Energetically modified cement

Energetically modified cements (EMCs) are a class of cements made from pozzolans (e.g. fly ash, volcanic ash, pozzolana), silica sand, blast furnace slag, or Portland cement (or blends of these ingredients). 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). 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". 
By improving the reactivity of pozzolans, their strength-development "rate" is increased. This allows for compliance with modern product-performance requirements ("technical standards") for concretes and mortars. In turn, this allows for the replacement of Portland cement in the concrete and mortar mixes. This has a number of benefits to their long-term qualities.
Energetically modified cements have a wide range of uses. For example, EMCs have been used in concretes for large infrastructure projects in the United States, meeting U.S. concrete standards.
Justification.
The term "energetically modified cement" incorporates a simple thermodynamic descriptor to refer to a class of cements produced using a specialised highly intensive milling process first discovered in 1993 at Luleå University of Technology (LTU) in Sweden. The transformatory process is initiated entirely mechanically as opposed to heating the materials directly. The mechanisms of mechanochemical transformations are often complex and different from "traditional" thermal or photochemical mechanisms. The effects of HEBM-transformation cause a thermodynamic change that resides ultimately in a modified Gibbs Energy. The process increases the binding capacity and chemical reactivity rates of the materials transformed.
Continuing academic work and research regarding "self-healing" properties of energetically modified cements is ongoing at LTU. For example, EMCs has received awards from the "Elsa ō Sven Thysells stiftelse för konstruktionsteknisk forskning" (Elsa & Sven Thysell Foundation for Construction Engineering Research) of Sweden.
Usage of the "EMC" term.
The term "energetically modified cement" was first used in 1992 by Vladimir Ronin, introduced in a paper by Ronin et al. dated 1993 and presented at a formal meeting of the academic Nordic Concrete Research group. The process was refined by Ronin and others, including Lennart Elfgren (now Professor Emeritus of LTU).
At the 45th World Exhibition of Invention, Research and Innovation, held in 1996 in Brussels, Belgium, EMC Activation was awarded a gold medal with mention by EUREKA, the European inter-governmental (research and development) organisation, for "modification énergique de ciments".
The term "energetically modified" has been used elsewhere—for example as recently as 2017—although such usage does not denote the method used was EMC Activation as defined here.
Overview.
The claims made include:
EMCs as "Low Carbon" cements.
Unlike Portland Cement, an EMC's production releases no carbon dioxide whatsoever. This makes EMCs "low carbon cements".
The first cited claims for EMC's CO2-reduction capabilities were made in 1999, when worldwide Portland cement production stood at 1.6 billion tonnes per year. From 2011 to 2019, worldwide Portland cement production increased from 3.6 to 4.1 billion tonnes per year. Energetically modified cement's potential for contributing to a worldwide reduction of CO2 has been "externally" recognised since 2002 and has been ongoing.
In its 2020 article "Laying the foundation for zero-carbon cement", McKinsey & Co stated:
Production and field-usage.
No noxious emissions or toxic chemicals during production.
EMC Activation is purely a mechanical process. As such, it does not involve heating or burning or indeed any chemical treatments. This means no fumes at all are produced during an EMC's manufacture.
History of Usage.
EMCs have been produced for project usage since 1992 for a wide range of uses. By 2010, the volume of concrete poured containing EMCs was about 4,500,000 cu yd (3,440,496 m3), largely on US DOT projects. To place this into context, that is more than the entire construction of the Hoover Dam, its associated power plants and appurtenant works, where a total of 4,360,000 cu·yds (3,333,459 m³) of concrete was poured—equivalent to a U.S. standard highway from San Francisco to New York City.
Early Usage in Sweden.
An early project using EMC made from fly ash was the construction of a road bridge in Karungi, Sweden, in 1999, with Swedish construction firm Skanska. The Karungi road bridge has withstood Karungi's harsh subarctic climate and divergent annual and diurnal temperature ranges.
Usage in the United States.
In the United States, energetically modified cements have been approved for usage by a number of state transportation agencies, including PennDOT, TxDOT and CalTrans.
In the United States, highway bridges and hundreds of miles of highway paving have been constructed using concretes made from EMC derived from fly ash. These projects include sections of Interstate 10. In these projects, EMC replaced at least 50% of the Portland cement in the concrete poured. This is about 2.5 times more than the typical amount of fly ash in projects where energetic modification is not used. Independent test data showed 28-day strength-development requirements were exceeded in all projects.
Another project was the extension of the passenger terminals at the Port of Houston, Texas, where energetically modified cement's ability to yield concretes that exhibit high resistances to chloride– and sulphate–ion permeability (i.e., increased resistance to sea waters) was a factor.
Properties of concretes and mortars made from EMCs.
Custom design for end-usage.
The performance of mortars and concretes made from EMCs can be custom-designed. For example, EMC concretes can range from general application (for strength and durability) through to the production of rapid and ultra-rapid hardening high-strength concretes (for example, over 70 MPa / 10,150 psi in 24 hours and over 200 MPa / 29,000 psi in 28 days). This allows energetically modified cements to yield High Performance Concretes.
Durability of EMC concretes and mortars.
Any cementitious material undergoing EMC Activation will likely marshal improved durability—including Portland cement treated with EMC Activation. As regards pozzolanic EMCs, concretes made from pozzolanic EMCs are more durable than concretes made from Portland cement.
Treating Portland cement with EMC activation will yield high-performance concretes (HPCs). These HPCs will be high strength, highly durable, and exhibiting greater strength-development in contrast to HPCs made from untreated Portland cement. Treating Portland cement with the EMC Activation process may increase the strength development by nearly 50% and also significantly improve the durability, as measured according to generally accepted methods.
Enhanced resistance to salt-water attack.
Concrete made from ordinary Portland cement without additives has a relatively impaired resistance to salt waters. In contrast, EMCs exhibit high resistances to chloride and sulphate ion attack, together with low alkali-silica reactivities (ASR). For example, durability tests have been performed according to the "Bache method" (see diagram). Samples made of HPC having respective compressive strengths of 180.3 and 128.4 MPa (26,150 and 18,622 psi) after 28 days of curing, were then tested using the Bache method. The samples were made of (a) EMC (comprising Portland cement and silica fume both having undergone EMC Activation) and (b) Portland cement. The resulting mass-loss was plotted in order to determine durability. As a comparison, the test results showed:
In other words, treating Portland cement with the EMC Activation process, may increase the strength-development by nearly 50% and also significantly improve the durability, as measured according to generally accepted methods.
Low leachability of EMC Concretes.
Leachability tests were performed by LTU in 2001 in Sweden, on behalf of a Swedish power production company, on concrete made from an EMC made from fly ash.  These tests confirmed that the cast concrete "showed a low surface specific leachability" with respect to "all environmentally relevant metals."   
EMCs using Pozzolans such as volcanic materials.
Self-healing properties of Pozzolanic EMCs.
Natural pozzolanic reactions can cause mortars and concretes containing these materials to "self-heal". The EMC Activation process can increase the likelihood of the occurrence of these pozzolanic reactions. The same tendency been noted and studied in the various supporting structures of Hagia Sophia built for the Byzantine emperor Justinian (now, Istanbul, Turkey). There, in common with most Roman cements, mortars comprising high amounts of pozzolana were used — in order to give what was thought to be an increased resistance to the stress-effects caused by earthquakes.
EMCs made from pozzolanic materials exhibit "biomimetic" self-healing capabilities that can be photographed as they develop "(see picture insert)."
EMCs using California Pozzolans.
Concretes made by replacing at least 50% of the Portland cement with EMCs have yielded consistent field results in high-volume applications. This is also the case for EMC made from natural pozzolans (e.g., volcanic ash).
Volcanic ash deposits from Southern California were independently tested; at 50% Portland cement replacement, the resulting concretes exceeded the requirements of the relevant US standard. At 28 days, the compressive strength was 4,180 psi / 28.8 MPa (N/mm²). The 56-day strength exceeded the requirements for 4,500 psi (31.1 MPa) concrete, even taking into account the safety margin as recommended by the American Concrete Institute. The concrete made in this way was workable and sufficiently strong, exceeding the 75% standard of pozzolanic activity at both 7 days and 28 days. The surface smoothness of pozzolans in the concrete was also increased.
Effect on Pozzolanic reactions.
EMC Activation is a process that increases a pozzolan's chemical affinity for pozzolanic reactions. This leads to faster and greater strength development of the resulting concrete, at higher replacement ratios, than untreated pozzolans. These transformed (now highly reactive pozzolans) demonstrate further benefits using known pozzolanic reaction-pathways that typically see as their end-goal a range of hydrated products. An NMR study on EMCs concluded that EMC Activation caused "the formation of thin SiO2 layers around C3S crystals", which in turn, "accelerates the pozzolanic reaction and promotes growing of more extensive nets of the hydrated products".
In simple terms, by using pozzolans in concrete, porous (reactive) Portlandite can be transformed into hard and impermeable (relatively non-reactive) compounds, rather than the porous and soft relatively reactive calcium carbonate produced using ordinary cement. Many of the end products of pozzolanic chemistry exhibit a hardness greater than 7.0 on the Mohs scale."Self healing" capabilities may also contribute to enhanced field-application durabilities where mechanical stresses may be present.
In greater detail, the benefits of pozzolanic concrete, starts with an understanding that in concrete (including concretes with EMCs), Portland cement combines with water to produce a stone-like material through a complex series of chemical reactions, whose mechanisms are still not fully understood. That chemical process, called mineral hydration, forms two cementing compounds in the concrete: calcium silicate hydrate (C-S-H) and calcium hydroxide (Ca(OH)2). This reaction can be noted in three ways, as follows:
</chem>
The underlying hydration reaction forms two products:
Portlandite makes up about 25% of concrete made with Portland cement without pozzolanic cementitious materials. In this type of concrete, carbon dioxide is slowly absorbed to convert the Portlandite into insoluble calcium carbonate (CaCO3), in a process called carbonatation:
In mineral form, calcium carbonate can exhibit a wide range of hardness depending on how it is formed. At its softest, calcium carbonate can form in concrete as chalk (of hardness 1.0 on Mohs scale). Like Portlandite, calcium carbonate in mineral form can also be porous, permeable and with a poor resistance to acid attack, which causes it to release carbon dioxide.
Pozzolanic concretes, including EMCs, however, continue to consume the soft and porous Portlandite as the hydration process continues, turning it into additional hardened concrete as calcium silicate hydrate (C-S-H) rather than calcium carbonate. This results in a denser, less permeable and more durable concrete. This reaction is an acid-base reaction between Portlandite and silicic acid (H4SiO4) that may be represented as follows:
Further, many pozzolans contain aluminate (Al(OH)4−) that will react with Portlandite and water to form:
Pozzolanic cement chemistry (along with high-aluminate cement chemistry) is complex and per se is not constrained by the foregoing pathways. For example, strätlingite can be formed in a number of ways, including per the following equation which can add to a concrete's strength:
The role of pozzolans in a concrete's chemistry is not fully understood. For example, strätlingite is metastable, which in a high temperature and water-content environment (that can be generated during the early curing stages of concrete) may of itself yield stable calcium aluminium garnet (see first bullet point above). This can be represented per the following equation:
Per the first bullet point, although the inclusion of calcium aluminium garnet per se is not problematic, if it is instead produced by foregoing pathway, then micro-cracking and strength-loss can occur in the concrete. However, adding high-reactivity pozzolans into the concrete mix prevents such a conversion reaction. In sum, whereas pozzolans provide a number of chemical pathways to form hardened materials, "high-reactivity" pozzolans such as blast furnace slag (GGBFS) can also stabilise certain pathways. In this context, EMCs made from fly ash have been demonstrated to produce concretes that meet the same characteristics as concretes comprising "120 Slag" (i.e., GGBFS) according to U.S. standard ASTM C989.
Portlandite, when exposed to low temperatures, moist conditions and condensation, can react with sulphate ions to cause efflorescence; pozzolanic chemistry reduces the amount of Portlandite available, to reduce efflorescence.
EMC Activation.
EMC Activation's purpose is to cause a fundamental destruction to the crystalline structure of the material processed, to render it amorphous. Although this change increases the processed material's chemical reactivity, no chemical reaction is caused "during" the EMC Activation process.
Mechanochemistry itself can be defined as a branch of chemistry which is concerned with the "chemical and physico-chemical transformation of substances in all states of aggregation produced by the effect of mechanical energy." IUPAC carries no standard definition of the term "mechanochemistry", instead defining a "mechanochemical "reaction"" as a chemical reaction "induced by the direct absorption of mechanical energy", while noting, "shearing, stretching, and grinding are typical methods for the mechano-chemical generation of reactive sites".
More narrowly, "mechanical activation" was a term first defined in 1942 as a process "involving an increase in reaction ability of a substance "which remains chemically unchanged"." Even more narrowly, EMC Activation is a specialised form of mechanical activation limited to the application of high energy ball milling (HEBM) to cementitious materials. More narrowly than that, EMC Activation uses vibratory milling, and even then, only by using its own "grinding media".
Thermodynamic Justification.
More particularly, HEBM can be described as increasing the chemical reactivity of a material by increasing its chemical "potential" energy. In EMC Activation, transferred mechanical energy is stored in the material as lattice defects caused by destroying the material's crystalline structure. Hence, the process transforms solid substances into thermodynamically and structurally more "unstable" states, allowing an explanation for that increased reactivity as an increase in Gibbs energy:
At its simplest, HEBM causes the destruction of crystalline bonds, to increase a material's reactivity. From the thermodynamic perspective, any subsequent chemical reaction can decrease the excess energy level in the activated-material (i.e. as a reactant) to produce new components comprising both a lower chemical energy and a more stable physical structure. Conversely, to render the pre-processed material into a more reactive physical state, the disordering process during the HEBM process can be justified as being equivalent to a "decrystallisation" (and hence an entropy increase) that in part yields a volume increase (decrease of bulk density). A reverse process, sometimes called "relaxation", can be almost immediate (10−7 to 10−3 seconds) or take much longer (e.g. 106 seconds). Ultimately, any overall "retained" thermodynamic effect can be justified on the basis that any such "reverse" process is incapable of reaching an ideal thermodynamic end-state of its own accord. As a result, in the course of the mechanical activation of minerals, reverse "relaxation" processes cannot completely decrease the Gibbs free energy that has been created. Hence, energy remains in the material, which is stored in the crystal-lattice "defects" created.
Net Thermodynamic Effect of HEBM.
Overall, HEBM renders a net thermodynamic effect:
Resulting Crystalline Disorder.
Where the crystal disordering is low, formula_7 is very small (if not negligible). In contrast, in highly deformed and disordered crystals, the values of formula_7 can have a significant impact on the rendered Gibbs free energy.
Leaving aside the heat generated during the process on account of friction etc. occasioned during the activation process, the excess Gibbs free energy retained in the activated material can be justified as being due to two changes, namely an increase in (formula_10) specific surface area; and (formula_10formula_10) defect structure. In successful HEBM processes such as EMC Activation:
An approximation for EMC Activation.
The relatively low value of (formula_10) as against the high value of (formula_10formula_10) serves to further distinguish HEBM from general grinding or "milling" (where instead the only aim there is to increase the surface area of the materials processed), thereby accounting for an explanation for the change in entropy formula_19 of the rendered material in the form of elastic energy (stored in lattice defects that can take years to "relax" ) that is the "source of excess Gibbs energy and enthalpy". As for enthalpy formula_20, four descriptors can be derived to provide an overview as to the total change during such an activation process:<br>
Because the majority of the work exacted during the EMC Activation process goes to aspect (formula_10formula_10) above, formula_25 is trivial. Hence the major functions for the change in enthalpy approximate to:<br>
In EMC Activation, the foregoing terms formula_22 and formula_24 are seen as being particularly prominent because of the nature of the changes in the physical structure observed. Hence, the change in enthalpy formula_20 occasioned during EMC Activation can be approximated to:
Low temperature reactivity.
From the above thermodynamic construct, EMC Activation results in a highly "amorphous" phase that can be justified as a large formula_24 and also a large formula_22 increase. The benefits of the EMC Activation being large in formula_20 means that an EMC's reactivity is less temperature dependent. In terms of any reaction's thermodynamic impetus, a reactant's overall formula_20 is not formula_2 dependent, meaning that a material having undergone HEBM with a corresponding elevation of formula_20 can react at a lower temperature (as the "activated" reactant is rendered less reliant on the temperature-dependent function formula_47 for its onward progression). Further, an EMC's reaction can exhibit physical mechanisms at extremely small scales "with the formation of thin SiO2 layers" to aid a reaction's pathway—with the suggestion that EMC Activation increases the ratio of favourable reaction sites. Studies elsewhere have determined that HEBM can significantly lower the temperature required for a subsequent reaction to proceed (up to a three-fold reduction), whereby a major component of the overall reaction-dynamics is initiated at a "nanocrystalline or amorphous phase" to exhibit "unusually low or even negative values of the apparent activation energy" required to cause a chemical reaction to occur.
Overall, EMCs are likely less temperature dependent for a chemical pathway's onward progression (see section above on Pozzolanic reactions), which may explain why EMCs provide "self-healing" benefits even at low arctic temperatures.
Physical Justification (Amorphisation).
Large changes in formula_48, more particularly in the resultant values of formula_24 and formula_22 provide an insight into EMC Activation's efficacy. The amorphisation of crystalline material at high-pressure conditions "is a rather unusual phenomenon" for the simple reason that "most materials actually experience the reverse transformation from amorphous to crystalline at high-pressure conditions". Amorphisation represents a highly distorted "periodicity" of a material's lattice element, comprising a relatively high Gibbs free energy. Indeed, amorphisation may be compared to a "quasi-molten" state.
All told, in common with other HEBM processes, EMC Activation causes crystalline destruction because of extremely violent and disruptive factors that are occasioned at the nanoscale of the material being processed. Although over in short duration and highly focal, the processes are repeated at a high frequency: hence those factors are thought to mimic pressures and temperatures found deep inside the Earth to cause the required phase change. For example, Peter Thiessen developed the "magma-plasma model" that assumes localised temperatures—higher than 103 Kelvin—can be generated at the various impact points to induce a momentary excited plasma state in the material, characterized by the ejection of electrons and photons together with the formation of excited fragments (see diagram above). Experimental data gathered from localised crack-generation, itself an important component of EMC Activation, has confirmed temperatures in this region as long ago as 1975.
Vibratory Ball Mills (VBMs).
For EMC activation, the HEBM method used is a vibratory ball mill (VBM). A VBM uses a vertical eccentric drive-mechanism to vibrate an enclosed chamber up to many hundreds of cycles per minute. The chamber is filled with the material being processed together with specialised objects called "grinding media". In their most simple format, such media can be simple balls made from specialised ceramics. In practical terms, EMC Activation deploys a range of grinding media of different sizes, shapes and composites to achieve the required mechanochemical transformation.
It has been suggested that a VBM will grind at 20 to 30 times the rate of a rotary ball mill, reflecting that a VBM's mechanism is especially rapacious.
VBM Kinetics.
In simple terms, the compressive force formula_51 acting between two "identical" colliding balls in a VBM can be expressed:<br>
<br>
<br>As can be seen, an increase in velocity of impact increases formula_51. The size and mass of the grinding media also contribute. formula_51's denominator term formula_60 incorporates formula_57 meaning that the nature of the material used for the grinding media is an important factor (formula_60 is ultimately squared in formula_51, so its negative value is of no consequence). More fundamentally, due to the rapid vibration a high acceleration is imparted to the grinding media, whereupon the continuous, short, sharp impacts on the load result in rapid particle-size reduction. In addition, high pressures and shear stresses facilitate the required phase transition to an amorphous state both at the point of impact and also during the transmission of shock-waves that can yield even greater pressures than the impact itself.
For example, the contact time of a two-ball collision can be as short as 20μs, generating a pressure of 3.3 GPa upwards and with an associated ambient temperature increase of 20 Kelvin. Because of the short duration of the impact, the rate of change in momentum is significant—generating a shock wave of duration only 1-100μs but with an associated pressure of 10 GPa upwards and a highly localised and focal temperature (i.e., at the nanoscale) up to several thousands of degrees Kelvin. To place this into context, a pressure of 10GPa is equivalent to about 1,000 kilometers of sea water. As a further example, the impact of two identical steel balls of 2.5 cm diameter of velocity 1 m/s will generate a collision energy density of over 109 joules/m2, with alumina balls of the same 2.5 cm diameter and velocity of 1 m/s generating an even greater energy density. The collisions occur in a very short timescale and hence the "rate of energy release over the relatively small contact area can be very high".
See also.
Background science to EMC Activation:
Academic: