onstruction and Bulding Materals 250 (2020) 118923 Contonts lists available at Scioncobirect, Construction and Building Materials journal homepage: www.elsevier.com/locate/conbuildmat = Ultra-lightweight cement composites with excellent flexural strength, ® thermal insulation and water resistance achieved by establishing ax interpenetrating network Qing Liu*, Wenjie Liu, Zongjin Li*, Siyao Guo“*, Guoxing Sun** sone Ky aboracry ofthe intr of Educa, nse of Applied Phys and Mates Engineering University of Mau, vended Universidade. Tip, Macey SAR, China acy of novation an Deen Cy Unversity of Maa, Tai Maca, Cina Seal of Ci Engineering, Qo Technologie Universi, Qn, China “+The PAM is formed through the inst free-radical polymerization during the cement hydration, {The flexural strength is increased by 100% with the addition of 3% PAM, {interactions between hydrated products and FAM significantly improve the flexural strength. SULCC incorporating PAM has higher water resistance. ARTICLE INFO ABSTRACT Are oy Receive 8 January 2020 Received in revised form 21 March 2020, DAecepted 26 Mare 2000 ‘This research sms at developing the ulightweight cement composites (ULEC) with high Nexural strength, good thermal insiaton. and great water resistance by incrporaing the acrylamide Dolyaciamite (DA) is ome by init fea! paymertaton during te hain of cement ‘he psie-mechania properties, thermal performance, iterations between ated cement nd PAM, microstrctreand water absorption af the computes are characte in deta ly ash ceno- spheres (FAC) is used to abicate the ULCC witha density and thermal conductty of approximately pe 1250 igi’ and 03 Wim Krexpectvy. The Neral strength impress improved by ang sural strength DA, whee the compostes with 3sPAM hve te highest Mex strength while till mina suicent a compressive stenath: The physic and hema interactions between PAM an hydrated product re iteration found t dominate the Metra strength and toughness ofthe composts. PAM-modifed ULCC displays Mc sotion mich higher resistance apsnst water in comparison to the nest mse a el 12020 sever Lid ahs served 1. Introduction Currently, energy savings and waste utilization have been ‘becoming an urgent demand for the sustainable and green devel- ‘opment of the economy and society. Lightweight concrete as an cenergy-savings material has been attracting lots of attention due to their excellent properties such as thermal insulation, fre resis- tance, acoustical insulation and reduced dead load for building structures. Owing to their superior performances mentioned above, lightweight concrete has been widely employed in the infrastructure constructions such as long-span bridges, marine structures, and high-rise buildings, etc. (1-3). Some lightweight * Gorespoting authors mal oddest enyoatecheds.en (8 Go) sxsaneumeds mo (6. Sam, naps: do.og/10.1016(conbuitanat2020118923 (950-0518) 2020 sevir Ld Al rigs reserve aggregates (basaltic pumice |4), expanded polyvinyl chioride (5, FAC [6-10], expanded perlite [11-13] and foamed plastic waste {14.15}) are extensively used in fabricating lightweight concrete Although using the lightweight aggregate to take the place of the normal weight aggregate reduces the self-weight, the mechanical strength and stifiness of lightweight concrete are reduced inevita- bly, especially for flexural strength. The reduction in strength and stiffness for lightweight concrete makes it incline to crack and ‘degradation, hindering its popularization and application in con- crete structures. ‘To overcome the low mechanical strength and brittleness of lightweight concrete, polymers as the cement-based reinforceable ‘material have been applied to these cementitious materials due to their excellent compatibility with the cement. tis well known that polymers have high elasticity, better toughness and high flexural2 tiv et ol /Consction and Buding Material 250 (200) 115525 ‘capacity, and, offer good adhesion to some inorganic materials (Such as cement) as well as better resistance to aggressive medi tums (sulfate and chloride ions, etc.) attack. Combining the excel- lent properties of both cement’ and polymers, the cement ‘composites with outstanding mechanical performances can be manufactured. Previous studies displayed that the inclusion of polymer could tune the workability and strength development of lightweight concrete. For example, Patsio and Assaad [16,17] ‘observed a considerable flow improvement for polymer-mocified ‘cementitious materials. Rossignolo et al. [18] mixed styrene-buta- diene rubber (SBR) latex to the lightweight aggregate concrete and found that the introduction of SBR latex increased the splitting ten- sile and flexural strengths approximately 18% and 26% at a polymer) ‘cement of 10%, respectively. The influence of polymer on the Young's ‘modulus for lightweight concrete composites was also investigated, Which indicated that for lower polymer content it has a positive effect on the modulus of elasticity |19], However, incomporating superfluous polymers results inthe entwinement and agglomeration ‘of the polymer in the cement matrix, leading to the formation of faultiness in lightweight concrete. When the defective materials cary the load, the crack will quickly initiate and propagate along, with these defects. Consequently, the mechanical performance of lightweight concrete is deteriorated remarkably due to the appear- ance of these defects. Chen et al. added styrene-butadiene rubber latex into lightweight concrete and found that the compressive sirength decreased with polymer-cement ratio exceeding 10% [20] ‘The polymer-lightweight mortar composites with a high proportion ‘of polymer content had a lower strength compared to composites ‘without using polymer [21] Durability isan essential property that affects the application of lightweight concrete in marine concrete structures. Lightweight ‘concrete usually has larger porosity than the ordinary Portland ‘concrete due to the fac thatthe lightweight aggregate is more por- ‘ous than the cement paste matrix, Therefore, aggressive substances ‘can easily intrude into conerete through porous structures. Al- Khalat [22] observed that the lightweight aggregate concrete had higher concentrations of chloride penetration than that of normal ‘weight concrete, However, when using 31% lightweight sand to replace normal sand, the lightweight mortar showed a 25% reduc- tion for chloride diffusivity [23] Polymers can be used to improve the durability of lightweight concrete because it has the capacity to ‘densify the internal structure and block the connectivity between pores. Neser {24] found that the existence of polymer additives led to the reduction of water absorption and enhanced the bonding between particles of the lightweight aggregate concrete, The SBR- ‘modified lightweight concrete displayed better resistance t0 corro- sion and chemical attack compared to the unmodified lightweight concrete [25], In this study, the monomer acrylamide was added to the ULCC to form the interpenetrating PAM by in situ free-radical polymer- ization in order to improve the mechanical and durable properties of the materials. The microstructures, pore size distribution, ther- mal conductivity, thermal stability and interactions between hnydrated products and PAM were investigated comprehensively. ‘The compressive and flexural strengths were tested to evaluate the influence of PAM concentration on the mechanical properties ‘of ULC, What's more, the capillary water absorption was also determined. 2. Materials and methods 2.1. Materials and mix design Portland cement type P1 52.5 and silica fume were used to manufacture the lightweight cement composites. Fly ash ‘cenospheres with a bulk density of roughly 425 kg/m” were pro- ‘duced by Henan Platinum Run Casting Material Co, Ltd. and were used in lightweight cement composites as micro-aggregates. The ‘chemical compositions of cement, silica fume, and FAC were ana- lyzed by X-Ray Fluorescence (ARL Perform’X), which were pre- sented in Table 1. The particle size distributions of FAC and silica fume were measured by Malvern laser particle size analyzer (Mastersizer 3000), which were from 44 to 350 jim and 8 to 200 um, respectively (see Fig. 1). Acrylamide (AM), ammonium per- sulfate (APS) and N,N,N’. N-tetramethyl-ethylenediamine (TEMED) were analytical reagents that were obtained from Aladdin Reagent Co, Ltd. A polycatboxylate-based superplasticizer (SP) was used to maintain the workability and consistency offesh mixtures. For this study, five batches of mix proportions for lightweight ‘cement composites were listed in Table 2. The ULCC had a constant watet}binder ratio of 0.7 and comprised 10% silica fume by mass of ‘cement. The AM, APS, and TEMED were the monomer, the initiator and the accelerator, respectively, which were added into aqueous solution of composition: water/AM/APS/TEMED = 60 g/15 g/0.03 g 48 uL to form a solution for in stu free-radical polymerization, The solution was stirred for 5 min until al the chemical reagents were dissolved. The tap water was used to prepare the mixture, The raw ‘materials of cement, FAC and silica fume were fist mixed in the mixer for two minutes followed by adding the PAM solution for ‘mixing another three minutes. During mixing the slurry, SP was gently added (0 the mixture to adjust the flowability and the flowability was remained at around 220 mm. The freshly mixed slurry was poured into the steel molds and ‘compacted on a vibration table. Cubes with a length of 40 mm, prisms with a size of 40 mm x 40 mm « 160 mm andl slabs with size of 150 mm x 150 mm x 30 mm were cast for compressive Strength, flexural strength, and thermal conductivity tests, respec- tively, The samples were covered with a plastic membrane after ‘casting and then demolded after 24 h. After that, the composites were cured in a moist room with relative humidity 295% and tem- perature 20 +1. 2.2. Test methods 22.1. Mechanical tests Compressive strength was measured at 7 and 28 days by using MTS (300 kN capacity) with a loading rate of 1 mm/min. The elastic ‘modulus was calculated based on ACI 318M-08 [26] and the for- ‘mula is presented in the following Ea, (1) F = We' oa ViFe a ‘where Es the elastic modulus (MPa). Weis the 28-day density of concrete (kg/m), isthe modification factor (2. = 0.75), and fe is the 28-day compressive strength (MPa}. ‘The flexural strength was determined by three-point bending test using the MTS (50 kN), where the span length ofthe sample is 100 mm and the loading rate is .01 mm/s. Then, the corre- sponding stress was calculated using Eq, (2): Tablet Chemical compositions of ements Fe and FAC a0 135 Ao 432 304 50, 2019 78 ease Ko 039 080 148 Go 552 35 2 Feo 307 ‘05 27(tiv ea /Comsracton and ung Meter 250 (2020) 118523 3 == Fly ash conosphere = sia fume Percent passing (%) 200 300 Particle size (ym) ‘400600 Fig 1 Patil sizeastbuions of fy ash cenospheres and sea fume. 3AL Bon? Where o isthe stress (MPa), Fis the ultimate load (N), Lis the span length (mm), bis the width ofthe beam (mm), and his the height of samples (mm). . @ 2.22. Thermal conductivity test ‘The transient plane source (TPS) method was adopted to deter- ‘mine the chetmal properties of the specimens by using DRE-2C thermal conductivity coefficient tester. The apparatus with a mea- surement accuracy of less than 5% can measure the thermal con- ductivity ranging from 0.01 W[mk to 100 WimK. In this method, the probe was manufactured by continuous double spiraled nickel ‘metal as shown in Fig. 2a and it acts as the heating source and the temperature sensor. When testing the samples, the probe was tightly sandwiched between two samples (Fig 2b). Then, the curves for time and temperature could be obtained. The thermal conductivity coefficient is calculated using the following Ea. (3) a, ao an! ain Where 7 is the thermal conductivity coefficient, q is the heating power and ¢is the time for testing Specimens with a size of 150 mm x 150 mm x 30 mm were applied to do the thermal conductivity measurements. Before the testing, samples were dried at 60 in a convection oven until a Constant weight was reached and cooled down to the ambient temperature in a sealed box to prevent water absorption after- ‘wards. The thermal conductivity coefficient was the average value for six ULCC samples. 8 223. Capillary water absorption test Cubes with a size of 40 mm were employed to do the water absorption test. The specimens were firstly dried in a ventilated (a) Fig. 2 The transiot plane source (TPs) meted fr thermal propertis measure meat (2) 7 Sensor: (thea eondoctiviy coefficient esting ‘oven at 60 C until the weight was measured to be constant. After that, the samples were taken out of the oven and cooled down in the sealed receptacte at ambient temperatuee for 24 h. Afterwards, four sides of the oven-dried samples were sealed with paraffin except for the bottom and top surfaces. Then, the cubes were put {in touch with water. In this way, there is no free water in the pores, ‘which guarantees that water can enter the samples in ane dimen sion, The samples were taken out and wiped off the water adhering, (on the bottom surface atthe contact time of 05h, 1,2h, 4, 8h, 12h, 24 h, 48 h, 3 d, and 7 d to measure the mass of water uptake [27.28}, After that, the capillary water absorption profiles can be ‘drawn with the variation of the square root of time and the capil- lary absorption coefficient can be obtained by fitting the curves of ‘water absorption (the first 24 h). 2.24, Microstructural characterization ‘The microstructures of the specimens were characterized by scanning electron microscopic (SEM) equipped with the Energy Dispersive X-ray Spectroscopy (EDS). The fragments of the tested cubes were collected and immersed in ethanol to suspend the ‘cement hydration before SEM imaging. The samples cured for 28 days were ground to powder and dried at 60 C in an oven for Fourier transform infrared spectrometer (FTIR) testing and thermo- gravimetric analysis (TGA), respectively. 22.5. Mercury intrusion porosimetry ‘The pore size distribution and otal porosity of the specimens ‘were measured by mercury intrusion porosimetry (MIP). Before MIP examination, the ULCC samples were soaked in anhydrous alcohol at 28 days to terminate the cement hydration reactions fol- lowing by dying them at 60'C in an oven until a constant weight ‘was achieved. 3. Results and discussion 3.1, Physico-mechanical properties “The densities for ULCC mixtures tested are listed in Table 3. The fresh density, 1-day density, 28-day density, and oven dry density Mix propotion of ULEC (by weight Kl?) MixiD Cement Sica tune Water FAC PAN (8) n0 50 0 350 350 ° a 430 50 330 350 3 a5 450 50 350 350 5 a 450 50 350 350 7 The PAN coment he porcntage ofthe binding mates cement» ies ame).4 tiv et ol /Consction and Buding Material 250 (200) 115525 Denes of nts Mind Fresh density i) 1 day density el) 28 day density ain”) “Oven dey density Cain) a 115 126 1250, too x 1358 1s ur 00s *s 120 1198, 157 295 a 134 230 1a 1 were determined in this work. It is notable that the 28-day density ranges from 1248 kg/m? to 1285 kg/m: as the content of PAM var- ies from 0 to 7%, The oven dry density is around 1000 kg/m’, where the lightest one is 981 kg/m’, which can be classified as ultra- lightweight concrete [29]. Nevertheless, the introduction of PAM has a limited influence on reducing the density of the mixtures. ‘The profiles of mechanical strength development against the concentration of PAM for ULCC are exhibited in Fig, 3. AS seen in Fig. 38, it is apparent that the compressive strength displays a decreasing trend with the rise of PAM content. However, the com- pressive strength reduces slightly when the content of PAM is below 3%, followed by a drastic reduction with the content of PAM exceeding 5%. Incorporating 1% PAM to the ULCC, the 28-d compressive strength is only about 3% lower than the control mix- ture, indicating that adding an appropriate amount of PAM has barely side effect on the compressive strength. As the content of PAM increases to 5%, the compressive strength of samples is 19.73 MPa at 28 days, which is much lower than the reference mix- ture with 28-d compressive of 35.75 MPa. The decrease of com- pressive strength with the addition of PAM can be ascribed to the softness nature of the PAM and the agglomeration of the AM chains, which becomes the defects thatthe stress and cracks can easily propagate along with. ‘The effect of the PAM on the flexural strength at varied dosage is shown in Fig. 3. The flexural strength shows an ascending trend a the concentration of PAM grows from 0 to 3% followed by a tremendous reduction after the content of PAM surpasses 3%. Spec- mens with 3% PAM have the largest 28-day flexural strength of 4.58 MPa, which is about two times larger than the control mixture (2:35 MPa). The flexural strength value for specimens with 1% PAM is the lowest in PAM-modified ULCC at 28 days, however, itis stil 30% higher than the plane mixture. The chemical interaction between PAM and metal cations such as Ca” and AD” from cement hydration is responsible for the improvement of the flexural strength, resulting inthe formation ofan interpenetrating network with FAC embedded. On the other hand, the PAM covers onto the hydrated products to form the flexible polymer film, which offers AQ AL OAS OAS AP Mixture improvement for the flexural strength, adhesion, and! microstruc- ture, The existence of this polymer film bridges the micro- fractures in the composites and prevents the micro-crack propagation among the cement matrix. PAM also has the filling and reinforceable effects on the composites and it fills the pores, ‘acts as reinforcement that improves intemal flexural strength ‘and adhesion strength [30,31]. In addition, the bonding strength, between cement and FAC is enhanced with the introduction of PAM, which is due to the reduction of Ca(OH)» concentration at the interfacial transition zone (ITZ) between cement matrix and FAC that condenses the ITZ 32]. The existence of the polymer also changes the size and spatial distribution of Ca(OH), crystals at the Tz, resulting in improving the ITZ’s performances. Moreover, the hydration products and the FAC are connected by the polymer film adhering around the FAC, limiting the propagation of eracks along, the ITZ. As a result, the flexural strength is significantly reinforced. ‘The content of PAM is presenting in ascending order so that the effect of the PAM content increase on the modulus of elasticity is presented in Fig. 4a. The elastic modulus of the ULCC reveals a descending trend as the content of PAM increases. The addition of 1 and 3% PAM slightly impairs the elastic modulus compared to the blank mixture, demonstrating that adding a small amount of PAM has limited side effects on the modulus of elasticity. How- ever, the elastic modulus drops deeply when the dosage of PAM reaches 5%, which has the same trend of variation as the flexural strength. The reduction of elastic modulus results from the lower stifiness and higher flexibility of PAM, leading to reducing the overall stiffness of the composite's matrix. ‘The strain capacity of ULCC is displayed in Fig. 4b. As we all know, the strain capacity describes the deformation capacity of cementitious materials. It is apparent that the strain capacity of PAM-modified ULCC is larger than the blank mixture except for the mixtures with 1% PAM. The largest strain capacity appears in {A3, which is about 37% higher than the control mixture and the mixture AS has the similar strain capacity with A3. The results demonstrate thatthe introduction of PAM can rematkably improve the toughness of these materials, which is attributed to the high ao ALAS ASAT Mixture Fig. 2. Mechanical strength with vation of PAM content (2 comprstve strength; (b) flexural strength,(tiv ea /Comsracton and ung Meter 250 (2020) 118523 5 (an é & 3 i ao AT AS ASAT Mixture (b) 07 06 MAL OAR OAS AT Mixture Fig 4. (a) laste modulus versus content of PAM: (b) ram capacity of UICC flexibility of polymers and the intense interaction between hhydrated products and polymers. The improvement of tougiiness for specimens with PAM indicates that the samples can absorb 'more energy and endure greater external loads ‘The specific strength is an important property that can be used to evaluate the mechanical performance of lightweight concrete Herein, the ratio of 28-day flexural strength and 28-day density is denoted as the specific strength, as illustrated in Fig. 9. The specific strength of samples with PAM is larger than the control ‘mixture as the concentration of PAM varies from 1% to 7%, where the highest specific strength is 3.67 which means that this mixture (A3) is equivalent in strength to an ordinary concrete (with a den- sity of 2400 kg/m’) owning flexural strength of 8.8 MPa that ‘demonstrates the normal level of mechanical properties, 3.2. Thermal conductivity ‘The thermal conductivity measured by the TPS method is plot- ted against the content of PAM in Fig. 6. The thermal conductivity ‘of construction materials isthe ability to conduct heat. which is an essential property for lightweight concrete. As the growth of the PAM content, the thermal conductivity of ULCC exhibits a slightly decreasing trend, The thermal conductivity of samples with 7% PAM is more than 6% lower than the control mixture. It is also apparent thatthe thermal conductivity goes down with the reduc- ton ofthe density for ULCC. The lower thermal conductivity of the ‘composites isnot only due to the hollow strueture of FAC that has [AU Sar AN Se EASSEISEAS SCAT: Mixture Fig 5. Specie strength of ULCC high heat-insulation capacity, but also due to the relatively low thermal conductivity of PAM [33]. Hence, the improvement of the thermal conductivity is conducive to the application of these composites in sustainable structures, which contributes to reduc- ing energy consumption. 2.3, Microstructures Fig. 7 illustrates the microstructures of the samples with and without PAM addition, The hydrated products of the blank com- posite have distinct corners and edges and the surface of the hydrated products is coarse (Fig. 7a). With the incorporation of PAM, the internal structure of the lightweight composite seems a gel-based material, where the morphology of hydrated products is blurry and they have unclear edges and comers in comparison to the control mixture (Fig. 7b). It is obvious that the needle- shaped etttingite and caleium hydroxide crystal are covered with the polymer film formed by the fluctuation of PAM and its chem ‘al reaction with metallic cations [32], This polymer film covers and wraps onto the cement particles and hydrated products to form an interweaving network structure, which results in the enhancement of the entirety for the matrix. The formation of the interweaving network structure conduces to improve the flexural strength and toughness of the specimens. What's more, the poly- ‘mer film overlaid onto the hydrated products with higher flexibil ity and deformability leads to higher absorption of energy when 035 1020 2 ‘Bo30 es 1010, Z é Zo20 z 1000 & gos 2 é . z e 0 8 Ecos i ooo! = 980, AD SAL AS TAS GAT Mixture Fie 6 losin basen tema cnt and deity of UCC The column and the pointtine curve are the thermal conductivity and. density, respectively (For interpretation ofthe references to aur inthis ie ese the reader eelerred tthe web weston oft ste)6 tiv et ol /Consction and Buding Material 250 (200) 115525 Fig 7. SEM images of UCC (a) composites without PANE (b) composites with 3 PAM: (cand) are the eistrbution of Cand clemensin the composites obtained rom the EDS mapping carrying the payload. The EDS mapping of C and N demonstrates that the hydrated products are covered by the polymer film and the polymer is evenly distributed in the composites, as shown in Fig. 7, 34, Interactions between PAM and cement hydration products ‘The FTIR results ofthe pure PAM, the plain composite (AO) and the PAM-modified composite (A3) are shown in Fig. 8. As for pure PAM, the wavenumber at 1659 em 1 isthe stretching vibration of CoO of the ~CO-NHt group [34]. The N-H deformation is observed at 1610 cm * and the band at 1412 cm "is assigned to the vibra- tion of C-N, The peak at 1129 cm is related to the NHs in-plane rocking vibration [35], There are some new bands that appeared in the specimen with PAM in comparison to the conttol specimen. The changes inthe band at 1643 cm ! can be ascribed tothe inter~ action between PAM and the ettringite phase produced from — PAM X 697% 29 16597 8 tat? Th ‘Transmittance (%) 38003000” 2500 2000” 1800 Wavenumber (em) 1000 500 Fig TR speceum of UICC cement hydration [36]. A new band at 1420 cm’ of A3 is due to the stretching, vibration of C-N from PAM, which is absent in the neat sample. The N-H characteristic band at 1129 cm” in PAM shifts to 1120 cm * in A3, confieming the formation of some new bonds between PAM and cement hydration products. The absorp- tion band of $0; moves from 522.cm * inthe unhydrated cement 0471 cm illustrating the hydration of ate and the formation of, C-S-H gel [37), The absorption peak of SO% at 471 cm * in the plain mixture moves toward a high wavenumber (479 cm *) with the introduction of PAM, which indicates the interaction of PAM ‘with the C-5-H phases. These interactions between hydrated prod Ucts and PAM are favorable for enhancing the flexural strength, providing the toughness and reinforcing the bonding strength of uiec, 3.5. Thermal stability The profiles of weight loss against the temperature and content of calcium hydroxide (CH) against the PAM content are plotted in Fig. 9 As can be seen from Fig. 9a, the decomposition of portlandite and C-S-H is affected with the increase of PAM content. The mass Toss curves ranging from 600 °C to 800 C approach to the x-axis as the polymer concentration increases, which indicates that there is more decomposition of hydration products. In the temperature range of 600-800 °C, carbonate phases decompose, and it corre- lates to an increasing polymer content, The decomposition temper- ‘ature of CH shifts (0 the let in comparison to the blank mixture, Which means that the addition of PAM results in the degradation of the thermal stability in the composite. In order to quantita- tively evaluate the change of CH content with the incorporation of PAM, TGA is employed to determine the total CH [38]. The amount of CH was calculated from TGA curves by the following Eq. (4): MWor cH%) WW Meu 4(tiv ea /Comsracton and ung Meter 250 (2020) 118523 7 (ay ( Weight bss 6) Temperature *C) ‘The content of CH (%) ) 10 «| 6 aD AL ASAT Fg 8.) Weight los curves fr samples afer 28 caring (b) calcium hydroxide (CH) content versus concentration of PAN ‘where Ml) isthe weight loss of CH, and MWe and MW20 are the relative molecular weights of CH and water, respectively [39]. It is also clearly seen thatthe content of CH is reduced as the content ‘of PAM varying from 0 to 7% (Fig. 9b}. The content of CH inthe ref= ference mixture is 9.33%, which is about 47% larger than the mixture {AL with the CH content of 6.62%. PAM can chemically react with CCa** formed from cement hydration, resulting in the reduction of (CH content and the concentration of CH crystal 40). Part of the PAM hydrolyzes to produce carboxyl groups that react with Ca? {0 form ionic compounds of COO-Ca-O0C and HO-Ca-00C [32 ‘The chemical reaction between PAM and Ca2* contebutes to the enhancement of the flexural strength and limits the formation land dissemination of micro-cracks when catrying load, which improves the mechanical performances of the composites, 3.6, Pore structure The pore size distribution and total porasity of the ULCC mi tures are displayed in Fig. 10. The most probable diameters shift towards finer pore sizes with the increase of PAM followed by ‘moving to coarser pore sizes when the PAM dosage varies from 3% to7% (Fig. 10a)-This variation may be attributed to the fact that the samples are dried before doing the MIP test leading tothe des- ication of PAM in the composites, which enlarges the pore size. In fact, the addition of PAM contributes to the refinement of the pore structure of ULCC. The total porosity is reduced with the incorpo- tation of PAM as shown in Fig. 10b. As the PAM content is increased from 0 to 3%, the total porosity is decreased from 49.74% to 46.38%, The reduction in total porosity may be ascribed to the fact that the (a) vor ou T Pore ameter (um) o ppores in the composites are blacked and filled by PAM. Although the total porosity goes up fractionally with 5% and 7% addition of PAM, it is stil lower than the control mixture. Te slight increase in the total porosity of samples with 5% and 7% PAM can be atrib- ‘uted to the fact that the air voids in the cement composites are padded with polymer and when the samples are dried to do the ‘MIP tests, the water retained in the polymer is evaporated, leading to the shrinkage of the polymer, which leaves the empty air voids inthe composites. 3.7, Water absorption ‘The profiles of water absorption against the square root of time nd capillary absorption coefficient against the content of PAM for the ULC are presented in Fig. 11a and 11b, respectively. The amount of water absorption initially increases with the time goes by, and then tends to be flat when the specimens are contacted with water for more than 72 h (Fig. 11a). However, the amount ‘of water absorption shows a descending trend as the content of PAM increases from 0 to 7% under the same exposure time. Mix- tures containing 5% and 7% PAM have the water absorption of 2.35 kg/m? and 0.44 kg/m? at the contact time of 24 h, which are approximately 72% and 95% lower than the blank mixture (AO), respectively. The reduction of water uptake indicates that the water resistance of ULCC can be significantly improved by intro- ‘ducing PAM. With the addition of PAM, the pores in the composites ‘an be filled or sealed by the polymer. On the other hand, the pro- tective coating created by PAM covers on the surface of hydrated products, resulting in the densification of the inner structure and ()., & z : 2, ast Mistere Fi 10, () Poe sze distribution; () ol prot,® tiv et ol /Consction and Buding Material 250 (200) 115525 Time") S 1 16 1 a 10 | oo) Content of PAM (%) lary sharpton event Ce Fig. 1, Water resistance of ULC: (a) amount of water sbsorion: (6) cailary wate absorption coin the reduction of water absorption [41]. Moreover, the PAM poly- mer in the composites can take in water rapidly and then swell, leading to blocking the pores. Fig. 11b shows the capillarity coefficient of ULCC against the content of PAM, where the capillaity coefficient was obtained by fitting the water absorption profile from 0 to 24 h. As can be seen, the water absorption coefficient decreases sharply as the content ‘of PAM increases and it shows a fairly linear trend with a correla tion coefficient of 0.96. The capillary water absorption coeflicent for specimens with 5% PAM is roughly 73% lower than that of the reference mixture, This demonstrates that the incorporation of PAM enhances the ability of water resistance for ULCC and further boosts the capacity of resisting aggressive substances, which beneficial to improving the durability and extending the service life of ULCe. 4. Conclusions This study aims to develop the ultra-lightweight cement com: posites with good mechanical properties, low thermal conduct ity, and great water resistance by adding PAM fabricated by in- situ polymerization. Based on the experimental result, the follow ing conclusions ean be drawn: 1. There is a slight decrease in compressive strength with the addition of 1% and 3% PAM in comparison to the control mix. ‘The elastic modulus of the composites decreases with increas- ing usage of PAM (1-73). 2, The flexural strength presents a pronounced increase as the PAM content ranges from 1 to 7% for the samples, while the ‘optimum ratio of PAM is determined by 3%, Similarly, the toughness of the mixtures is also improved tremendously due to the high flexibility of PAM. 3. The polymer covered onto the hydrated cement results in the formation of the continuous reinforcing network, which enhances the strength ofthe hydrated product. The filing effect, of PAM contributes to the decrease of porosity. Compasites with PAM are found to be more water resistant as compared to the blank mixture. (CRediT authorship contribution statement Qing Liu: Writing - original draft, Wenjie Liu: Data curation. Zongjin Li: Funding acquisition. Siyao Guo: Writing - review & ‘editing. Guoxing Sun: Supervision, Writing - review & editing Declaration of Competing Interest ‘The authors declare that they have no known competing finan- ial interests or personal relationships that could have appeared to influence the work reported in this paper. Acknowledgements This work was funded by The Science and Technology Develop- ment Fund, Macau SAR (File no. 0083/2018/A2); Multi-Year Research Grant (File no. MYRG2019-00135-IAPME), Research & Development Grant for Chair Professor (File no. CPG2020-00002- TAPME), and Start-up Research Grant (File no. SRG2017-00093- IAPME) fom University of Macau, Macau SAR, China. 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