This article has multiple issues. Please help improve it or discuss these issues on the talk page . (Learn how and when to remove these template messages)
|
A geopolymer is an inorganic, typically ceramic-like, material that forms covalently bonded, non-crystalline (amorphous) networks. Many geopolymers may also be classified as alkali-activated cements or acid-activated binders. They are mainly produced by a chemical reaction between a chemically reactive aluminosilicate powder (e.g. metakaolin or other clay-derived powders, natural pozzolan, or suitable glasses), and an aqueous solution (alkaline or acidic) that causes this powder to react and re-form into a solid monolith. The most common pathway to produce geopolymers is by the reaction of metakaolin with sodium silicate, which is an alkaline solution, but other processes are also possible. [1]
Commercially produced geopolymers may be used for fire- and heat-resistant coatings and adhesives, medicinal applications, high-temperature ceramics, new binders for fire-resistant fiber composites, toxic and radioactive waste encapsulation, and as cementing components in making or repairing concretes. The properties and uses of geopolymers are being explored in many scientific and industrial disciplines: modern inorganic chemistry, physical chemistry, colloid chemistry, mineralogy, geology, and in other types of engineering process technologies.
The original raw materials used in the synthesis of geopolymers were mainly rock-forming minerals of geological origin, hence the name: geopolymer was coined by Joseph Davidovits in 1978. [2] These materials and associated terminology were then popularized over the following decades via his work with the Institut Géopolymère (Geopolymer Institute).
Geopolymers can be synthesized in one of two conditions:
The alkaline route is the most important in terms of research and development and commercial applications and will be described below. Details on the acidic route have also been published. [3] [4]
In the 1950s, Viktor Glukhovsky developed concrete materials originally known under the names "soil silicate concretes" and "soil cements", [5] but since the introduction of the geopolymer concept by Joseph Davidovits, the terminology and definitions of the word geopolymer have become more diverse and often conflicting. The word geopolymer is sometimes used to refer to naturally occurring organic macromolecules; [6] that sense of the word differs from the now-more-common use of this terminology to discuss inorganic materials which can have either cement-like or ceramic-like character.
In the following presentation, a geopolymer is essentially a mineral chemical compound or mixture of compounds consisting of repeating units, for example silico-oxide (-Si-O-Si-O-), silico-aluminate (-Si-O-Al-O-), ferro-silico-aluminate (-Fe-O-Si-O-Al-O-) or alumino-phosphate (-Al-O-P-O-), created through a process of geopolymerization. [7] This method of describing mineral synthesis (geosynthesis) was first presented by Davidovits at an IUPAC symposium in 1976. [8]
Even within the context of inorganic materials, there exist various definitions of the word geopolymer, which can include a relatively wide variety of low-temperature synthesized solid materials. [9] The most typical geopolymer is generally described as resulting from the reaction between metakaolin (calcined kaolinitic clay) and a solution of sodium or potassium silicate (waterglass). Geopolymerization tends to result in a highly connected, disordered network of negatively charged tetrahedral oxide units balanced by the sodium or potassium ions.
In the simplest form, an example chemical formula for a geopolymer can be written as Na2O·Al2O3·nSiO2·wH2O, where n is usually between 2 and 4, and w is around 11-15. Geopolymers can be formulated with a wide variety of substituents in both the framework (Si,Al) and non-framework (Na) sites; most commonly K or Ca takes on the non-framework (Na) sites, or Fe or P can in principle replace some of the Al or Si.
Geopolymerization usually occurs at ambient or slightly elevated temperature; the solid aluminosilicate raw materials (e.g. metakaolin) dissolve into the alkaline solution, and then cross-link and polymerize into a growing gel phase, which then continues to set, harden and gain strength.
The fundamental unit within a geopolymer structure is a tetrahedral complex consisting of silicon or aluminum coordinated through covalent bonds to four oxygens. The geopolymer framework results from the cross-linking between these tetrahedra, which leads to a 3-dimensional aluminosilicate network, where the negative charge associated with tetrahedral aluminium is balanced by a small cationic species, most commonly an alkali metal cation (Na+, K+ etc). These alkali metal cations are often ion-exchangeable, as they are associated with, but only loosely bonded to, the main covalent network, similarly to the non-framework cations present in zeolites.
Geopolymerization is the process of combining many small molecules known as oligomers into a covalently bonded network. This reaction process takes place via formation of oligomers (dimer, trimer, tetramer, pentamer) which are believed to contribute to the formation of the actual structure of the three-dimensional macromolecular framework, either through direct incorporation or through rearrangement via monomeric species. These oligomers are named by some geopolymer chemists as sialates following the scheme developed by Davidovits, [2] although this terminology is not universally accepted within the research community due in part to confusion with the earlier (1952) use of the same word to refer to the salts of the important biomolecule sialic acid. [10]
The image shows 5 examples of small oligomeric potassium aluminosilicate species (labelled in the diagram according to the poly(sialate) / poly(sialate-siloxo) nomenclature), which are key intermediates in potassium-based alumino-silicate geopolymerization. The aqueous chemistry of aluminosilicate oligomers is complex, [11] and also plays an important role in the discussion of zeolite synthesis, a process which has many details in common with geopolymerization.
Example of geopolymerization of a metakaolin precursor, in an alkaline medium [12]
The reaction process broadly involves four main stages:
The reaction processes involving other aluminosilicate precursors (e.g. low-calcium fly ash, crushed or synthetic glasses, natural pozzolans) are broadly similar to the steps described above.
Geopolymerization forms aluminosilicate frameworks that are similar to those of some rock-forming minerals, but lacking in long-range crystalline order, and generally containing water in both chemically bound sites (hydroxyl groups) and in molecular form as pore water. This water can be removed at temperatures above 100 – 200 °C. Cation hydration and the locations and mobility of water molecules in pores are important for lower-temperature applications, such as in usage of geopolymers as cements. [13] [14] The figure shows a geopolymer containing both bound (Si-OH groups) and free water (left in the figure). Some water is associated with the framework similarly to zeolitic water, and some is in larger pores and can be readily released and removed. After dehydroxylation (and dehydration), generally above 250 °C, geopolymers can then crystallise above 800-1000 °C (depending on the nature of the alkali cation present). [15]
There exist a wide variety of potential and existing applications. Some of the geopolymer applications are still in development whereas others are already industrialized and commercialized. [16] They are listed in three major categories:
This article contains content that is written like an advertisement .(November 2013) |
From a terminological point of view, geopolymer cement [17] is a binding system that hardens at room temperature, like regular Portland cement.
Geopolymer cement is being developed and utilised as an alternative to conventional Portland cement for use in transportation, infrastructure, construction and offshore applications.[ citation needed ]
Production of geopolymer cement requires an aluminosilicate precursor material such as metakaolin or fly ash, a user-friendly alkaline reagent [18] [ promotional source? ] (for example, sodium or potassium soluble silicates with a molar ratio (MR) SiO2:M2O ≥ 1.65, M being Na or K) and water (See the definition for "user-friendly" reagent below). Room temperature hardening is more readily achieved with the addition of a source of calcium cations, often blast furnace slag.[ citation needed ]
Geopolymer cements can be formulated to cure more rapidly than Portland-based cements; some mixes gain most of their ultimate strength within 24 hours. However, they must also set slowly enough that they can be mixed at a batch plant, either for precasting or delivery in a concrete mixer. Geopolymer cement also has the ability to form a strong chemical bond with silicate rock-based aggregates.
There is often confusion between the meanings of the terms 'geopolymer cement' and 'geopolymer concrete'. A cement is a binder, whereas concrete is the composite material resulting from the mixing and hardening of cement with water (or an alkaline solution in the case of geopolymer cement), and stone aggregates. Materials of both types (geopolymer cements and geopolymer concretes) are commercially available in various markets internationally.
There exists some confusion in the terminology applied to geopolymers, alkali-activated cements and concretes, and related materials, whcih have been described by a variety of names including also "soil silicate concretes" and "soil cements". [5] Terminology related to alkali-activated materials or alkali-activated geopolymers is also in wide (but debated) use. These cements, sometimes abbreviated AAM, encompass the specific fields of alkali-activated slags, alkali-activated coal fly ashes, and various blended cementing systems.
Geopolymerization uses chemical ingredients that may be dangerous and therefore requires some safety procedures. Material Safety rules classify the alkaline products in two categories: corrosive products (named here: hostile) and irritant products (named here: friendly).[ citation needed ]
The table lists some alkaline chemicals and their corresponding safety label. [19] Alkaline reagents belonging to the second (less elevated pH) class may also be termed as User-friendly, although the irritant nature of the alkaline component and the potential inhalation risk of powders still require the selection and use of appropriate personal protective equipment, as in any situation where chemicals or powders are handled.
The development of some alkali-activated-cements, as shown in numerous published recipes (especially those based on fly ashes) use alkali silicates with molar ratios SiO2:M2O below 1.20, or are based on concentrated NaOH. These conditions are not considered so user-friendly as when more moderate pH values are used, and require careful consideration of chemical safety handling laws, regulations, and state directives.
Conversely, geopolymer cement recipes employed in the field generally involve alkaline soluble silicates with starting molar ratios ranging from 1.45 to 1.95, particularly 1.60 to 1.85, i.e. user-friendly conditions. It may happen that for research, some laboratory recipes have molar ratios in the 1.20 to 1.45 range.
The categories comprise:
The first geopolymer cement developed in the 1980s was of the type (K,Na,Ca)-poly(sialate) (or slag-based geopolymer cement) and resulted from the research developments carried out by Joseph Davidovits and J.L. Sawyer at Lone Star Industries, USA and yielded the invention of Pyrament® cement. The American patent application was filed in 1984 and the patent US 4,509,985 was granted on April 9, 1985 with the title 'Early high-strength mineral polymer'.
In the 1990s, building on the works conducted on geopolymeric cements and on the synthesis of zeolites from fly ashes on the other hand, Wastiels et al., [27] Silverstrim et al. [28] and van Jaarsveld and van Deventer [29] developed geopolymeric fly ash-based cements.
Presently two types based on siliceous (EN 197) or class F (ASTM C618) fly ashes:
Ferro-sialate-based geopolymer cement The properties are similar to those of rock-based geopolymer cement but involve geological elements with high iron oxide content. The geopolymeric make up is of the type (Ca,K)-(Fe-O)-(Si-O-Al-O). This user-friendly geopolymer cement is in the development and commercialization phase.[ citation needed ]
This section needs expansion. You can help by adding to it. (April 2024) |
Geopolymer cements may be able to be designed to have a lower attributed emission of carbon dioxide CO2 than some other widely-used materials. [30] Comparing to Portland cement, geopolymer is using industrial byproducts/waste, containing aluminosilicate phases (that has low negative environment impact), which minimize CO₂ emissions. [31]
In June 2012, the institution ASTM International organized a symposium on Geopolymer Binder Systems. The introduction to the symposium states:[ citation needed ]When performance specifications for Portland cement were written, non-portland binders were uncommon...New binders such as geopolymers are being increasingly researched, marketed as specialty products, and explored for use in structural concrete. This symposium is intended to provide an opportunity for ASTM to consider whether the existing cement standards provide, on the one hand, an effective framework for further exploration of geopolymer binders and, on the other hand, reliable protection for users of these materials.
The existing Portland cement standards are not adapted to geopolymer cements. They must be elaborated by an ad hoc committee. Yet, to do so, requires also the presence of standard geopolymer cements. Presently, every expert is presenting his own recipe based on local raw materials (wastes, by-products or extracted). There is a need for selecting the right geopolymer cement category. The 2012 State of the Geopolymer R&D, [32] suggested to select two categories, namely:
along with the appropriate user-friendly geopolymeric reagent.
This section needs expansion. You can help by adding to it. (April 2024) |
This section needs expansion. You can help by adding to it. (April 2024) |
Geopolymers can be used as a low-cost and/or chemically flexible route to ceramic production, both to produce monolithic specimens, and as the continuous (binder) phase in composites with particulate or fibrous dispersed phases.
Geopolymers produced at room temperature are typically hard, brittle, castable, and mechanically strong. This combination of characteristics offers the opportunity for their usage in a variety of applications in which other ceramics (e.g. porcelain) are conventionally used. Some of the first patented applications of geopolymer-type materials - actually predating the coining of the term geopolymer by multiple decades - relate to use in automobile spark plugs. [33]
It is also possible to use geopolymers as a versatile pathway to produce crystalline ceramics or glass-ceramics, by forming a geopolymer through room-temperature setting, and then heating (calcining) it at the necessary temperature to convert it from the crystallographically disordered geopolymer form to achieve the desired crystalline phases (e.g. leucite, pollucite and others). [34]
Because geopolymer artifacts can look like natural stone, several artists started to cast in silicone rubber molds replicas of their sculptures. For example, in the 1980s, the French artist Georges Grimal worked on several geopolymer castable stone formulations. [35]
In the mid-1980s, Joseph Davidovits presented his first analytical results carried out on samples sourced from Egyptian pyramids. He claimed that the ancient Egyptians used a geopolymeric reaction to make re-agglomerated limestone blocks. [36] [37] [38] Later on, several materials scientists and physicists took over these archaeological studies and have published results on pyramid stones, claiming synthetic origins. [39] [40] [41] [42] However, the theories of synthetic origin of pyramid stones have also been stridently disputed by other geologists, materials scientists, and archaeologists. [43]
It has also been claimed that the Roman lime-pozzolan cements used in the building of some important structures, especially works related to water storage (cisterns, aqueducts), have chemical parallels to geopolymeric materials. [44]
Concrete is a composite material composed of aggregate bonded together with a fluid cement that cures to a solid over time. Concrete is the second-most-used substance in the world after water, and is the most widely used building material. Its usage worldwide, ton for ton, is twice that of steel, wood, plastics, and aluminium combined.
A cement is a binder, a chemical substance used for construction that sets, hardens, and adheres to other materials to bind them together. Cement is seldom used on its own, but rather to bind sand and gravel (aggregate) together. Cement mixed with fine aggregate produces mortar for masonry, or with sand and gravel, produces concrete. Concrete is the most widely used material in existence and is behind only water as the planet's most-consumed resource.
In chemistry, a silicate is any member of a family of polyatomic anions consisting of silicon and oxygen, usually with the general formula [SiO(4-2x)−
4−x]
n, where 0 ≤ x < 2. The family includes orthosilicate SiO4−4, metasilicate SiO2−3, and pyrosilicate Si2O6−7. The name is also used for any salt of such anions, such as sodium metasilicate; or any ester containing the corresponding chemical group, such as tetramethyl orthosilicate. The name "silicate" is sometimes extended to any anions containing silicon, even if they do not fit the general formula or contain other atoms besides oxygen; such as hexafluorosilicate [SiF6]2−.Most commonly, silicates are encountered as silicate minerals.
Slag is a by-product of smelting (pyrometallurgical) ores and recycled metals. Slag is mainly a mixture of metal oxides and silicon dioxide. Broadly, it can be classified as ferrous, ferroalloy or non-ferrous/base metals. Within these general categories, slags can be further categorized by their precursor and processing conditions. "Slag generated from the EAF process can contain toxic metals, which can be hazardous to human and environmental health".
Sodium silicate is a generic name for chemical compounds with the formula Na
2xSi
yO
2y+x or (Na
2O)
x·(SiO
2)
y, such as sodium metasilicate Na
2SiO
3, sodium orthosilicate Na
4SiO
4, and sodium pyrosilicate Na
6Si
2O
7. The anions are often polymeric. These compounds are generally colorless transparent solids or white powders, and soluble in water in various amounts.
Pozzolana or pozzuolana, also known as pozzolanic ash, is a natural siliceous or siliceous-aluminous material which reacts with calcium hydroxide in the presence of water at room temperature. In this reaction insoluble calcium silicate hydrate and calcium aluminate hydrate compounds are formed possessing cementitious properties. The designation pozzolana is derived from one of the primary deposits of volcanic ash used by the Romans in Italy, at Pozzuoli. The modern definition of pozzolana encompasses any volcanic material, predominantly composed of fine volcanic glass, that is used as a pozzolan. Note the difference with the term pozzolan, which exerts no bearing on the specific origin of the material, as opposed to pozzolana, which can only be used for pozzolans of volcanic origin, primarily composed of volcanic glass.
Concrete recycling is the use of rubble from demolished concrete structures. Recycling is cheaper and more ecological than trucking rubble to a landfill. Crushed rubble can be used for road gravel, revetments, retaining walls, landscaping gravel, or raw material for new concrete. Large pieces can be used as bricks or slabs, or incorporated with new concrete into structures, a material called urbanite.
Joseph Davidovits is a French materials scientist. He posited that the blocks of the Great Pyramid are not carved stone but mostly a form of limestone concrete or man-made stone.
Metakaolin is the anhydrous calcined form of the clay mineral kaolinite. Rocks that are rich in kaolinite are known as china clay or kaolin, traditionally used in the manufacture of porcelain. The particle size of metakaolin is smaller than cement particles, but not as fine as silica fume.
Ground granulated blast-furnace slag is obtained by quenching molten iron slag from a blast furnace in water or steam, to produce a glassy, granular product that is then dried and ground into a fine powder. Ground granulated blast furnace slag is a latent hydraulic binder forming calcium silicate hydrates (C-S-H) after contact with water. It is a strength-enhancing compound improving the durability of concrete. It is a component of metallurgic cement. Its main advantage is its slow release of hydration heat, allowing limitation of the temperature increase in massive concrete components and structures during cement setting and concrete curing, or to cast concrete during hot summer.
Pozzolans are a broad class of siliceous and aluminous materials which, in themselves, possess little or no cementitious value but which will, in finely divided form and in the presence of water, react chemically with calcium hydroxide (Ca(OH)2) at ordinary temperature to form compounds possessing cementitious properties. The quantification of the capacity of a pozzolan to react with calcium hydroxide and water is given by measuring its pozzolanic activity. Pozzolana are naturally occurring pozzolans of volcanic origin.
Cement clinker is a solid material produced in the manufacture of portland cement as an intermediary product. Clinker occurs as lumps or nodules, usually 3 millimetres (0.12 in) to 25 millimetres (0.98 in) in diameter. It is produced by sintering limestone and aluminosilicate materials such as clay during the cement kiln stage.
Coal combustion products (CCPs), also called coal combustion wastes (CCWs) or coal combustion residuals (CCRs), are categorized in four groups, each based on physical and chemical forms derived from coal combustion methods and emission controls:
The alkali–silica reaction (ASR), also commonly known as concrete cancer, is a deleterious internal swelling reaction that occurs over time in concrete between the highly alkaline cement paste and the reactive amorphous silica found in many common aggregates, given sufficient moisture.
The pozzolanic activity is a measure for the degree of reaction over time or the reaction rate between a pozzolan and Ca2+ or calcium hydroxide (Ca(OH)2) in the presence of water. The rate of the pozzolanic reaction is dependent on the intrinsic characteristics of the pozzolan such as the specific surface area, the chemical composition and the active phase content.
Energetically modified cements (EMCs) are a class of cements made from pozzolans, silica sand, blast furnace slag, or Portland cement. The term "energetically modified" arises by virtue of the mechanochemistry process applied to the raw material, more accurately classified as "high energy ball milling" (HEBM). At its simplest this means a milling method that invokes high kinetics by subjecting "powders to the repeated action of hitting balls" as compared to (say) the low kinetics of rotating ball mills. This causes, amongst others, a thermodynamic transformation in the material to increase its chemical reactivity. For EMCs, the HEBM process used is a unique form of specialised vibratory milling discovered in Sweden and applied only to cementitious materials, here called "EMC Activation".
Gyrolite, NaCa16(Si23Al)O60(OH)8·14H2O, is a rare silicate mineral (basic sodium calcium silicate hydrate: N-C-S-H, in cement chemist notation) belonging to the class of phyllosilicates. Gyrolite is also often associated with zeolites. It is most commonly found as spherical or radial formations in hydrothermally altered basalt and basaltic tuffs. These formations can be glassy, dull or fibrous in appearance.
Polymer soil stabilization refers to the addition of polymers to improve the physical properties of soils, most often for geotechnical engineering, construction, or agricultural projects. Even at very small concentrations within soils, various polymers have been shown to increase water retention and reduce erosion, increase soil shear strength, and support soil structure. A wide range of polymers have been used to address problems ranging from the prevention of desertification to the reinforcement of roadbeds.
Geopolymer bonded wood composite (GWC) are similar and a green alternatives to cement bonded wood composites. These products are composed of geopolymer binder, wood fibers/ wood particles. Depending on the wood and geopolymer ratio in the material, the properties of the wood-geopolymer composite material vary. The main functions of wood in the composite material are weight reduction, reduction of thermal conductivity and the fixture function whereas the main functions of geopolymer are bonding of wood particles, improvement of fire resistance, providing mechanical strength, improvement of humidity resistance and protection against fungal and insect damages.
Susan Andrea Bernal López is a Colombian materials scientist who is Professor of Structural Materials at the University of Leeds. Her research considers design, development and characterisation of novel cements. She was awarded the 2020 Institute of Materials, Minerals and Mining Rosenhain Medal and Prize.