3.1 Mechanical properties of artificial aggregate
The evolution of apparent density, crushing strength, and water absorption of artificial aggregates with different time are shown in Fig. 5. It can be clearly observed that with the presence of microorganisms, the mechanical properties of artificial aggregates (B or B-C group) are better than that of NB or NB-C. As for the group of NB and B (In curing (b) condition), the mechanical properties have a little change with the increase of curing time. As for the group of NB-C and B-C, the value of apparent density and crushing strength gradually increase and then keep stable.
As for NB group, the mechanical properties are improved because during the hardening process of aggregates, the cement hydration products (mainly calcium hydroxide (CH) and calcium silicate hydrates (C-S-H)) were gradually produced (Bye, 1999), which improved the performance of the aggregates. And with adding the microorganisms, the mechanical properties improvement effect is not apparent because of low CO2 concentrate. When cured in the CO2 concentration above 95% ((b) condition), the mechanical properties of artificial aggregates were improved a lot. For example, after curing for 24 h, the apparent density of the NB-C group was 2520 kg/m3, crushing index was 4.4 MPa, and water absorption was 9.7%, while NB of those were 2400 kg/m3, 2.3 MPa, and 11.5% respectively, which was consistent with other studies (Jiang and Ling, 2020). The above phenomenon could be explained by the reaction of calcium hydroxide from WCP/cement hydration and carbon dioxide then produced calcium carbonate with higher elastic modulus. More carbonated productions also compacted the microstructure(Ashraf, 2016; Zhan et al., 2016). Furthermore, the microorganisms show a huge promotion effect in high CO2 concentration. Compared with the NB-C group, the apparent density of aggregates in B-C was 2620 kg/m3 (an increase of 4%), crushing strength was 9.1 MPa (an increase of 106.8%), and water absorption was 4.8% (decrease of 50.5%) after cured 24 hours. Obviously, the presence of microorganisms accelerated the carbonation process, and more carbonated productions change the microstructure of artificial aggregates, which made the strengthening effect more conspicuous.
3.2 3D pore structure of artificial aggregate
X-CT is reviewed as the most advanced non-destructive test methodologies for the evaluation of cement-based materials at the micro-structural level(Lu et al., 2007; Prasad, 2020). The distribution of pores and the connectivity of the pores with respect to their location can be visualized by reconstructing three/two-dimensional sections. The pore structure of 4-types artificial aggregates was investigated by X-ray computed tomography to explore the effect of mineralization by microorganisms. Figure 6 shows the X-CT 3D reconstruction of artificial aggregates, form from blue to red, the defect volume gradually increased. For the NB group, the whole structure showed many properties, with a maximum detect volume of 1.84mm3. After curing 95% CO2 condition (curing (b) condition), it was worth noting that the porosity of NB-C showed an apparently gradient porosity structure. From the edge to the center of the pellet, the colored area gradually became denser, which indicated that the porosity gradually raised. Because the CO2 concentration at the edge was higher than inside. With the increased depth, the concentration of carbon dioxide gradually reduced.
Furthermore, the products generated at the edge hindered the transmission of carbon dioxide, resulting in a slower rate and lower degree of internal carbonation reaction. However, the presence of microorganisms in artificial aggregate increased the CO2 concentration inside. For the B group, the blue-colored area was sparse than the NB group because the microorganism uniformly distributed in the whole aggregate in advance accelerated the capture of CO2. In high CO2 concretion, the microorganism increased the carbonated depth. For the B-C group, gradient structure in a shell of artificial aggregate was not detected, and deeper distances from the surface show less pore. That means microorganisms could make the carbonation reaction more complete and the aggregate structure more uniform.
In X-CT, quantitative analysis on void content and size of pores was determined by obtaining the two-dimensional images as the result of the various intensities with correlation to the material’s density (Seibert and Boone, 2005; Wei et al., 2011). Figure 7 shows the 2D of artificial aggregates, and the black spots were identified as the voids in the cementitious matrix. It can be found that the B-C are denser than other groups, also reflect the improvement of microorganisms on the microstructure of artificial aggregate. Additionally,
3.3 Porosity of artificial aggregate shell
In order to analyze the improvement of microorganisms on porosity of artificial aggregate, the specimens of shell structure were tested by MIP. The porosity content is obtained as the total volume of the mercury intruded into the aggregates pellet to the total volume of the sample was used to accurately analyze the micropores of aggregates ranging from 3 nm to 5000 nm. The integral curves and differential curves of the pore size distribution of artificial aggregates with and without bacteria under different curing conditions are shown in Fig. 8. Formerly, the calculation of the results data is listed in Table 3. It can be found that the porosities of NB and B group are similar, which are 30.45 and 29.78 respectively, indicating that the addition of microorganism would not improve porosity. But the average pore diameter and most probable aperture decreased because mineralization productions originated by microorganisms and WCP/cement filled the pore. However, after cuing in CO2 with a concentration above 95%,it was worth mentioning that the porosity of the B-C group had the most significant decline, which was only 13.88%. Meanwhile, the average pore diameter and most probable diameter also decrease. That can be concluded that the microorganism can significantly modify the micro-pore structure of artificial aggregates. It should be specially pointed out that the most aperture of B was only 9.02 nm, which was classified as harmless pore (ZhongWei, 1979), which was greatly beneficial for aggregates to resist the invasion of foreign harmful substances.
Table 3
Pore structure characteristics of four types of artificial aggregate
Samples
|
Porosity/%
|
Average pore diameter/nm
|
Most probable aperture/nm
|
NB
|
30.45
|
208.45
|
793.12
|
B
|
29.78
|
186.65
|
609.53
|
NB-C
|
20.98
|
41.25
|
348.90
|
B-C
|
13.88
|
12.44
|
9.02
|
3.4 Micro-morphology of carbonated and mineralized products in shell
The artificial aggregates after curing 95% concentration CO2 condition showed better mechanical and denser microstructure. Therefore, the shell parts of artificial aggregates without and with microorganisms (NB-C and B-C groups) were adopted to study the effect of microorganisms by SEM. Figure 9 and Fig. 10 showed the SEM images of micro-morphology of carbonated and mineralized products in the shell, respectively. There were obvious crystal depositions on the surface of the artificial aggregates. From the analysis of the EDS (Fig. 9 (d)), the major elements NB-C are C, Ca, and O, which proves that carbonated products are calcium carbonate. The other products may be calcium silicate hydrate because the detection of tiny Si elements. The crystal morphology of products deposited of NB-C shows mainly ellipsoidal and massive, and relatively sparse. Figure 10(d) also proved the mineralized products are calcium carbonated. Differently, the crystal on the surface shown in Fig. 10(c) was mainly irregular with crisscross growth and denser, which was just the favorable evidence of microbial promoting calcium carbonate deposition.
3.5 Analyze the mechanical of artificial aggregate concrete
The artificial aggregate was replaced by 10%, 30%, 50%, 70% and 100% of natural aggregate to prepare concrete. The apparent density surface of nature and artificial aggregate is 2730 kg/ m3, 2600 kg/m3, and the water absorption of 0.7% and 3.0%. There is a certain gap in the apparent density of both aggregates. The specific mix proportion was calculated based on the volume method. The proportion of various materials with 1 m3 are shown in Table 4.
Table 4
Mix proportion of concrete (kg)
Code
|
Replace ratio/%
|
Cement
|
Water
|
Sand
|
Nature aggregate
|
Artificial aggregate
|
NC
|
0
|
360
|
180
|
640
|
1114
|
0
|
AC-10
|
10
|
360
|
180
|
640
|
1003
|
107
|
AC-30
|
30
|
360
|
180
|
640
|
780
|
321
|
AC-50
|
50
|
360
|
180
|
640
|
557
|
535
|
AC-70
|
70
|
360
|
180
|
640
|
334
|
749
|
A-100
|
100
|
360
|
180
|
640
|
0
|
1070
|
Figure 11 shows the strength of natural aggregate concrete (NC) and artificial aggregate concrete (AC) with a different replacement under curing seven days and 28 days. The compressive strength of NC or AC shows a similar strength-development trend. The compressive strength increases with age, and the strength with curing 7-day can reach above 70% of the 28-day strength. When the replacement rate of artificial aggregate is less than 30%, the compressive strength of AC has little change and slightly increases compared with that of NC. However, when the replacement rate reaches 50%, the compressive strength of concrete reaches NC concrete. When more than 50%, the compressive strengths decrease sharply, with the maximum reduction of 22.4% at AC-100 group. The low replacement rate has little effect on the concrete strength because the water absorption rate of aggregate is higher than that of natural aggregate. Increasing the replacement material within a certain range reduces the effective water-cement ratio of concrete, which reduces the porosity. And in the long-term curing, the moisture absorbed by artificial aggregate will be released to the matrix gradually with the hydration process of concrete cement, which is conducive to the development of strength. In addition, part of the cement slurry is easily attached to the surface micropores of coarse aggregate, making the mosaic structure between aggregate and matrix. However, there is no doubt that the compressive strength of concrete mainly depends on the coarse aggregate. The high replacement rate will inevitably lead to a significant reduction in the strength of concrete due to the low strength of artificial aggregate. Therefore, the artificial aggregate prepared in this study can replace the natural aggregate in a certain proportion to prepare concrete, and the maximum content should be controlled within 50%.
3.6 CO2 fixation of artificial aggregate
The thermogravimetric (TG) and differential thermogravimetric (DTG) curves of artificial aggregates are plotted in Fig. 12. The peaks observed in DTG curve (600 ~ 800℃) were mainly denoted the decomposition of calcium carbonates(Shah et al., 2018). According to Eqs. (2) and (3), CO2 change (ΔCO2) and fixation of artificial aggregate are listed in Table 5. It should be specially pointed out that CO2 fixation in the table refers to the result after deducting the CO2 content of WCP itself (2.34 wt. % detected). The CO2 content in WCP was derived from the absorption of CO2 in the atmosphere by the waste concrete matrix. The CO2 fixation of NB and B groups were similar and less than 1 wt. % due to the low CO2 concentration, indicating that the CO2 fixation ability of is weak. However, under 95% CO2 concentration, the CO2 fixation increase a lot. And with the presence of microorganisms, the CO2 fixation of B-C increase from 7.39 wt. % to 16.00 wt. %, illustrating that microorganism further enhanced the carbon fixation capacity of artificial aggregates under high CO2 concentration. The artificial aggregates mixed with bacteria show great carbon fixation potential. The production of the per-ton artificial aggregate product can fix 160 kg CO2, which has remarkable economic and social significance for the construction industry to reduce carbon footprint.
Table 5
ΔCO2 and CO2 fixation of artificial aggregates (wt. %)
|
NB
|
B
|
NB-C
|
B-C
|
ΔCO2
|
2.52
|
2.98
|
9.06
|
16.81
|
CO2 fixation
|
0.19
|
0.66
|
7.39
|
16.00
|
3.7 Economic and Environmental analysis of artificial aggregate
The production cost of artificial aggregate mainly includes raw material and process cost. The WCP and WACP are parts of waste concrete, by-products produced in the process of crushing and screening of constructions. Therefore, the utilization of solid waste can get government support and government support and preferential policies. According to the relevant tax law of China, the nature aggregate of sand and stone is subject to resource tax of 1% ~ 5%. In addition, 10% of the goods value-added tax is required for production and sales. However, the artificial aggregate produced with construction waste shall be exempted for the sale of self-produced construction aggregates. As a result, the cost and profit are considerable.
The CO2 fixation content of per ton artificial aggregate with adding microorganisms can reach 154.3 kg, calculating based on the CO2 fixation of shell parts with 16.0%. The annual output of waste concrete in China is about 1.5 billion tons in 2020. The WCP reach 10% ~ 20%, above 150 million tons in 2020. If all of them are used to prepare artificial aggregate, about 200 million tons of artificial aggregate can be produced, and 31 million tons of CO2 can be fixed. According to the carbon emission report of “carbonate dioxide emission report of China building materials industry (2020)”, the CO2 emission of building materials industry in 2020 is 1.48 billion tons. The rate of reduction CO2 by produced artificial aggregate can reach 2.09%, which is better for the construction industrial carbon reduction. In the process of production artificial aggregate, it can not only use the waste concrete but also fix CO2 from cement production process. This method can effectively realize the utilization of waste concrete resources, reduce the exploitation of natural aggregate, and reduce concrete carbon emissions in the whole life cycle, which provided significant economic and environmental benefits.