immersed into ethanol in order to stop hydra-tion e pieces were dried in a vacuum drier at 60degC esamples were prepared for the measurement of chloride-binding capacity Additionally these specimens were alsopowdered by hand and the powder which could pass througha 63 μm sieve was prepared for the phase analysis(ie hydration products)

22 Test Methods

221 Chloride-Binding Capacity e sample (about 20 g)was dried in a vacuum drier at a temperature of 60plusmn 5 degC for

Table 1 Chemical compositions of cement and FA

Loss SiO2 Al2O3 Fe2O3 SO3 CaO MgO K2O Na2OCement (wt) 382 2408 472 246 231 5824 195 102 027FA (wt) 597 4833 3169 414 137 412 050 134 037

HO CH

H2C

CH3 H2C

HCOH

CH3

CH2

CH

HO CH3

N

Figure 1 Schematic diagram of molecular structure of TIPA




P CV3 times 003545

G times V2V1( 1113857times 100 (1)




P0times 100 (2)















18+74 times MCO2

44 (4)









MCL 2I Q1( ) + 2I Q2( ) + 3I Q2(Al)[ ]

Q1

AlSi

05I Q2(Al)[ ]I Q1( ) + I Q2( ) + I Q2(Al)[ ]

(5)


AFA() 1minus I Q3 + Q4( )I0 Q3 + Q4( )


(6)











000

100

1088 1111

1228

003 006 01030

35

40

45

50

55

60

TIPA content (wt)

Chlo

ride-

bind

ing

rate

()






10 7050 60402θ (degree)

Blank

006 TIPA

3020

Δ


Δ

(a)

90 1151101052θ (degree)

10095

AFtAFm

Friedelrsquos salt

C-FAC-FA + 006 TIPA

(b)





75

80

85

90

95

100

C-FAC-FA + 006 TIPA

Mas

s los

s (

)

(a)

C-FAC-FA + 006 TIPA


ndash10

ndash08

ndash06

ndash04

ndash02

00

02

DTG

(m

in)

Free water + C-S-H


FS









Stre

ngth

(MPa

)

50

60

70

80

90

100

1283

1155

1344


30

25

20

15

10

05

000

Hea

t flo

w (m

Wg

)

1681441209672Time (h)

4824


(a)

300

250

200

150

100

50

00

Hyd

ratio

n he

at (J

g)

1681441209672Time (h)

4824


(b)








(7)



Q4Q3

Q0

Observed

Generated


(a)

Observed

Generated



Q4Q3

Q2(1A1)Q2

Q1 Q0

(b)


Observed

Generated

Q4

Q3

Q2 Q2(1A1)Q1

Q0

(c)






















0 5 10 15 200

200

400

600

800

1000

1200

1400

TIPA content (gL)

Con

cent

ratio

n (m

gL)

(a)

0 5 10 15 200

50

100

150

200

250

300

350

TIPA content (gL)

Con

cent

ratio

n (m

gL)

(b)

0 5 10 15 200

200

400

600

800

1000

1200

1400

1600

1800

TIPA content (gL)

Con

cent

ratio

n (m

gL)

(c)





4 Conclusion




Data Availability




Acknowledgments


References















































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls






P CV3 times 003545

G times V2V1( 1113857times 100 (1)




P0times 100 (2)















18+74 times MCO2

44 (4)









MCL 2I Q1( ) + 2I Q2( ) + 3I Q2(Al)[ ]

Q1

AlSi

05I Q2(Al)[ ]I Q1( ) + I Q2( ) + I Q2(Al)[ ]

(5)


AFA() 1minus I Q3 + Q4( )I0 Q3 + Q4( )


(6)











000

100

1088 1111

1228

003 006 01030

35

40

45

50

55

60

TIPA content (wt)

Chlo

ride-

bind

ing

rate

()






10 7050 60402θ (degree)

Blank

006 TIPA

3020

Δ


Δ

(a)

90 1151101052θ (degree)

10095

AFtAFm

Friedelrsquos salt

C-FAC-FA + 006 TIPA

(b)





75

80

85

90

95

100

C-FAC-FA + 006 TIPA

Mas

s los

s (

)

(a)

C-FAC-FA + 006 TIPA


ndash10

ndash08

ndash06

ndash04

ndash02

00

02

DTG

(m

in)

Free water + C-S-H


FS









Stre

ngth

(MPa

)

50

60

70

80

90

100

1283

1155

1344


30

25

20

15

10

05

000

Hea

t flo

w (m

Wg

)

1681441209672Time (h)

4824


(a)

300

250

200

150

100

50

00

Hyd

ratio

n he

at (J

g)

1681441209672Time (h)

4824


(b)








(7)



Q4Q3

Q0

Observed

Generated


(a)

Observed

Generated



Q4Q3

Q2(1A1)Q2

Q1 Q0

(b)


Observed

Generated

Q4

Q3

Q2 Q2(1A1)Q1

Q0

(c)






















0 5 10 15 200

200

400

600

800

1000

1200

1400

TIPA content (gL)

Con

cent

ratio

n (m

gL)

(a)

0 5 10 15 200

50

100

150

200

250

300

350

TIPA content (gL)

Con

cent

ratio

n (m

gL)

(b)

0 5 10 15 200

200

400

600

800

1000

1200

1400

1600

1800

TIPA content (gL)

Con

cent

ratio

n (m

gL)

(c)





4 Conclusion




Data Availability




Acknowledgments


References















































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls






MCL 2I Q1( ) + 2I Q2( ) + 3I Q2(Al)[ ]

Q1

AlSi

05I Q2(Al)[ ]I Q1( ) + I Q2( ) + I Q2(Al)[ ]

(5)


AFA() 1minus I Q3 + Q4( )I0 Q3 + Q4( )


(6)











000

100

1088 1111

1228

003 006 01030

35

40

45

50

55

60

TIPA content (wt)

Chlo

ride-

bind

ing

rate

()






10 7050 60402θ (degree)

Blank

006 TIPA

3020

Δ


Δ

(a)

90 1151101052θ (degree)

10095

AFtAFm

Friedelrsquos salt

C-FAC-FA + 006 TIPA

(b)





75

80

85

90

95

100

C-FAC-FA + 006 TIPA

Mas

s los

s (

)

(a)

C-FAC-FA + 006 TIPA


ndash10

ndash08

ndash06

ndash04

ndash02

00

02

DTG

(m

in)

Free water + C-S-H


FS









Stre

ngth

(MPa

)

50

60

70

80

90

100

1283

1155

1344


30

25

20

15

10

05

000

Hea

t flo

w (m

Wg

)

1681441209672Time (h)

4824


(a)

300

250

200

150

100

50

00

Hyd

ratio

n he

at (J

g)

1681441209672Time (h)

4824


(b)








(7)



Q4Q3

Q0

Observed

Generated


(a)

Observed

Generated



Q4Q3

Q2(1A1)Q2

Q1 Q0

(b)


Observed

Generated

Q4

Q3

Q2 Q2(1A1)Q1

Q0

(c)






















0 5 10 15 200

200

400

600

800

1000

1200

1400

TIPA content (gL)

Con

cent

ratio

n (m

gL)

(a)

0 5 10 15 200

50

100

150

200

250

300

350

TIPA content (gL)

Con

cent

ratio

n (m

gL)

(b)

0 5 10 15 200

200

400

600

800

1000

1200

1400

1600

1800

TIPA content (gL)

Con

cent

ratio

n (m

gL)

(c)





4 Conclusion




Data Availability




Acknowledgments


References















































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls







10 7050 60402θ (degree)

Blank

006 TIPA

3020

Δ


Δ

(a)

90 1151101052θ (degree)

10095

AFtAFm

Friedelrsquos salt

C-FAC-FA + 006 TIPA

(b)





75

80

85

90

95

100

C-FAC-FA + 006 TIPA

Mas

s los

s (

)

(a)

C-FAC-FA + 006 TIPA


ndash10

ndash08

ndash06

ndash04

ndash02

00

02

DTG

(m

in)

Free water + C-S-H


FS









Stre

ngth

(MPa

)

50

60

70

80

90

100

1283

1155

1344


30

25

20

15

10

05

000

Hea

t flo

w (m

Wg

)

1681441209672Time (h)

4824


(a)

300

250

200

150

100

50

00

Hyd

ratio

n he

at (J

g)

1681441209672Time (h)

4824


(b)








(7)



Q4Q3

Q0

Observed

Generated


(a)

Observed

Generated



Q4Q3

Q2(1A1)Q2

Q1 Q0

(b)


Observed

Generated

Q4

Q3

Q2 Q2(1A1)Q1

Q0

(c)






















0 5 10 15 200

200

400

600

800

1000

1200

1400

TIPA content (gL)

Con

cent

ratio

n (m

gL)

(a)

0 5 10 15 200

50

100

150

200

250

300

350

TIPA content (gL)

Con

cent

ratio

n (m

gL)

(b)

0 5 10 15 200

200

400

600

800

1000

1200

1400

1600

1800

TIPA content (gL)

Con

cent

ratio

n (m

gL)

(c)





4 Conclusion




Data Availability




Acknowledgments


References















































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls










Stre

ngth

(MPa

)

50

60

70

80

90

100

1283

1155

1344


30

25

20

15

10

05

000

Hea

t flo

w (m

Wg

)

1681441209672Time (h)

4824


(a)

300

250

200

150

100

50

00

Hyd

ratio

n he

at (J

g)

1681441209672Time (h)

4824


(b)








(7)



Q4Q3

Q0

Observed

Generated


(a)

Observed

Generated



Q4Q3

Q2(1A1)Q2

Q1 Q0

(b)


Observed

Generated

Q4

Q3

Q2 Q2(1A1)Q1

Q0

(c)






















0 5 10 15 200

200

400

600

800

1000

1200

1400

TIPA content (gL)

Con

cent

ratio

n (m

gL)

(a)

0 5 10 15 200

50

100

150

200

250

300

350

TIPA content (gL)

Con

cent

ratio

n (m

gL)

(b)

0 5 10 15 200

200

400

600

800

1000

1200

1400

1600

1800

TIPA content (gL)

Con

cent

ratio

n (m

gL)

(c)





4 Conclusion




Data Availability




Acknowledgments


References















































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls









(7)



Q4Q3

Q0

Observed

Generated


(a)

Observed

Generated



Q4Q3

Q2(1A1)Q2

Q1 Q0

(b)


Observed

Generated

Q4

Q3

Q2 Q2(1A1)Q1

Q0

(c)






















0 5 10 15 200

200

400

600

800

1000

1200

1400

TIPA content (gL)

Con

cent

ratio

n (m

gL)

(a)

0 5 10 15 200

50

100

150

200

250

300

350

TIPA content (gL)

Con

cent

ratio

n (m

gL)

(b)

0 5 10 15 200

200

400

600

800

1000

1200

1400

1600

1800

TIPA content (gL)

Con

cent

ratio

n (m

gL)

(c)





4 Conclusion




Data Availability




Acknowledgments


References















































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls























0 5 10 15 200

200

400

600

800

1000

1200

1400

TIPA content (gL)

Con

cent

ratio

n (m

gL)

(a)

0 5 10 15 200

50

100

150

200

250

300

350

TIPA content (gL)

Con

cent

ratio

n (m

gL)

(b)

0 5 10 15 200

200

400

600

800

1000

1200

1400

1600

1800

TIPA content (gL)

Con

cent

ratio

n (m

gL)

(c)





4 Conclusion




Data Availability




Acknowledgments


References















































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls





4 Conclusion




Data Availability




Acknowledgments


References















































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls



























Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls




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