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                                 The pore structure is one of the most significant characteristics of cementitious materials, and it has major
                                 impacts on both mechanical p     roperties1–4 and d
                                                                                     urability5–7. The pore structures of cementitious materials deter-
                                 mine important properties such as s trength3,8, permeability9,10, and s hrinkage11,12. Cement-based materials with
                                 the same total porosity may also exhibit different properties. Therefore, it is important to investigate the porosity
                                 size distributions of cementitious materials to explain their properties.
                                     Pore sizes, arrangements, and connections in cement-based materials are random and include gel pores (the
                                 interlayer pores in cement hydration produce calcium-silicate-hydrate gels), capillary pores, and air v oids13.
                                 The pore distributions of cementitious materials are extremely complex because of the wide range and random
                                 distribution of pore s izes14. MIP is commonly used to investigate the pore structures of cementitious materi-
                                 als and is also one of the most widely used methods. The total porosity, pore size distribution, and density of a
                                 cementitious material can be obtained by MIP. The pores in cementitious materials are formed during hydra-
                                 tion in the cement, and they mainly comprise two types of p         ores1,15: (a) gel pores, with sizes ranging from 0.5
                                 to 10 nm, are mainly related to the cement hydration process and do not have a major impact on the strength
                                 of cementitious materials but have greater effects on the shrinkage and creep of the material; (b) capillary pores
                                 with sizes distributed primarily from 10 to 10,000 nm are strongly associated with the strength of a cementitious
                                 material, which is generally determined by the water-to-cement ratio of the material.
                                     With the rapid developments occurring in the field of construction materials, synthetic polymer latexes, such
                                 as epoxy resin latex in cementitious material systems, have been used in many projects16–19. Polymer-modified
                                 cement mortar (PMM) is commonly used to enhance the physical properties and durabilities of structures
                                 1
                                  Department of Harbor, Waterway, and Coastal Engineering, Chongqing Jiaotong University, Chongqing 400074,
                                 China. 2State Key Laboratory of Hydroscience and Engineering, Tsinghua University, Beijing 100084,
                                 China. 3Geotechnical Engineering Department, Nanjing Hydraulic Research Institute, Nanjing 210024,
                                 China. 4Huaneng Tibet Hydropower Safety Engineering Technology Research Center, China Huaneng Group Co.,
                                 Ltd., Beijing 100031, China. *email: anxue@mail.tsinghua.edu.cn
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                                            Chemical component    CaO     SiO2   Fe2O3   Al2O3   SO3   MgO    K2O    TiO2    BaO     SrO     Na2O
                                            Content (wt.%)        69.42   14.7   4.21    3.67    3.2   1.55   1.42   0.597   0.489   0.265   0.184
                                           because the reticulated film structure in the PMM can improve the pore structure20–23. Ordinary mortars have
                                           relatively more p  ores24. However, PMM fills the pores created during hydration of the cement by forming a
                                           polymer film in the mortar s ystem25. As a result, PMMs based on various synthetic polymeric latexes are already
                                           being applied in the construction industry. Generally, the porosity and pore size distribution of the PMM system
                                           need to be considered when investigating the mechanical properties and durability of the m  aterial26. The physical
                                           properties and durability of ordinary cementitious materials are affected by pore structure parameters such as
                                           porosity and pore size distribution. However, the pore structure parameters of PMM materials may affect the
                                           mechanical properties and the durability of the material more than any other characteristic27. Therefore, the
                                           strengths, durabilities, and permeabilities of PMMs are strongly impacted by their pore structure parameters,
                                           such as porosities and pore size d istributions28,29.
                                               The microstructures of PMMs reported in the literature are mainly described by porosity and pore structure
                                           distribution. Then, the relationships between pore structure parameters and macroscopic properties are estab-
                                           lished to guide the application of PMMs in practical engineering. However, there are few accurate simulations
                                           of the pore structures of PMMs. The use of mathematical models to accurately describe the pore structure dis-
                                           tribution has important implications for studies of PMM microstructures. Additionally, accurate descriptions
                                           of the pore structure and predictions of void structure parameters are important to promote the design of PMM
                                           mixtures. In view of the above, the pore structure parameters of PMMs obtained through MIP experiments, such
                                           as porosity and pore size distribution, can be used to investigate the relationships between polymer addition and
                                           pore structure distributions of cement mortars. This paper investigates the effects of different polymer-cement
                                           ratios and curing ages on the pore size structures of epoxy latex-modified cement mortars. MIP was used to
                                           obtain the pore structure changes of the specimens. The pore size distributions of epoxy latex-modified mortars
                                           were simulated with a compound log-normal distribution model. The model results were also compared with
                                           the test results of this study.
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Figure 2. Particle size distribution curve for the quartz sand used in this investigation.
                                 Specimen preparation. Previous studies showed that polymer-to-cement ratios of 5–15% were optimal
                                 for preparation of epoxy latex-modified mortars20,27. In our previous research30,31, we found that the compressive
                                 strengths of epoxy-modified mortars tended to decrease and the flexural strengths of epoxy-modified mortars
                                 tended to increase with increasing epoxy latex content. Therefore, epoxy resin-to-cement ratios of 0, 5%, 10%,
                                 15%, and 20% were chosen to investigate the effects of the various contents of epoxy latex. The volumetric water-
                                 to-cement ratios of all mortar specimens were kept at 1.10. The cement-to-sand volume ratio was maintained
                                 at 1.00 for all specimens. Referring to the provisions of JC/T 986-201832, all mortars were adjusted to exhibit a
                                 flowability of 200–210 mm by adding superplasticizers. The superplasticizer used has been applied in many pre-
                                 vious studies33–38. Table 2 shows the mixing ratios for the materials in the epoxy latex-modified mortar. Further-
                                 more, the P/C of the modified mortar indicates the dry epoxy resin-to-cement ratio of mass. The prepared epoxy
                                 emulsion-modified mortar was cast in square molds with dimensions of 70.7 mm. All specimens were cured at
                                 100% RH and 20 °C for 1 day and then demolded. Then, the specimens were cured in a standard maintenance
                                 (60 ± 5% RH, 20 ± 1 °C) chamber for 7, 14, 28, or 90 days.
                                 Experimental tests.         Mercury intrusion porosimetry (MIP). The MIP test is one of the most widespread
                                 methods used to investigate pore size distributions of cementitious materials. It provides accessible information,
                                 such as total pore volume, density, and pore size distribution for the cementitious material. MIP is very simple
                                 in principle. It is based on the physical principle that the applied pressure determines the extent of mercury
                                 intrusion into a porous medium. In the MIP experiment, the prepared sample is put into a chamber filled with
                                 mercury, and then the pressure applied to the mercury is steadily raised. With increasing pressure applied to
                                 the mercury, the volume of mercury pressed into the pores of the specimen also increases. To fill a pore with a
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                                                Table 2.  Mix proportions for epoxy latex-modified mortars (kg/m3). C, S, W, ER, and H are the quantities of
                                                cement, quartz sand, water, dry epoxy resin, and dry hardener, respectively.
                                                diameter d with a nonwetting fluid, a pressure P that is inversely proportional to the diameter of that pore must
                                                be applied39. The Washburn equation, as shown below, can be utilized to express the association between applied
                                                pressure and pore size40:
                                                                                                         −4γ cos ϕ
                                                                                                    D=                                                            (1)
                                                                                                            P
                                                where P = the absolute pressure applied; φ = the contact angle of the sample and mercury (132° used here); γ = the
                                                surface tension of mercury; and D = the diameter of the intruded cylinder.
                                                    MIP tests were performed herein on a Micromeritics Poresizer AutoPore IV 9500 instrument with a maximum
                                                intrusion pressure of 61,000 psi (420 MPa). The pores of two different specimens were tested, and average values
                                                were calculated for the test results. If the results of the two tests differed by more than 5%, it may have been due
                                                to experimental error, and a third specimen was tested.
                                                Scanning electron microscopy (SEM). SEM was conducted to obtain a clearer perspective on the microscopic
                                                effects of epoxy latex on cement mortar. The samples were immersed in absolute ethanol for 24 h to terminate
                                                hydration of cement and when the mortar specimens reached the ages of 7, 14, 28, or 90 days of maintenance.
                                                After drying the samples, SEM was conducted directly.
                                                Compound log‑normal distribution for pore size distributions. According to previous studies42,
                                                the pore size distribution determined by MIP can be simulated with a mixture of log-normal or composite log-
                                                normal distributions. It was found that the pore distributions of cement paste and mortar were well simulated by
                                                the composite log-normal distribution.
                                                   When a variable x (0 < x < ∞) meets the log-normal distribution, the function y = lnx is normally distributed.
                                                The probability density function is shown as follows:
                                                                                                                          
                                                                                                              1 ln x − µ 2
                                                                                                                
                                                                                                1
                                                                                   p(x) = √            exp −                                                  (2)
                                                                                              2πσ 2 x         2      2
                                                where x is a variation, μ is defined as the location parameter, and σ is the shape parameter. In the log-normal
                                                distribution model, there are several relevant characteristics, as follows:
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                                 Figure 4.  Relationship between the cumulative pore size distribution and P/C ratio of epoxy latex-modified
                                 mortar at different ages, (a) 7, (b) 14, (c) 28, and (d) 90 days.
                                     Generally, the hydration process for cement can be considered a process of dividing the voids of the cement
                                  system or the spaces between particles in the cement system. In the early stages of hydration, there are large
                                  voids in the cement paste system, i.e., voids between cement particles. As curing progresses, the cement particles
                                  are connected by cement hydration products. Therefore, the large voids in the cement paste system are divided
                                  into smaller pores. This suggests a physical basis for the log-normal model of pore size distribution in cement
                                 systems42.
                                     The probability density function of the composite log-normal distributions model is shown as follows:
                                                              p(x) = f1 p(x, µ1 , σ1 ) + f2 p(x, µ2 , σ2 ) + f3 p(x, µ3 , σ3 )                  (8)
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                                           Figure 5.  Pore volume distribution of epoxy latex-modified mortar with pore classifications at (a) 7, (b) 14, (c)
                                           28, and (d) 90 days.
                                                                                               3
                                                                                               
                                                                                                      fi = 1                                               (9)
                                                                                                i=1
                                           where μi = the location parameter, σi = the shape parameter, fi = the weight coefficient, and p(x, μi, σi) = the ith
                                           log-normal subdistribution. Research showed that if two or more log-normal distributions explained an attribute
                                           of a system, it is likely that there were multiple distinct response processes occurring in that system43. This may
                                           indicate that the different size ranges of pores in cementitious materials had different sources and generation
                                           mechanisms.
                                               The method for modeling pore size distributions in this study was obtained from a group of cumulative prob-
                                           ability data. The relationship between P(x) and x is shown in Fig. 6. In this investigation, x = the pore diameter
                                           and P(x) = the ratio of the volume of the cumulative pore to the total pore determined by MIP tests. In general,
                                           the distribution model and the initial values of the parameters are frequently determined by graphical analysis.
                                           This graphical approach first requires the logarithmic transformation of x to obtain lnx. Then, the standard
                                           normal distribution table is used to determine the quantiles of N(0,1) determined by P(x). For instance, if the
                                           cumulative percentage is 80%, the corresponding quantile is 0.86. With lnx as the vertical axis and the quantiles
                                           of N(0,1) as the horizontal axis, if the curve of lnx versus quantiles of N(0,1) is linear in shape, then x can be
                                           considered to obey a single log-normal distribution.
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Figure 6. Cumulative pore volumes in epoxy latex-modified mortars hydrated in P/C = 5% for 90 days.
Figure 7. Plot of lnx versus the quartiles of N(0,1) obtained based on the data in Fig. 6.
                                     The curves for plots of lnx versus the quantiles calculated from the MIP data for epoxy latex-modified mortar
                                 specimens are shown in Fig. 7. Notably, the curves comprised three straight line segments. As shown in Fig. 8,
                                 the slope and intercept of the straight line represented the location (μi) and shape (σi) parameters of the corre-
                                 sponding subdistribution, respectively. The horizontal axis at the intersection points of adjacent line segments
                                 determined the weighting factor. As shown in Fig. 8, the first segment of the line intersected the second segment
                                 at quantile − 0.91, and the corresponding cumulative probability was identified as 0.18 by consulting the standard
                                 normal distribution table. Thus, f1 = 0.18.
                                     The test results for epoxy latex-modified mortars of different ages were compared with the results from the
                                 distribution fitted using the χ2 fitting technique. It is well known that the χ2 test is one of the important indica-
                                 tors used to evaluate whether the fitted data are good or not. This method for evaluating the goodness of fit is
                                 as follows:
                                                                                        k
                                                                                         (Oi − Ei )2
                                                                                χ02 =                                                             (10)
                                                                                                Ei
                                                                                        i=1
                                 where χ2 = the test statistic, k = the number of bins, Oi = the observed frequencies, and Ei = the expected frequen-
                                 cies. The most appropriate distribution is obtained by adjusting the initially predicted distribution parameters of
                                 the model to obtain the smallest possible test statistic. Subsequently, the critical values of χα,k−β−1
                                                                                                                                 2       with k − β − 1
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Figure 8. Initial prediction parameter acquisition method for the composite log-normal distribution.
                                           Table 3.  Compound log-normal distribution parameters for the pore size distributions of epoxy latex-
                                           modified mortars.
                                           degrees of freedom are calculated. The α-error is considered to be 0.05. If χ02 > χα,k−β−1
                                                                                                                                   2       , the hypothesis that
                                           the pore size data for the epoxy latex-modified mortar followed a compound log-normal distribution should
                                           be rejected.
                                               Table 3 and Fig. 9 indicate the differences in pore size distribution between the model and experimental
                                           results. For all mortars, the inequalities χ02 < χα,k−β−1
                                                                                              2        were satisfied, and their correlation coefficients were
                                           close to 1. As shown in Fig. 9, the experimental data for the pore size distribution of epoxy latex modified mortar
                                           were in excellent agreement with the model curves obtained. Therefore, the composite log-normal distribution
                                           used in this study predicted the cumulative pore size distribution curves of epoxy latex-modified mortars with
                                           different P/C ratios effectively.
                                           Pore parameters of epoxy latex‑modified mortars. The composite model with three log-normal dis-
                                           tributions may provide considerable information on the origins and formation methods for pores of various
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                                 Figure 9.  Relationships between predicted and tested cumulative pore size distributions of epoxy latex-
                                 modified mortars at (a) 7, (b) 14, (c) 28, and (d) 90 days.
                                 sizes. Physically, the size distribution of macropore pores (D > 100 nm) can be described by the first subdistribu-
                                 tion. The size distribution of gel pores (D < 10 nm) can be described by the third subdistribution. The middle
                                 subdistribution represents micropore pores (10 nm ≤ D < 100 nm). Table 3 showed that f2 decreased continu-
                                 ously with increasing P/C ratio. In this case, the micropores in the modified mortar system decreased as the P/C
                                 ratio increased, which is consistent with the results of previous studies30 showing that the proportion of pores
                                 with sizes ranging from 50 to 100 nm tended to increase with increasing polymer dosage. As the P/C ratios
                                 increased from 5 to 20%, the proportion of macropore pores increased, and f3 increased to a small degree; this
                                 can be explained by the fact that some of the micropores were filled by the hardened epoxy. A mass of aggregated
                                 epoxy resin particles adsorbed cement particles, which led to an increase in macropores. This result is consistent
                                 with literature44 indicating that the number of pores (with size ranges 0.1 μm to 1 μm and 10–200 μm) increased
                                 with increasing incorporation of polymer. Adsorption of the epoxy emulsion on cement particles hindered the
                                 hydration process in the mortar system, which resulted in an increased number of gel p         ores30,44.
                                     Figure 10 shows Q-ln plots for epoxy latex-modified mortar samples cured for 90 days. Initial estimates for
                                 the slopes of the three fairly linear segments were designated σ1, σ2, and σ3. Initial estimates for the intercepts of
                                 the three segments were designated μ1, μ2, and μ3, respectively. The two deflection points were the initial estimates
                                 for f1 and f2. It is obvious what the weighing factors f1, f2, and (1- f1- f2) mean. Therefore, it is necessary to investi-
                                 gate the relationships among location parameters, shape parameters and P/C ratios of the epoxy latex-modified
                                 mortar pore structures. As shown in Fig. 10, the linear segments at the ends of the curves were almost parallel to
                                 each other. This indicates that the shape parameters σ1, σ2, and σ3 of the log-normal pore size distributions in the
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Figure 10. Q-ln plots for epoxy latex-modified mortar samples cured for 90 days.
                                           modified mortar systems remained essentially constant as the P/C rate increased. Therefore, in the epoxy latex-
                                           modified mortar system, the shape parameter in the composite log-normal distribution may be related to other
                                           factors. Thus, it is necessary to investigate the relationship between the position parameter and the P/C ratio.
                                           Prediction of the location parameter of epoxy latex‑modified mortar. The location parameter
                                           (μi) relative to the polymer-to-cement ratio (P/C) was studied first. It was found that μ1, μ2, and μ3 may be related
                                           to the epoxy latex. For the same curing age, it was shown that variations in the location parameters with respect
                                           to the P/C ratio were best represented by the relationship µi = a(P/C) + b. A plot of the location parameter
                                           against the P/C ratio is shown in Fig. 11. The regression equation and the corresponding correlation coefficients
                                           are shown in Fig. 11. As shown, the location parameter increased with increases in the P/C ratio. This indicates
                                           that the pore structure of epoxy latex-modified mortar evolved toward large pores as the P/C ratio increased,
                                           which further supports previous fi   ndings45 that increases in the polymer latex percentage increased the total
                                           porosity for a constant water-to-cement ratio. The relationships between the location parameters and the P/C
                                           ratios were linear with correlation coefficients as high as R2 > 0.960.
                                               Furthermore, the values a and b for the linear plots of location versus the curing age are plotted in Fig. 12. It
                                           has been observed that the variations of a and b with age t are best expressed as a relationship of the following
                                           form; a, b = c ln (t) + d , where t is the curing age. The regression equation and the corresponding correlation
                                           coefficients are also shown in Fig. 12. It is interesting to note that the plots of values a and b of the linear func-
                                           tion versus the curing age showed logarithmic relationships with correlation coefficients as high as R2 > 0.980.
                                               As concluded above, Equations a and b were substituted into the equation µi = a(P/C) + b. Accordingly,
                                           the relationships between location parameters (μi) and polymer-to-cement ratios (P/C) and curing age (t) can
                                           be expressed as follows:
                                                                                                       
                                                                                                        P
                                                                          µ1 = (3.815 ln t − 4.881)          + 0.483 ln t − 0.973,
                                                                                                        C
                                                                                                       
                                                                                                        P
                                                                          µ2 = (0.408 ln t + 1.642)          + 0.273 ln t + 2.894,
                                                                                                        C
                                                                                                       
                                                                                                        P
                                                                          µ3 = (0.438 ln t + 1.167)          + 0.272 ln t + 3.412.
                                                                                                        C
                                           Effect of epoxy latex on the microstructure of mortar.                 The microstructures of an ordinary cement
                                           mortar and an epoxy latex-modified mortar are shown in Figs. 13 and 14, respectively. Figure 13 shows that a
                                           large number of plate-like and needle-like products were generated in the normal mortar. These needle-like
                                           ettringite products and plate-like Ca(OH)2 crystals were the main products of cement hydration, and these prod-
                                           ucts interwove to form a dense structure, which contributed to improvements in the pore structures of cementi-
                                           tious materials46. Figure 14 shows that, as with the control mortar, Ca(OH)2 crystals and ettringite products were
                                           formed in the epoxy latex-modified mortar. However, polymer films were observed for the epoxy latex-modified
                                           cement mortar, and these films were beneficial to improving the pore structure of the cement m     ortar21. As seen
                                           from Fig. 14a, when 5% epoxy latex was added to the cement mortar, pores were observed on the surfaces of
                                           the plate-like Ca(OH)2 crystals. As shown in Fig. 14b, at a P/C ratio of 10%, round lumps were formed in the
                                           modified mortar. This may be due to adsorption of cement particles by epoxy aggregates. Figure 14c shows the
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                                 Figure 11.  Relationships between location parameters (μi) and polymer-to-cement ratios (P/C); (a) 7, (b) 14,
                                 (c) 28, and (d) 90 days.
                                 microstructure of an epoxy latex-modified mortar with P/C = 15%. This showed that the round lumps formed by
                                 the epoxy aggregates completely covered the hydration products, which led to generation of more macropores.
                                 As shown in Fig. 14d, when the addition of epoxy latex was increased to 20%, a large number of macropores and
                                 round lumps were formed in the mortar system. More macropores were formed in the modified mortar system
                                 as the amount of epoxy latex added was increased, which was consistent with previous fi ndings27.
                                 Conclusions
                                 This paper investigated the effects of different polymer-to-cement ratios (P/C) and curing ages on the pore size
                                 structures of epoxy latex-modified cement mortars. The following conclusions can be drawn from this research:
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Figure 12. Relationships between the values a and b of a linear function and curing ages, (a) a and (b) b.
Figure 13. SEM images of ordinary cement mortar specimens cured for 28 days.
                                           (1)      With increasing P/C ratios, the proportion of micropores in epoxy latex-modified mortars tended to
                                                    decrease, while the proportion of macropores tended to increase. The addition of epoxy latex hindered the
                                                    hydration process of cement in the mortar system, which led to an increase in the proportion of gel pores.
                                           (2)      The addition of epoxy latex was only associated with the location parameters. The shape parameter in the
                                                    composite log-normal distribution was independent of epoxy doping.
                                           (3)      With increases in the P/C ratio, the epoxy latex-modified mortar developed larger pores.
                                           (4)      A composite logarithmic model was used to describe the pore size distribution of epoxy latex-modified
                                                    mortar. The relationships between pore size distribution location parameters and the polymer-to-cement
                                                    ratio and curing age were also obtained. The analytical methods proposed in this study can be applied in
                                                    other studies of pore size distributions.
                                           (5)      With increases in the amount of epoxy latex added, larger numbers of epoxy groups were formed in the
                                                    modified mortar system, which led to the generation of more macropores.
                                           (6)      From the above test results, polymer to cement ratios ranging from 10 to 15% were considered optimal for
                                                    preparation of such epoxy latex cement mortars.
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                                 Figure 14.  SEM images of modified mortar specimens containing epoxy latex cured for 28 days: (a) P/C = 5%,
                                 (b) P/C = 10%, (c) P/C = 15%, and (d) P/C = 20%.
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                                           Acknowledgements
                                           This research was supported by the Foundation of China Huaneng Research Project [Grant Number HNKJ19-
                                           H13] and Major projects of Chongqing Education Committee [Grant Number KJZD-M201900702].
                                           Author contributions
                                           Conceptualization, P.L. and X.A.; Data curation, L.Z. and S.D.; Funding acquisition, P.L. and C.W.; Investigation,
                                           C.W. and X.H.; Methodology, X.A. and X.H.; Validation, W.L. and L.Z.; Visualization, W.L. and S.D.; Writing–
                                           original draft, P.L. and W.L.; Writing–review & editing, P.L. and X.A.
                                           Competing interests
                                           The authors declare no competing interests.
                                           Additional information
                                           Correspondence and requests for materials should be addressed to X.A.
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