(Cement and Conerete Composites 136 (2023) 104857 Contents lists available nt ScienceDirect Cement and Concrete Composites ELSEVIER journal homepage: wr elsevier-comilocateleemconcomp Internal curing for high-performance concrete by a green composite capsule |S Xiaoyu Shang””*”, Na Qu” {Seo fC ngnering ad Artec Nore Herts Power nie 132012 Che ower nea ewig (iguie sd inxeaie composts High peromaeseooeete Improving concrete ecofciency is a challenging and ongoing topic in response 10 the sustainability Fe quirements for modern concrete infastuerure. This sy propose a novel biobased intemal ewing CIC) agent ‘hateial for high-performance eoneete A Two sep physical method was suecessily developed ro tn oie alginate and inorganic ty ash into ahigh-value-added geen composite capsule, wet de intel alginate Bea eserves abundant IC water andthe extemal robust sell supplies the protection to elie steady water release, ‘The composite capsules with a core shell suture havea partie sizeof 850 +20 ym, shell hcknes of 10 ya ated water content of 40 wis. Moreover, the IC effet of composite capes on cement pase was tuonitoned by the hydration proces, the setting tte and microstructal observation Fuster ICeiceacy a ‘quantified by autogenous shinkage and compressive stength. The rests indicate that is Feasble to se the propose green composite capsules fo inernally cued high performance concrete. The compose capsules ean hoe only eeevely decrease the autogenous siviakage Dut aso eliminate the negative degradation of the compresive suengt of concrete due 10 the incorporation of IC agen Te novel IC agent represents supe ities in terms of IC efieney and sustainability 1. Introduetion Internal curing (1G) has been a cutting-edge technology in the field of high-performance concrete (HPC) i seceat years [1,2]. Although the strength of concrete is periodically iniproved by means of a low w/e ‘tio, a high cement content, and the incorporation of admsatares (3,4), the deformation ise seems fo be more sigaifinnt for either the eon. crete materials or structures. Early-age cracking associated. with self desiccation and autogenous shrinkage restriets the application of high-performance eonerete [5]. Conventional external curing methods lose their curing function for HPC or large-scale concrete specimens to limited curing water transportation from the dense surface to the Interior (61. In view of ths limitation, 1C was found to be a practical pathisay 10 retain the relative humidity of eonerete by internal water feleased From IC agent materials, This technique can mitigate the shrinkage and erack risk of high-performance concrete early om in the process ‘Current frequenty-used IC agents can be malaly divided into two ‘categories: porous materials, such as ightweight aggregates (LWAS) (7), ‘and physical absorption materials, such as superabsorbent polymers (SAPS) [8]. Porous LWAs rely on the capillary action from the micro cellular structure to store water [9]. However, ics fast internal water release and low water absorption decrease the IC efficiency due to its week water recaining capacity [8,10]. In comparison, SAPs are superior because they contain crosslinked polyeleetrolyes, which would convert into n high seater content hydrogel when in contact with water oF aqueous solution (11). Water molecules diffusing in the polymer network lead to swelling and water uptake of thousands of tines their dry weight {12,15}. By vite oftheie strong water absorption capacity, SAPs were introduced as an alternative Co mineral LWAS to realize 1C functions with only a small aniount of material [14]. Different from LAs, SAPS can be added to fresh concrete to absorb water without any presaturation process. Thus, the mixture design must be precisely controlled to compensate for absorption/ desorption with ry SAPs [15, ‘ok In fact, the substantial reduetin in strength of prepared concrete indiced by the incorporation of SAPs or LWAs sa miajor problem to be solved due othe undesired abundant pores in the matrix [2,11,17].This Issue is related to the competition of two mechanisms between the pore that deflects the 1g 1C agents and the densification of te matrix from further hyération [17,18]. Thus IG effieeney is of signifieance to * Conesponding author. School of Civil Engleeting and Architecture, Nowtheast Eechie Power University, iin, 132012, China * Conesponding author. Shoo! of Civil Engineering and Architect, Northeast Eleeie Power Univesity, a, 132012, China Email addresershangaoy gueeps. eden, xnoyushangGvelac ik Cf. Shang), qunaGneped.cn (8. QU). ups /éoLor/10.1016/eemeoncomp.2022 104867 Received 22 Jly 2022; Reveved in cevised frm 20 October 2022; Accepted 21 Noveber 2022 ‘Availabe online 25 November 2022 ‘099894650 2029 Eee Lid Al rights reserved,X Shag and iitgate this issue. For SAPS/LWAs-containing cement paste with @ relatively low IC efficiency, a required increase in SAPS/LWAs dose te duces the strength of concrete due to increased pore production by 'SAPS/LWAs while Increasing the economile cost [19]. Previous studies Indicated that the type, content, particle size and water release behav- Jour of I agents would significanty influence the IC efficiency (2,19) Zhutovsky et al. [20] demonstrated an interesting finding that decreasing the IC agent particle size would increase IC eifiiency Hovsever, further rection of parte size below 2 mum led row decrease ln IC efficiency eather than enhancement. Thelt Further investigacon indicates chat although smal particles can enfance IC efficiency with & sual spacing factor, small particles possess reatvely small pores that tend to retain water more ily. The most important parameter seen to be the availability of IC water and the internal structure of the 1C agent (21,22) A recent study stated hat green biobased alternatives represent a Hsing field of research considering synthesized SAPs based on acrylate chemistry [11]. Since crude oll is becoming expensive and nonrenew. fable, more green polymers should be explored with an emphasis on ‘cot effcieney and sustainability [29-25]. Sodium alginate fs a nararal Diobased polymer obtained by extraction from the cell walls of brown, algae, and has been reported to be @ renewable, low-cost and plentiful resouree [26]. It sa linear copolymer composed of mannuronie and Juronie nei, covalently inked in various sequences and blocks (171 ‘When sodium alginate is mixed with calcium solution, an insoluble gli formed with « physically cross-linked network. The carboxyl group on sodium alginate and calcium ious are combined by an ionic bond and chelation bond with an eggbox seructure (27,28). tn addicon, ‘compared with SAPs, alginate hydrogels possess Tower swelling rae, less excess water and stronger hygtoscopicity [17]. Importantly, the previous studies reported that the sttength of concrete mixed with ‘alginate hydrogel is higher than that mised with SAPs [17,29,90] This paper proposed a novel IC agent with a eavity structure for IG high-performance concrete. The green composite capsules were ‘composed ofan organi alginate core and an inorganic fly ash shell. The IC effects with composite capsules were monitored by the hydration ‘proces, setting time aud microstructural observation. IC efficiency was ‘also quantified by autogenous shrinkage and compressive strength ‘analysis, The proposed composite capsules have three features ‘compared with the eurent IC agents of SAPS or LWAS: 1. green and low cost, the rate materials are derived from renewable bio-based alginate and reeyeled My as 1 excellent morphology and structre, stall size ‘ould contribu to the improved distribution of 1¢ water, and a single ‘cavity conduces ro the stable release of 1C wate, snd II simple prep aration, only two-step complete physical fabrication is required in the ‘overall process. These features suggest that the composite capsules would be & promising eandidate for IC agents for high-performance 2. Materials and methods 2.1. Materials {Class F fly ash (FA) and ASTM 525 ordinary Portland eement (OPC) ‘wore ised as raw inorganic materials snd provided by Green Island Ltd ‘The specific gravity of cement and fly ash was 2.60 and 8.10 g/t, respectively. The mean particle sizes were 624 yn a 54.6 ym. Table T hows their detailed chemieal composition. Sodium alginate with 9 purity of 959% was used as the organic raw material and purchased from ‘Table 1 Ghenical composition of FA and OPC. SO: GO MgO ADs Ss KO Feds cme an Conc Compacts 195 (2023) 104867 Dongfang Chemical Lid, and its viscosity grade was 160 mPa s in 2% solution at 20 °C, Caleium chloride dihydrate with a purity of 759% was used for alginate gelation. Quartz sand with over 92% SiO content was purchased fron ISO Standard Sand Lid and used as aggregates. The particle size ranged from 0.15 mm to 2:36 mm. A commercial polyearboxylate-based superplasticizer with 25% solid content and specific gravity of 1.05 was provided by Sobute Materials Ltd for pre paring all mixtures 22, Fabrication of composite capsules ‘The composite capsules (CC) were fabricated by two processes vd coating. tn the fist process of extrusion, the sodinm lginae solution was dripped into calcium chloride solution by a pet stalie pump with a low rate of 60 rpm. immediate gelation generated a single bead when the droplet comes into contact with caleium io ‘These beads experienced 2 h of curing in caleium chloride solution to fully complete the crosslinking reaction. Then, the hardened beads were Immersed ina sodium hydroxide solution for another 2 to densify the crosslinking and undergo solidiietion, The alginate beads (AB) were retrieved vi filtration to reach saturated surface dry (SSD) conditions for use inthe following coating. During the process of filtration, the AB solution was poured into the perforated sereen and washed with pure water to remove the chemical residues. Then the semiwet beads were sequentially placed inthe screen in the curing chamber (Cemperate of 23°C, relative humidity of 659 and airflow of 21/8) for 2h to leach the ‘water on the surface of AB. In the second costing proces, a cementitious power with 80 Wi FA and 20 wI88 OPC wins mixed ns aa inorganic coating material. A high-speed disepelletizer was used fo evar cemen Uitious powder on the beads. The angle of 45° and speed of 180 rpm were seca the pelletizer parameters after the retrial experiaents The whole process of pellet coating is finished in a limited 1 min. During the pro ee, strong impact counterforee compels the elastics beads to be sep rated into’ a condition of dispersion. with cementitious material hardening, the organie beads would be encapsulated by a robust inor- sane shell. Ir should be noted that the water for shell material hydration was provided by internal AB without any additional water, After taese ‘neo misin processes, the semifinished capsule powder was taken out, purified by sieving to remove the excess cementiions powder, paced into a sealed environment, cured for 1 day until the inorganic shell hardened, and then stored In sealed container at room temperature. Fig. 1 describes the fabrication process of composite capsules. After fabrication, some base properties of matired eapsiiles were tested, sich aspartic sie, shell thickness and water content. The particle sie of AB sand shell thickness of CC were measured by an optical microscope (OM, [Nikon $M21270). The Fresh AB were dispersed into the water soliton to show an intact shape and seale. Dry CC wore spit to reveal the clear shell thickness, The average particle size and shell thickness values were recorded from atleast 20 individual AB of CC. The water content was recorded by a determination balance (MD, Shinko Denshi, Series 83) 2.3. Water release behaviour of compasze capsules ‘When AB and CC were added for internally cuting the concrete, thet internal water was released into the surroundings inthe high moistare feavironment. Weight changes in AB and CC were used to represent the water release elivour, 50% RE and 959 RH were selected asthe early tind later stages, respectively. ASTM S11 reported that these fa bi tmidity levels could also simulate the moist and aie curing conditions. Freshly prepared AB and CC were placed inthe camber. Weights of CC snd AB were reguatly recorded by the balance, and he test ended when the welt change was les than 196. 24, Setting tne cn hydration process ‘The setting time and the hydration process were tested to assess theX Shag and cme an Conc Compacts 195 (2023) 104867 ‘Alginate |_ Extrusion = Coating = solution | Peristaltic pump Pelletization disc Dissolution Solidification & Fiation Sieving & Curing Fig. 1. Fabvication process of composite capsules. I effect of CC on the coment paste. The paste witha we ratio oF 0.35 conformed tothe condition of high-performance concrete (22,51,52). A total of 10 9 IC water to cement was selected and provided by the CC and AB, as described in previous studies [51,95], The contol samples without CC and with non-eater dry CC were also studied as the cou parison group. The initial and final setting times of the internally cured system were recorded by Vicamatic (CONTROLS) in general compliance ‘with the standard procedure in ASTM C807-1/ [2]. The inital seting ‘was achieved when the needle with «2mm diameter penetrated into the str for less than 25 sun, The final setting was obtained when there was no indentation on the specimen surface. drop number of 31 was Komatially conducted to search for the right setting time ofthe ma trix. The final setting time will be used as the start of the autogenous shrinkage measurement, The test was performed three times to better estimate the setting time. Correspondingly, the hydration process of Internally eured and noninerally cured systems was monitored by an Isothermal calorimeter (Calmetrix-L-al 8000). According 10 the designed amount of curing water, each sample contained 30.0 g of Portland cement, 10.5 g of water, and 5.0 g of curing water provided by 3.1 gof AB or 75 g of CC. All samples were mixed by a suall-scle vi bration for 15 sand then east into a specific plastic cup. These prepared paste samples were placed in the channel ofthe calorimeter. For elarity, the heat powder results were plotted up to 24 b, while the cumative heat was recorded for 72 h continuously. The record of an initial 20 min was deleted due o the wastable hydration process. 2S. Autogenous shrinkage and compressive srength Autogenous shrinkage and compressive strength were measured (0, ‘reflec the IC efficiency af CC on the cement mortar. The mix proportion Is shown in Table 2. There were four groups of samples, including 1 em cementitious slice containing th intact CC and the clear Interfacial transition was selected and then dried by cold airflow to avoid unnecessary damage. The shell of the exposed CC in the cemen- tions paste was manually tom by tweezers to display 9 clear core. 3. Results and discussion, 3.1. Characteristics of compasive capsules ‘The prepared CC demonstrated an organic—inorganic composite system (Fig. d), where soft organic hydrogel beads were covered with a hrdening inorganie cementitious shell (Fig. Sa and b). Internal water release induced the formation ofthe cavity structure and a few yellow alginate residues remained in the core (Fig. 3e)- The initial hydrogel beads were spheriel with a uniform size of 800 um, and futher shrunk {o an appropriate 720 ym with hydrogel hardening in alkaline soliton. “These vulnerable hydrogel beads had a low capacity to retain the water Inthe crosslinked chains (Pig. a). Thus, the excess water on the surface was removed by filtration to reach the SSD condition. Hydration of shell materials occurred when the cenentitions particles contacted the water released from alginate beads rater than the residual water attached to the surface (Fig. Se). These processes contribute to obtaining the thin shell and maximizing the water content for eapstles. Internal and fexteral gelation rely on different mechauists, For internal gelation of AB (Pig. SD, alginate Is composed of two building blocks, namely a xguluronie ace (G block) and f->-manntronie aed (Mt block). When so dium alginate is placed into a celcium chloride solution, ealeium ions Induce a cooperative effect between G-blocks wnt forming @ 3D network, asin an egg-box model. Water uptake eccurs because of the hydrogen bonds formed berween water molecules and earboxslate groups in the M block, For external gelation of the shell, the cement Hows particles absorb the water fom the internal hydrogel for hydra tion, ‘The robust shell rooted in the hardening of the inorganic ‘composites, The amount of water involved i the hydration is limited by the iydrogen bonds of AB, thus contributing to redicing the thickness of the shell. Table 9 lists the physical properties of AB and CC. AfterX Shag and cme an Conc Compacts 195 (2023) 104867 Comma Mic i i sed or2min [cc [ane ort min Wa Taewaped | 5 Pwangimest] fan fatale | MO Fig. 2. ising procedate for mora geACK Aan FERRIC Fig. 3. Morphology of AB and CC a) lsh AB; (b) hardened CC; () cementitious parison the hydrogel susac; (sketch structure of CC (6 setion of éry CC; (© egg-box mode for alginate gelation with alum ins. ‘Tables lyse properties f AB and Cc ‘Metids Se Sarue Fake Shel Water 3B Beaton Sphee Sold 720m 38 wo CC elltsing Sphere Holew S50 20 5.410 Oe ‘oting, the particle size an shell thickness of Cc were 850 4.20 ym and (65 £ 10 pm, respectively. The uniform AB resulted in dhe singe size ‘characteristics of the prepared CC. The water content was decreased from 98 wes (0 40 wr in the capsules, The rato reduction occurred because of the conted dense cementitious shell. After removing the exterior shell, the water content of the Internal alginate beads still reached 80 wr96. Par of the weight loss was due tothe hydration of the ‘cementitious particles of the shell The hardening shell finaly tras formed into thin protective fin for the internal vulnerable hydrogel beads (ig. Se). 12, Water release of capsules ig. 4 deseribes the weight loss of AB and CC under 50% RH and 95% RH during the period of 72 b, fe can be observed thatthe samples took ferent time to reach the stable stages with different weight losses, More and faster weight losses of AB and CC occurred atthe low humidity level. Ac the level of 5096 RH, the weight losses of ABand OG were 98.1% ‘and 28.4%, respectively, AB represented a faster water teense rte thas (CC inthe inital 2 h. The unstable water on the AB surface may be the main reason, The small amount of water paticipated in the hydration of the shell materials. Then, the moisture gradient drove nearly all internal water roleased for exposed beads. The thin shell of CC blocked the in ternal water to slow down the release rate. At the level of 95% RH, the €C-50% RH ‘A AB-05% RH [# 60.9% RII Weight loss (24) ° 06 «12 18 24 30 36 42 48 34 60 66 72 ‘Time (hows) Fig. 4. Weter release of AB and CC at SO¥6 RH and 95% RH, trend of weight loss i similar. The stable values for AB and CC were 51.89 and 7.6%, respectively. The reduction of the moisture gradient decreased the amount and rate of water released. For CC, it took proximately 24 reach the stable state at 50% RH and extended to 448 at 959% RH, Ie seems that these characterises could mitigate the cement paste shrinkage that usually occurs from the final seting 1024 h-96 h [971 23, Seng ime Fig. 5 demonstrates the Vieat needle penetration forthe seting time of both control and incerally cured cement pastes. The inital and finalX Shag and ae asso TBA a0 om cme an Conc Compacts 195 (2023) 104867 : " 4 i Bos fo] & & Fig. 8. Vien nde penetaton for cone and intemal cuted pastes setting ines were 170 min and 270 main forthe contol sample without ‘any CC, 245 min atid 910 main forthe control sample with dry CC, 250 ‘in ad 850 min fr the CC-paste intemal euged sample, nd 295 min ‘and 70 min for the AB paste Inemnlly cured sample. Bodh the initial ‘nd final setting times were prolonged hy the incorporation of either CC, |ABor dry CC. By comparing the control sample without any CC, the final ‘setting ime ofthe ry CC-paste system was retarded by approximately 40 min. The retarding elect was further enhanced for the OC-paste and AAB.paste samples, However, the different reasons result in thele retards “The AB-paste sample ean be atibted to dhe inerease in the initial w/e ‘ratio with the water released from AB. Increasing w/c results in later Inia and final secting times of cement pase. Previows sts [35,99] reported the same result that additional water lead to an increase in the setting time of cement paste. For the OC paste and dry CC paste systems, the reduction of cement paste volume may be the main reason for the Incorporation of CC. The existence of either CC or dry CC diluted the concentration of cement and water, thus slowing dovn the seting process. The relatively long retard time of the CC-paste sample was ‘enuse by the internal water of GC. When studying diferent IC agents, previous scholars found a siniar phenomenon (31,59) 34, Hydration process ig 6 displays the heat evolution ofthe four mentioned types of paste ‘systems. As shoven in the hydration rate curve in Fig. (a, the peak of the curve Is induced by the rection of C3, gypsum and aluminate for ‘cement dissolution [51,40] ean he observed char the peak was slightly ‘echoed with the addition of either CC or non-water dry CC and shifted to the right. Peak reduction and right sifting ofthe curve indicated & slowing of hydration, which induced a decrease in the maximum heat release rate and the hydration duration delay. The deerease could be ‘ase bythe fet tha the inorganic shell of CC absorbed the free water In the cement paste. The water involved in cement hydration was redliced to slow the heat power. The absorption effet was enhanced for the dry OC and thus the lowest peak was observed in the Contrel-C¢-0% sample. Interestingly, different results were obtained by introducing the ‘AB and CC. The peak ofthe eurve was ineteased for the AB: paste system ther than the sight reduction inthe CC-paste system, but the amount of IC water was the same. The apparent delay ofthe peak occurred even greater an the result in the CC paste system, Ths rest is Because of the excess water involved in hydration. The intial we ratio might be increased by the water released from AB too early. Ths miny inyply that the AB hed a low water retaining eapaeity. By virtue of the thin shell procecton, the CChad sonte effect on the hydration power with slight delay inthe peak ine inthe initial 24 h These results correspond to the longer setting tine in dhe control samples compared with the internally ‘red samples, The slower hydration rate resulted in a longer setting time [31,38] ig. 6() deseibes the total hydation heat released from the emtent pastes with or without IC agents. Inthe initial hous, all the eurvs have f similar processing trend. The total hydration heat of cement pastes Increases widh hydration te. The sample with dry CC (Control-CC-0%6) released a lover ent than the control one without any eapsules (Cam: ‘101-0%) due fo the reduction inthe hydration water content. The free water in the fresh cement paste vas absorbed by the dry shell and cavity of CC. At approxiniely 42 h, the amount of hydration heat was dramatically inereased in de sample with CC and surpassed chat of the control sample (Contol-O3), which revealed thatthe IC water partic pated in hydration. A previous study also reported that higher hydration Theat was released from the IC effect than ia the nox: 1C sample (1,39,411 ‘This enhancement of the cement hydration can have @ positive impact fm the strength of the prepared concrete [42]. By comparison, the sample with AB (IC-AB-10%) released the highest hydration heat after the initial 12 h, The werk water-retaining capacity of the hydrogel promoted the mass of C water released into che eeqent paste, This, ass water wes involved in cement hydration rather than. being remained to the 1C process. The results agree with the previous ndings that the cunilative heat of hydration increases with increasing W/C (1, ‘38}. Tis pheuomenon also resulted ina reduedon inthe IGeiclency of| the AB agent. However, the cotal hydration heat after 72 h was simile for the pastes with AB an CC due fo dhe same total Water iow, whieh slso indicated that most of te water in AB nnd CC was released daring ‘he initial 72 to parleipate inthe hydration. A similar Finding has been reported in SAP-based IC systenis [38X Shag and 4 = Control% Control-CC-0% | Ic-aB-10% 0 4 ie 0 @ Time (hy —Conirol0% —Control-C-0% —1e-ce-10% 8 g Heat W/g) s 0 20 30 40 30 60 70 80 Oo) Time (h) Fig. 6, 1C effect on the hyération process. (a) hydration rte; (b) total ya tion Bet. 500 Conia Contol-CC-0%% —Ic-ap-10% 10% Autogenous shrinkage (ne) om Ws 2 96 120 1 168 Time (hour) Fig. 7. Antoenous suka enves of contol a 1 cemen morta cme an Conc Compacts 195 (2023) 104867 3.5. Autogenous shrinkage Fig. 7 showed the autogenous shrinkage of control and internally ‘ured samples smal expansion was noted for control samples after the final seting. This expansion might be caused by the crystallization pressure of calcium hydroxide [43]. The control0% sample had @ ‘maxinium autogenous shrinkage of S40 pe at 7 days. The autogenous shrinkage of control-CC-OM6 decreased to 458 je du to the reduction in hhyeration water. The incorporation of ary CG absorbed the verter in the cement paste and similarly decreased the initial w/e ratio, whieh was consistent with the hydration process results, The hydration rate had & Positive corelation with autogenous shrinkage (2). From the shrinkage ‘uve of IC samples, #reduetion was realized by the IC agents of AB and CC. Autogenous shrinkage of 301 pe was obtained for the AB paste sample at approximately 90 h (IC-AB-10%). The aéition of AB pro: oted a slight reduction in shrinkage, although it was not sufficient co eliminate autogenous shrinkage. Previous studies indicate that the fective IC was supposed to be released around che time of the matrix setting and lasted fora sufficient period (23,4445). AB agents tended to be released too early for cement hydration rather than contributing to the reduction of autogenous shrinkage. Ie was observed tata precipi tous decline occured in the shrinkage ofIC-AB-10% although shrinkage was relieved compared tothe control sample. The result indieted that the 1C-AB-10%6 saple nd denmatie vohine change ding the ering process and there might be inferior damage caused by the stress can centration, The microstructure analysis will further diseuss the phe- romenon. For the CC-paste sample (1C-CC-10%), a stable expansion of 426 ue was observed. The expansion might be explained by the IC water released from CC after the final setting. From the results of 1C-CC-10%, the expansion remained constant after approximate 24h. IC water from (CC fully compensated forthe self desiccation induced by cement hy Aration, Previous IC based ont SAPs tended to mitigate a similar expan sion (19,45,46]. The enhancement of internally cured efficiency for CC was eansed by two reasons. The inorganic shell delayed che internal water release and made the internal curing process more sustainable. Increasing the water retention capacity of the IC agent or effective 1C water content can improve IC efiiency (19]. Additionally, AB volume Aeformation induced by water loss and possible mechanical damage ‘might promoce agglomeration and decrease the IC efficiency. A previous study stated that agglomerated SAP particles eause the formation of large voids and a reduction in compressive strength [47]. With the hardening shell, the stable morphology promotes CC to be well distribuced in the cement paste. The water travelling distance was rediced by the well distributed curing water to tedhice autogenons shrinkage (22,48) 3.6. Compressive srength As another key indicator reflecting the IC efficiency, the compressive strength rests forthe control and IC mortars are shown in this serio. From Fig, 8, i can be observed thar the compressive strength of all roups of mortars increased with the hydration age. The compressive strength of cotrol-CC-10% decreased with the incorporation of dy CC. “The strength reduction can be attributed to the hollow structure of dry (CC. These hollow eapsuies have weak strength a lightweight aggregate fillers. Previous studies on lightweight aggregates or cenospheres also shoved that the strength of the prepared concrete decreased [31,49] For internally cured mortars, the additional pores left wich 1 water Toss decreased the compressive strength when IC water was introduced into the cement paste by AB and CC. On the other hand, the densification of the cement paste around the eapsules by the IC effet contributed othe bnhancensent of the compressive strength, These two competing mech: anisms mutually affected the final mechanical properties. From the te sults, the 2 day compressive strength of C-AB-1096 was lower than that of control 0%, although autogenous shrinkage decreased by the internal ‘uring ftom AB. The results indicated that the detrinental effects fromX Shag and 90 | wContol-0%% ‘= Control-CC-0%6 a Se BD 2 mt ia F 30 Fo i ° : % 7 a ratans Fig. ®. Compressive stent of contol snd HC mortars a 3, 7 and 28 days the resultant pore deflection surpassed the improvement from IC. An Increase in the initial w/e ratio might be another possible reason. Aldhough AB had a controled capacity for IC weter-etaining toa certain ‘extent, AB cannot eliminate the fast water release that was driven by moisture gradients at the inital time (18). This result corresponded 0 previous reports about IC based of SAPs [17]. For the IC-CC-10% ‘sample, the 3-day compressive strength was sil lower than that ofthe contol samples. However, ater further 7-day curing, the compressive ‘engi aught up with the conttol groups, and even a 59 enhancement was obtained afer 28 day curing. The iniprovement was eaused by the face thatthe water release from CC contibte to the cement hyraton ‘and strength enhancement for morta. The results indiated tha the lmproventent ofthe strength from cement hydration products exceeded ther detrimental effets from the pore defects. n previous studies, using ‘SAPS or LWAsas an IC agent enused an approximate 8-12% reduction in 28.day compressive strength [22,99]. The satisfactory IC effect and ef ficiency of CC were attributed to the structure ofthe robust shell and hydrogel core, by which CC possessed stable water-tetaining and water releasing capacity. Moreover, ideal spherical CC benefited from the droplet method of inner AB could deeresse the sess concentration ‘of hardening cement paste rather than iregular pores left by SAPS oF LWAs [28,90] 3.7. Microsticrre of cement mortar With the comparison between control and IC samples, the ) cme an Conc Compacts 195 (2023) 104867 racroproperies IC samples were improved by AB and CC in terms of autogenous shrinkage and compressive strength. However, the above results show that the cement pastes mixed with IC agent capsules ‘demonstrated different properties. The IC effec aud efficiency ofthe AB: paste sample are lower than these ofthe Cc-paste sample, Thus, their ticrostructure will be discussed in this part. fis, 9 desribes the microstructure of hardening AB-paste, CCpaste and dry CC paste Apparent differences were observed in the pastes mixed with various capsules. The increasing w/e ratio of the cement paste around AB formed a weak region due fo the fas relewse of IC water. AB Was sur rounded by cement paste with a loose steueture. The propagation of inultipe cracks ereated a collapsed cavity. Multilayer cracks reflected the moisture gradient induced by 16 water release aud transportation. ‘The results indicnted thatthe deformation oF AB eaused by water loss affected the stable state ofthe AB paste system. Thus, the werk cement peste around AB collapsed when the defornied AB left the pate space to lose support for the interfacial aree. This might be the reason why @ precipitous deeline occurred in the autogenous shrinkage eurve of the AB paste sample. The collapsed pores aside the sample led toa dramatic volume change. Nonprogressive autogenons shrinkage of IC-AB-10% can be observed in Fig, 9). after coating with a robust shell, CC effectively controlled the original fast IC water release. No collapse of the AB paste system was observed in the CC-paste system (Fig. 9b). The area around the CC in dhe cement paste remained intact afer hardening. Incemal water of CC was steadily released into the cemtent paste t0 realize IC function, From the SEM ofthe CC-past sample (ig. 94), itean be seen that CC was effectively inserted into the cement paste with good ‘compatibility de tothe same inorgane nature forthe shell and mattis ‘A mass of hydration product accumulated ia the interfacial zone co densify the microstructure of the paste. Intact morphology indicated thatthe CC could withstand the shearing foree from mixing. By add ‘ional handling, clear cavity left with IC water los was observed in the cement paste, whieh would be a possible defect for the strength of the Drepared concrete. In contrast, dry CC without internal water broke down the IC function tothe surrounding cement paste, and cracks even occurred in the interfacial area (Pig. Se), The hydration water in the ‘cement paste was reversely absorbed by the dry CC with the cavity strenie. The nonequilibrium stress between the shrinkage of the cement paste and restraint of the hardened shell induced crack props: sation along with the interfacial area. It seems that the dry CC reab Sorbing free water fom the fresh cement paste didnot supply enough IC water fo the hardened cenent paste. This is a possible factor that resulted in the lower strength of the dry Cc paste sample (control Cc: 1%). This phenomenon corresponds to the previons rest about LAVAS tL © mi Cement paste Interfacial zone Water Fig. 0, Micostructs of internally cued cement moras afte ial eting(a) OM of hardening AB paste; (b) OM of hardening CC paste; () OM of hardening dry (CC paste; SEM of dening dy CC-pte,X Shag and 4. Conclusions Based on the above discussion, the conception of inuovatively ‘combining the renewable resourcealginate with cutting-edge IC agents ‘conformed to the advanced circular economy strategy of tuning waste into high-value-added products. Thus, this study proposed green con posite capsules for IC of high-performance conerete, The major conclu sions are sumamarized below. (1) A vwo.step physical method was suecessflly developed to wen lorganie alginate and inorganic Ay ash into a high-value-added sreen 1G agent for high performance couerete, The composite capsules with a core shell structure had a particle size of 850 +: 20 4m, shell thickness of 65 + 10 ym and water eontent of 40 wt It took approximate 24 h for te eapstles to reach the stable sate at 509% RH and extended 10-48 hat 9596 RH. (2) The internal AB reserved the abundant IC water and the external robust shell supplies protecton to realize steady water release ‘Ths, the incorporation of both AB and CC retarded the setting time of mortars and a weaker retard effect from the CC-paste system, The IC effect of CC led to a slow hydeation rate and & high amount of hyération heat. (8) OC represented a postive IC efifeeney In the mitigation of autogenous shrinkage of mortar, and iC also promoted compres sive strength. The CC-paste sample expanded slightly during the initial 24 hand then stopped autogenous shrinkage, Although the 3day compressive strength of the sample was lower than the control samples, ater further 7-day curing, compressive strength caught up with the control sarupls, and even a 5% enhancement twas obtained after 28-day curing. 4) Microstrucre observation demonstrated that both exposed AB and dry CC would further damage or crack their leaving pore structure in the cement paste wich also induced low IC eff cleney for the autogenous shrinkage and compressive strength. With a coated robust shell, CC could resist the shrinkage stress of the surrounding cenient matrix, and the alginate core supplied sufficient IC water. CC also showed good compatibility with cement paste and stable microstructure. 1 ean be seen that the proposed CC is entirely derived from an. artificial design and fabrication process. Thus, in future work, by virtue ‘of te adjustable characteristis of the organle core and inorganic shel, the snag release behaviour will be further analysed to explore some fundamental fsues of I, such as minimum IC agent dose and effective IC transport distance. Declaration of competing interest ‘The authors declare that they have no known competing financial Interest or personal relationships that eould have appeared c influence the work reported in this pape. Data availability Data wil be made available on request Acknowledge ‘We would like to acknowledge the financial suppor from the Natural, Science Foundation of Jilin provinee, China (20210402076 GH). 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