| Citation: |
LUO Wenqian, HE Liqiu, LI Jinghong, et al. Preparation of flake Ca-Mg composite carbonate by ultrasonic assisted method and its effect on the properties of PBAT composites[J]. Acta Materiae Compositae Sinica, 2025, 42(1): 323-335. DOI: 10.13801/j.cnki.fhclxb.20240329.002
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Flaky carbonate materials have become important thermoplastic polymer reinforced rigid inorganic fillers due to their advantages of non-toxicity, low cost and abundant raw materials. However, their preparation process is complex and difficult to achieve mass production. In this paper, combined with the problem of low added value of low-grade limestone in limestone industry, flaky Ca-Mg complex carbonates (FCM) were prepared by ultrasonic-assisted carbonization method using Mg-containing limestone as raw material. The effects of process parameters such as different Mg contents, different carbonization reaction temperatures and different ultrasonic powers on the morphology of the product were investigated. On this basis, the active FCM and poly(butylene adipate-co-terephthalate) (PBAT) resin were blended and extruded into composites. The effects of different kinds of fillers and different ratios on the properties of composites were compared. The results show that Mg content, ultrasonic power and reaction temperature have a significant effect on the morphology of Ca-Mg composite carbonate. With the increase of Mg content to 20.61wt%, reaction temperature to 70℃ and ultrasonic power to 400 W, Ca-Mg composite carbonate products with a large number of flake structures and a specific surface area of 23.5 m2/g are obtained. The composites with active FCM showed excellent mechanical properties. When the content of active FCM was 20wt%, the impact strength, flexural strength and flexural modulus of the composites were 1 time, 2 times and 2.8 times higher than those of pure PBAT, respectively. When the addition amount is 40wt%, these performance indexes are further improved, which are 1.2 times, 2.6 times and 4.8 times higher than that of pure PBAT, respectively. More importantly, the soil degradation rate of the composite material added with the active FCM is significantly improved, which will effectively promote the degradation of the composite material after use, so that it can quickly integrate into the natural environment after completing the service mission, further reflecting its environmental protection and sustainable characteristics.
Plastics are widely used in various fields and have made great contributions. However, the application of plastics also brings problems, and the problem of plastic pollution is becoming more and more serious. Therefore, how to use plastics efficiently and correctly and realize its wide application has become a research hotspot. Based on this, the use of biodegradable plastic matrix is considered. Among them, PBAT is widely used due to its rich raw materials, excellent processing performance and wide application. However, the high viscosity of PBAT limits its performance in practical applications. In order to overcome these problems, researchers have proposed to improve these deficiencies by physical (blending with other polymers or using inorganic fillers to enhance the matrix) or chemical modification. Among them, the enhancement and stiffening effect of flake inorganic fillers in composite materials has been widely confirmed. Common flaky inorganic fillers include montmorillonite, talc, mica, etc. Most of these fillers with lamellar structure are naturally formed, non-renewable, and may contain harmful substances such as asbestos. Considering these factors, scholars have begun to explore other alternatives. The study found that carbonate products have the characteristics of easy availability of raw materials, non-toxicity, and easy processing, and have become an ideal candidate. The preparation of carbonate products with flake morphology to replace talc and other flake inorganic fillers opens up a broader development prospect for the carbonate industry.
Flaky Ca-Mg Complex Carbonates (FCM) were prepared by ultrasonic-assisted carbonization method. The phase composition and morphology of the products were studied by adjusting the Mg content in limestone, the reaction temperature of the system and the ultrasonic power, combined with XRD and SEM. The growth process of FCM was further explored, and the optimum process conditions for the formation of flake morphology were analyzed in detail. After the ideal flake morphology of Ca-Mg complex carbonate was obtained, FCM/PBAT composites with different filling amounts were prepared by melt blending method. At the same time, the composites prepared by the other three commonly used CaCO under different filling amounts were compared. By analyzing the mechanical properties, microscopic properties and soil degradation test results of PBAT matrix composites, the effects of different fillers on the properties of PBAT matrix under different filling amounts were obtained.
The Ca-Mg composite carbonate with a large number of lamellar structures and a specific surface area of 23.5 m/g was successfully prepared by ultrasonic-assisted carbonization without adding a crystal-directing agent. The prepared FCM and different types of commercially available CaCO were blended with PBAT resin and extruded into composites. The properties of the composites prepared by different types of fillers with different filling amounts were compared. The results showed that the composites with active FCM showed excellent mechanical properties. When the addition amount of FCM was 20 wt%, the impact strength, flexural strength and flexural modulus of the composites were 1 time, 2 times and 2.8 times higher than those of pure PBAT, respectively. When the addition amount increased to 40 wt%, these performance indicators were further improved, which were 1.2 times, 2.6 times and 4.8 times higher than that of pure PBAT, respectively. More importantly, the soil degradation rate of the composite material added with the active FCM is significantly improved, which will effectively promote the degradation of the composite material after use, so that it can quickly integrate into the natural environment after completing the service mission, further reflecting its environmental protection and sustainable characteristics.Conclusions: Based on the problem of low added value of low-grade limestone, FCM was successfully prepared by using low-grade limestone containing Mg as raw material. On this basis, the structure and properties of FCM/PBAT composites prepared by melt blending were further explored, and their properties were compared with those of different kinds of CaCO3, which further verified the enhancement and rigidity of inorganic flake fillers in the matrix, and provided a reference for the effective application of FCM.
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