Properties of Geopolymer Composites Reinforced with Basalt Chopped Strand Mat or Woven Fabric

Geopolymers or polysialates are inorganic polymeric, ceramic‐like materials composed of alumina, silica, and alkali metal oxides that can be made without any thermal treatment. Additions of reinforcing phases vastly improve the mechanical properties and high‐temperature stability of the geopolymer. The processing and mechanical properties of both chopped strand mat as well as 2‐D woven fabric‐reinforced potassium geopolymer composites have been evaluated. Hand lay‐up and hydraulic press processing methods were used to produce composite panels. The room‐temperature tensile and flexural strength of chopped strand mat composites was 21.0 ± 3.1 and 31.7 ± 4.4 MPa, respectively, while those of basalt weave‐reinforced geopolymer composites reached 40.0 ± 5.9 and 45.2 ± 9.3 MPa, respectively. Composite microstructures were examined using optical microscopy as well as scanning electron microscopy (SEM). Mass, volume, and porosity fractions were also determined. The effect of high‐temperature treatments at 25°C, 300°C, 600°C, and 800°C were analyzed. Finally, Weibull statistical analysis was performed, which showed an increase in reliability when a reinforcement phase was added to K‐geopolymer.     

Synthesis and mechanical properties of novel composites of inorganic polymers (geopolymers) with unidirectional natural flax fibres (phormium tenax)

This study reports the synthesis and mechanical properties of new inorganic polymer (geopolymer) composites unidirectionally reinforced with 4–10 vol.% natural cellulose-based fibres (NZ flax, phormium tenax). The geopolymer matrix was derived from dehydroxylated kaolinite-type clay. The mechanical properties of the fibre-reinforced composites improve with increasing fibre content, achieving ultimate flexural strengths of about 70 MPa at 10 vol.% fibre content. This represents a significant improvement on the flexural strength of the unreinforced geopolymer matrix (about 5.8 MPa), and all the composites show graceful failure, unlike the brittle failure of the matrix. Scanning electron microscopy was used to study the morphology of the fibre-matrix regions and a combination of thermogravimetric analysis (TGA) and thermal shrinkage measurements of these composites suggests that despite the formation of microcracks due to water loss from the geopolymer matrix, the fibres are thermally protected by the matrix up to 400 °C. The flax fibres do not appear to be compromised by the alkaline environment of the matrix, suggesting new possible applications for these low-cost simply prepared construction materials.     

3D打印混凝土技术在澳大利亚的最近研究进展

3D打印,又被称为增材制造,是通过逐层累积叠加制造三维物体的一种技术手段。过去几年中,这种技术吸引了越来越多来自建筑业的关注。与传统混凝土浇筑技术相比,3D打印混凝土的应用可以实现更加高效的自由建筑制造,同时减小对人工劳动力的依赖。在全球范围内,由于相关高校和科研单位的积极参与,关于3D打印混凝土的研究工作取得了巨大的进展,其中包括澳大利亚的相关研究。本文主要对澳大利亚在3D打印混凝土研究方面有代表性的两所高校的最新进展进行介绍,两所学校分别是皇家墨尔本理工大学(RMIT大学)和斯威本科技大学。本文首先介绍了两所高校的打印设备及其特点,随后讨论了具体研究领域和近期发表的相关文章。RMIT大学主要侧重于研究纤维增强对3D打印混凝土力学性能方面的影响,而斯威本科技大学则着重研究3D打印地聚物混凝土的性能。本文旨在促进相关领域研究人员对澳大利亚3D打印混凝土研究团队和研究进展的理解。     

Bone ash reinforced geopolymer composites

Potassium-based, geopolymer composites were made with BASF^® metakaolin and Mymensingh clay-derived metakaolin from Bangladesh. Since the natural Mymensingh clay contained 40 wt.% quartz, this same amount of quartz particulates was added to the BASF^® metakaolin to make a synthetic analog of the natural calcined clay. By analogy with bone china, bone ash or calcined hydroxyapatite (5CaO•3P₂O₅ or “HA”) particles, having a Ca: P ratio of 3.3:1, were added to make the three types of geopolymer-based composites described above. For less refractory particulate additions, dicalcium phosphate (DCP) (2CaO•P₂O₅ or “DCP”) particles, having a Ca: P ratio of 2:1, were also added to another set of geopolymers. The ambient temperature compressive and flexural strengths were measured for all of the geopolymer composites. The HA or DCP reinforced geopolymer composites were fabricated and heat-treated to 1150°C/1 h, after which they were converted to their mineralogical analogs. Their mechanical properties of compressive and 3-point flexural strengths were again measured. Flexural strengths of 22.42 ± 11.0 MPa and 31.97 ± 8.3 MPa were measured in 1 × 1 × 10 cm³ heat-treated geopolymer bars reinforced with 10 wt.% of DCP and in geopolymer reinforced with 10 wt.% DCP +40 wt.% quartz additions, respectively. Significant improvements to ambient temperature properties were observed due to the self-healing effect of the flowing amorphous DCP, whose presence was verified by SEM. The geopolymer samples exhibited reduced water absorption (WA) (on a percentage dry weight basis) of within 0.03-0.5% after being heated at 1100℃/1 h and 1125℃/1 h, as compared with those at room temperature, which varied between 2.56% and 7.89%.     

Synthesis of heat and ambient cured one-part geopolymer mixes with different grades of sodium silicate

The use of solid activators in the manufacture of geopolymer enhances its commercial viability as it aids the development of a one-part “just add water” geopolymer mixture, similar to the conventional Portland cement-based materials. This study is aimed to synthesize heat and ambient cured one-part geopolymer mixes. Appropriate combinations of low calcium (Class F) fly ash, slag and hydrated lime as the aluminosilicate source materials were activated by three different grades of sodium silicate and a combination of sodium silicate and sodium hydroxide powders. A conventional two-part geopolymer mix with the commonly used sodium hydroxide and sodium silicate solutions was also made for comparison. Effects of the type and amount of the solid activator, the amount of fly ash replacement with slag and hydrated lime and water content on short term mechanical properties of the heat cured one-part geopolymer mixtures including workability of the fresh mix, hardened density and compressive strength were evaluated. Subsequently, effects of ambient curing on the properties of the developed one-part geopolymer mixes were also investigated. Moderate to high compressive strength of over 37 MPa developed for the heat and ambient cured one-part geopolymer mixes. The 28-days compressive strengths of the ambient cured one-part geopolymer mixtures, regardless of the type of activator and geopolymer source materials, were comparable to those of the counterpart heat cured one-part geopolymer mixes. Such one-part geopolymer mixes could enhance the commercial viability and large-scale applications of the geopolymer in the construction industry.     

Direct ink writing of chopped carbon fibers reinforced polymer-derived SiC composites with low shrinkage and high strength

The chopped carbon fiber reinforced SiC (C_f/SiC) composite has been regarded as one of the excellent high-temperature structural materials for applications in aerospace and military fields. This paper presented a novel printing strategy using direct ink writing (DIW) of chopped fibers reinforced polymer-derived ceramics (PDCs) with polymer infiltration and pyrolysis (PIP) process for the fabrication of C_f/SiC composites with high strength and low shrinkage. Five types of PDCs printing inks with different C_f contents were prepared, their rheological properties and alignment of carbon fiber in the printing filament were studied. The 3D scaffold structures and bending test samples of C_f/SiC composites were fabricated with different C_f contents. The results found that the C_f/SiC composite with 30 wt% C_f content has high bending strength (～ 7.09 MPa) and negligible linear shrinkage (～ 0.48%). After the PIP process, the defects on the C_f/SiC composite structures were sufficiently filled, and the bending strength of C_f/SiC composite can reach up to about 100 MPa, which was about 30 times greater than that of the pure SiC matrix without C_f. This work demonstrated that the printed C_f/SiC composites by using this method is beneficial to the development of the precision and complex high-temperature structural members.     

连续碳纤维增强热固性酚醛树脂复合材料的3D打印工艺及性能研究

针对连续碳纤维增强热固性酚醛树脂复合材料3D打印成型工艺的技术难题,本文提出了浸渍-原位预固化-后固化的3D打印成型方案,实现了连续碳纤维增强热固性酚醛树脂复合材料的3D打印成型,并研究浸渍温度对酚醛树脂接触角与表面张力,以及打印工艺对样件形貌和力学性能的影响规律。结果表明:当浸渍温度为40 ℃,预固化温度为180 ℃时,纤维-树脂界面结合效果最佳,原料具备成型条件;当打印间距为0.5 mm时,样件的弯曲强度及模量达到最大值,分别为660.00 MPa和57.99 GPa,层间剪切强度达到20.14 MPa。此连续碳纤维增强热固性酚醛树脂复合材料一体化制备工艺解决了3D打印热固性树脂原位成型难的问题,为制备具有复杂结构的连续纤维增强热固性树脂复合材料提供了参考。     

Additive manufacturing of Al2O3 ceramic core with applicable microstructure and mechanical properties via digital light processing of high solid loading slurry

Ceramic cores are essential intermediate mediums in casting superalloy hollow turbine blades. The developing of additive manufacturing (AM) technology provides a new approach for the preparation of ceramic cores with complex structure. In this study, alumina oxide (Al₂O₃) ceramic cores with fine complex geometric shapes were fabricated by digital light processing (DLP) in high resolution. The maximum solid content of 70 vol% of ceramic slurry was adopted in the printing process, which is important for the regulation of deformations and mechanical properties. The effects of the printing parameters, including exposure intensity, printing layer thickness and sintering temperature on the microstructures and mechanical properties of printed samples were investigated. The decrease of residual stress and similar shrinkage in X, Y, and Z directions could be obtained by adjusting the printing parameters, which are crucial to prepare complex ceramic cores with high quality. Besides, the flexure strength and open porosity of ceramic cores reached 34.84 MPa and 26.94%, respectively, which were supposed to meet the requirement of ceramic cores for the fabrication of superalloy blades.     

Mechanochemical fabrication of geopolymer composites based on the reinforcement effect of microfibrillated cellulose

In this study, microfibrillated cellulose-reinforced geopolymer organic/inorganic hybrid materials, were prepared via a simple green mechanochemical method. The interaction between microfibrillated nanocellulose and geopolymer was further investigated by molecular dynamics simulation. The study established that mechanical ball milling could effectively promote the microfibrillation of bamboo pulp fibers to form reinforced geopolymer composites with a uniformly distributed cellulose skeleton network. The compressive strength of geopolymer blended with 2% microfibrillated cellulose was shown to be 85.1% higher than that of the pristine geopolymer after 30 days. In addition, the hybrid system was found to maintain excellent thermal stability due to the effective protection of the biomass components by the inorganic matrix. This one-step mechanochemical process provided an efficient approach for preparing geopolymer composites, which offers significant application potential for use in road repairs, high-temperature-resistant materials, and additive manufacturing via 3D printing.     

煤气化粗渣-矿渣基地质聚合物的制备与性能

在煤气化粗渣基地质聚合物中复掺矿渣可改善其早期力学性能。本文以煤气化粗渣和矿渣为原料制备地质聚合物,系统研究了不同矿渣掺量对煤气化粗渣基地质聚合物早期力学性能及微观结构的影响。利用X射线衍射、压汞测试、扫描电镜、傅里叶红外光谱等方法对煤气化粗渣-矿渣基地质聚合物的微观结构进行分析表征。结果表明,当矿渣掺量增加时,地质聚合物抗压强度呈逐渐增大趋势。矿渣掺量为40%(质量分数)时,样品28 d抗压强度高达53.1 MPa。由微观分析可知,掺入矿渣后地质聚合物表面生成了大量水化硅铝酸钙/钠(C(N)-A-S-H)凝胶,使地质聚合物微观结构更为致密,力学性能得到改善。     

Synthesis and mechanical properties of lightweight hybrid geopolymer foams reinforced with carbon nanotubes

A lightweight hybrid geopolymer foams reinforced with carbon nanotubes (CNTs) was exploited by adding the CNTs into geopolymeric matrix through hydrogen peroxide method. The synergistic effects of nanotubes and foaming agent on the phase evolution, microstructure, and mechanical properties were investigated. After introduction of nanotubes, the geopolymer foams reinforced with CNTs (CNTs/KGP) still showed amorphous structure. Porosity of the foams increased with the H₂O₂ content and decreased with the increase in CNTs content. The addition of CNTs (1-9 wt%) in foams refined the distribution of pore size from 523 to 352 μm. Compression strength of the CNTs/KGP samples elevated with the increasing content of CNTs, which was contributed to the crack propagation and bridging of CNTs in foams. The CNTs/KGP foams with considerable porosity show potential applications in adsorption, filtration, membrane supports, other industries, etc     

Mechanical behavior of K-geopolymers reinforced with silane-coated basalt fibers

A potassium-based geopolymer (KGP) was produced through the combination of metakaolin and a K-based alkali metasilicate solution (K₂O•Al₂O₃•4SiO₂•11H₂O). Two types of silane-coated chopped basalt fibers, manufactured for cement or epoxy-based applications, were used in order to compare their effects. The fibers had a 12.7 mm (½ inch) length and were incorporated initially in 10 wt % contents, due to the limited fluidity of the matrix. The effect of the addition of Sapetin® superplasticizer in varying weight percentages was examined through consistency tests. 0.5% by weight of the matrix was established to be an adequate amount to improve the geopolymer workability, allowing a greater incorporation of both types of fibers into the matrix (20 wt%). The mechanical properties were analyzed through compression and 4-point flexural tests. Pull-out and direct tensile tests were also performed. Additionally, X-ray diffraction (XRD) was conducted with the KGP material and scanning electron microscopy (SEM) was used to measure the fiber cross sections. Both composites manufactured with 10 wt % of fibers reached similar high flexural strengths (~30 MPa), suggesting a suitable crack propagation at higher stresses due to strong fiber-matrix adhesions. The fibers manufactured for epoxy applications presented a greater compatibility in 20 wt % contents, reaching 37.8 MPa in flexural tests. This was attributed to a better dispersion of such fibers in a fresh mix with reduced friction, such as KGP with the addition of superplasticizer, suggesting an improved use of this reinforcement in such contents.     

PVA纤维类型对应变硬化地聚合物基复合材料力学性能的影响

本文对比分析了4种不同聚乙烯醇(PVA)纤维分别在不同配合比地聚合物基体中的增韧作用,为利用国产无表面涂油PVA纤维制备应变硬化地聚合物基复合材料(SHGC)提供实验数据。主要研究矿渣与粉煤灰的比例、碱溶液的浓度、纤维尺寸以及纤维表面特性等因素对地聚合物基复合材料抗压和直接拉伸性能的影响。结果表明,经过7 d室温养护,含矿渣的地聚合物基体和复合材料的抗压强度均高于30 MPa,而纯粉煤灰地聚合物基体和复合材料的抗压强度较低,为12~15 MPa。表面涂油PVA纤维SHGC的延展性普遍高于无表面涂油PVA纤维SHGC。然而,通过调节地聚合物基体配合比,可以提高无表面涂油PVA纤维的增韧效果。当粉煤灰质量分数为33%时,无表面涂油PVA纤维SHGC的极限拉伸应变达1.44%,与表面涂油PVA纤维SHGC相当。在纯粉煤灰的情况,4种PVA纤维复合材料均呈现出稳定的多缝开裂和应变硬化特征。     

Mechanical properties of natural fiber hybrid composites based on renewable thermoset resins derived from soybean oil,for use in technical applications

Natural fiber composites are known to have lower mechanical properties than glass or carbon fiber reinforced composites. The hybrid natural fiber composites prepared in this study have relatively good mechanical properties. Different combinations of woven and non‐woven flax fibers were used. The stacking sequence of the fibers was in different orientations, such as 0°, +45°, and 90°. The composites manufactured had good mechanical properties. A tensile strength of about 119 MPa and Young's modulus of about 14 GPa was achieved, with flexural strength and modulus of about 201 MPa and 24 GPa, respectively. For the purposes of comparison, composites were made with a combination of woven fabrics and glass fibers. One ply of a glass fiber mat was sandwiched in the mid‐plane and this increased the tensile strength considerably to 168 MPa. Dynamic mechanical analysis was performed in order to determine the storage and loss modulus and the glass transition temperature of the composites. Microstructural analysis was done with scanning electron microscopy. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of sodium polyacrylate on mechanical properties and microstructure of metakaolin-based geopolymer with different SiO2/Al2O3 ratio

The mechanical properties and microstructure of geopolymer are affected by the molar ratio of SiO₂/Al₂O₃. Meanwhile, organic polymer has the effect of improving the toughness of geopolymer, which depends on the SiO₂/Al₂O₃ ratio of geopolymer inevitably. Therefore, it is important to investigate the effect of the organic polymer on the mechanical properties and microstructure of geopolymer with varying SiO₂/Al₂O₃ ratio for using organic polymer to modify geopolymer. In this work, the SiO₂/Al₂O₃ ratios of metakaolin-based geopolymers are adjusted to 2.0, 2.5, 3.0, 3.5 and 4.0 by adding silica fume and β-Al₂O₃, with Na₂O/SiO₂, H₂O/SiO₂ being maintained at 0.2, 4.0, respectively. The geopolymers with each SiO₂/Al₂O₃ ratios are modified by addition of 0, 0.4, 0.8, 1.2 and 1.6?wt% of sodium polyacrylate (PAAS).The mechanical properties of these samples are measured and the rate of change is used to characterize the effect of PAAS on the metakalin-based geopolymers. The mechanism is also shown by 29Si NMR, XPS and FTIR. The results show that the effects of polymer on the mechanical properties of metakaolin-based geopolymer are affected by SiO₂/Al₂O₃ ratio and the effect becomes less obvious with SiO₂/Al₂O₃ ratio increasing from 2.0 to 4.0. Incorporation of PAAS can reduce the degree of polymerization of [SiO]₄ or [AlO]₄ in geopolymer and form the Si?O?C bond, which are two main reasons for polymer improving the toughness of geopolymer. But these effects decrease when the SiO₂/Al₂O₃ ratio of geopolymer increases from 2.0 to 4.0, which is corresponding to the effect on the mechanical properties. The toughening effect of organic polymer on geopolymer depends on the SiO₂/Al₂O₃ ratio of geopolymer, and only the geopolymer with lower SiO₂/Al₂O₃ ratio (no more than 2.5 in this work) can be significantly toughening modified by organic polymer. Therefore, it is necessary to consider the SiO₂/Al₂O₃ ratio of the geopolymer when geopolymer modified by organic polymer is designed.     

One-step synthesis of improved silica/epoxy nanocomposites with inorganic-organic hybrid network

High performance silica/epoxy nanocomposites were prepared through mixing epoxy, tetraethyl orthosilicate (TEOS), γ-aminoproplytriethyoxy siliane(APTES), and triethyltrtramine (TETA) at 25 °C via sol-gel method on one-step. The effects of content of TEOS and coupling reagents on the mechanical and thermal properties of SiO₂/EP composites were studied. Microcosmic morphology and properties of the hybrid materials were characterized by FT-IR, TEM, FESEM, and DSC. Results revealed that SiO₂/EP composites achieve the optimal mechanical and thermal properties when the composites prepared with mass ratio of TEOS/APTES/epoxy for 3/2/100 without acetone. Compared with pristine epoxy, the tensile strength, elongation at break, impact strength and bend strength increased 67.6 %, 190 %, 82.1 % and 15.7 %, respectively. The further study was to investigate the content of TEOS and APTES effecting on mechanical properties and water sorption of fiber reinforced composites, which used the above compound as matrix resin.     

Rubberized geopolymer composites: A comprehensive review

The construction sector has been addressing the issue of integrating sustainability into production processes over the last few years, either through solid waste materials as aggregates in concrete or the search for more eco-friendly raw materials. Besides, the global trends group focused on developing an alternative to cement, which is a significant contributor to pollution of the environment due to its greenhouse gas emissions. Geopolymer (GP) is one of the most acceptable solutions for utilizing all industrial by-products containing an alumino-silicate (A-S) source material. However, one method to recycle waste rubber tires is incorporating them into geopolymer concrete (GPC) as an alternative to natural aggregates. Recently, the potential of combining the advantages of GPC with rubberized concrete to produce rubberized geopolymer concrete (Ru-GPC) as a viable, sustainable building material has been recognized. This paper presents a state-of-the-art review of the waste rubber's environmental and economic impact, resources, recycling, classifications, and physicochemical properties. Besides, this article provides in-depth studies on the behaviors and properties of Ru-GPC composites, such as their basic components, preparation and curing processes, fresh and physical properties, mechanical properties, dynamic properties, durability properties, microstructures, and insulation properties. The effect of crumb rubber (CRu) substitution on critical properties is addressed critically. Also, it highlights the applications, embodied CO₂ emissions, and cost analysis of Ru-GPC. Moreover, gaps in the literature and recommendations for future study have been identified to support further developments in the investigation and future publication of Ru-GPC materials in practice.     

激发剂对赤泥地聚物砂浆力学性能的影响

以热活化氧化铝赤泥为主要原料制备赤泥地聚物砂浆,对比研究了激发剂种类和掺量对赤泥地聚物力学性能的影响及其合成机理。结果表明,水玻璃、石灰-碱（质量比为2∶1）、石膏-碱（质量比为2∶1）均能改善氧化铝赤泥的反应活性,促进赤泥地聚物的合成,其中水玻璃（氧化硅与氧化钠物质的量比为1.5）的改性效果最为显著。水玻璃、石灰-碱、石膏-碱的最佳掺量分别为20%、7%、10%。水玻璃掺量为20%时,赤泥地聚物砂浆28 d抗压强度和28 d抗折强度分别为32.1 MPa和6.0 MPa。改变激发剂的种类和掺量,可以调整赤泥地聚物砂浆体系的碱度,改变铝硅酸结构的解聚和地聚物的缩聚过程,从而影响其力学性能。     

Additive manufacturing of carbon fiber reinforced ceramic matrix composites based on fused filament fabrication

For the first time, carbon fiber reinforced ceramic matrix composites (CMC) were successfully fabricated by additive manufacturing (AM) using the fused filament fabrication (FFF) technology, filaments (“CF-PEEK”) with thermoplastic polyetheretherketone (PEEK) as the matrix and C-precursor, and carbon short-fibers (< 250 μm) as reinforcements. In order to prevent a re-melting of the as-printed CFRPs (C-fiber reinforced plastics) during pyrolysis at 1000 °C in N₂ensuring the freedom of design and complex parts, a prior crosslinking step at 325 °C with a dwell time of 48 h in air was introduced to stabilize and crosslink the CFRP. Due to the stabilization and the printing of degassing channels for the pyrolysis, near net shape and complex CMC parts with different C-fiber orientations (0°; ±45°; 90°) were obtained by the liquid siliconization infiltration process (LSI). The manufactured C/C-SiC parts were characterized regarding their microstructure and mechanical properties. The reinforcing C-fibers were successfully protected during the LSI-process and flexural strengths of almost 60 MPa were obtained.     

Synthesis and thermal behavior of inorganic–organic hybrid geopolymer composites

Inorganic geopolymer potassium aluminosilicate was prepared at room temperature by the reaction of kaolin, potassium silicate, and potassium hydroxide solution and was dispersed in situ into an epoxy matrix by various proportions to fabricate novel inorganic–organic hybrid geopolymer composites. The formation of inorganic geopolymer with respect to time was monitored by X‐ray diffraction and FT‐IR analysis and confirmed that 30 min is required to complete the geopolymerization. When geopolymers were properly mixed at different ratios with organic polymers such as epoxy and cured, these hybrid polymers exhibit significant thermal stability. Pure kaolin was also incorporated into the epoxy matrix to compare the change in chemical and thermal properties. Cone calorimetry results showed about 27% decreased in rate of heat release (RHR) on addition of 20% pure kaolin. However, about 57% of RHR was decreased on addition of only 20% geopolymer. Evaluation of CO₂ and CO were found to be minimum 2.0 and 0.7 kg/kg, respectively, for hybrid geopolymer composites compared to very high yield for epoxy at 3.5 kg/kg after 200 s of ignition. The current study shows that due to the high thermal stability of hybrid geopolymer composites, the novel hybrid geopolymer composites have the ability to be potential candidates to use in practical application where fire is of great concern. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 112–121, 2005