Milena Adams

Dr. Juan Pablo Gevaudan Burgos

MATSE 496

5 May, 2021

An Overview of the Intersection of Sustainable Materials, Rheology, and Structural

Engineering

Introduction

Materials science and engineering play a crucial role in the architecture and construction

of all types of tangible infrastructure. Starting any structural project with the fundamentals of

materials is a bottom-up type of approach that can make a huge difference in the technology,

sustainability, and functionality of any design [1]. As structural technology advances, it is

important to integrate a more holistic view of materials selection that considers sustainability

metrics such as carbon emissions and energy consumption throughout the life cycle of the

structure and materials. Despite the relatively small carbon footprint by mass of concrete, it

makes up 70% of all structural materials in the world [1] and is responsible for the majority of

emissions from construction [2]. Therefore, there is a specific focus in this field on alternative

cementitious materials (ACMs).

Concrete is a particularly popular construction material due to its ease of formability in

the fresh state as well as its mechanical properties and durability in the hardened state [1]. In

order to move forward with the innovative technology of additive manufacturing (AM) of

alkali-activated materials (AAMs), we must understand the effects of fundamental materials

science phenomena, including rheology, shear stress vs. shear strain rate, mixture composition,
characterization, surface chemistry, and kinetics. Here, we examine established research and

potential future research on these phenomena and the role they play in the progressing

technology of AAMs.

Rheology of Alkali-Activated Materials

Alkali-activated materials (AAMs) are a popular, more sustainable alternative to

conventionally implemented Portland cement materials (PCMs), consuming less energy and

emitting less CO2. They can be manufactured using an alkaline activator (usually an aqueous

solution of alkali hydroxide, silicate, or carbonate) to activate a reactive solid aluminosilicate

such as blast furnace slag, fly ash, or metakaolin [3].

Although there are established studies on rheology of AAMs and this technology is

progressing, a better understanding of materials science phenomena is needed for better mix

design in order for more substantial and widespread implementation of AAMs in industry. There

are several empirical models that describe the relationships between shear stress, shear strain

rate, and viscosity depending on starting aluminosilicate and activator composition. AAMs may

be described by the Bingham, modified Bingham, or Herschel-Bulkley (H-B) equations,

depending on these factors. Other components of the paste also affect the rheological parameters

in these equations. Activators also affect rheological behavior depending on ion nature,

concentration, viscosity of initial activator solution, and method of activation, as well as

admixtures and mineral additions, aggregates, and fibers. In order for research to continue

progressing on this topic, we must better understand the effects of shrinkage risk of AAMs and

inconsistency of raw materials and activators. It is necessary to improve the workability and

viscosity of AAMs due to the fact that rheological additives don’t work as well in AAMs as they
do in Portland cement materials (PCMs). This can be attributed to chemical stability and

solubility in the alkaline environment as well as competitive adsorption between multiple anionic

species [3].

Figure 1. The yield stress (a) and plastic viscosity (b) of fresh fly ash-slag blended pastes activated by

different concentrations of NaOH [3]

Additive Manufacturing of Construction Materials

Additive manufacturing builds a structure in successive layers, which can provide the

benefits of automatic construction while reducing excess material waste and labor. AM of

cementitious materials especially has potential for constructing freeform components in

buildings [4]. Rheology modifier agents and reinforcing additives, such as PVA, PP, attapulgite,

and nano-graphite particles may eventually lead to more widespread implementation of AAMs,

due to their ability to improve mechanical properties and workability for printing [5].

There are two types of AM in this field: extrusion 3D printing and powder-based 3D

printing. The extrusion method is usually used for on-site construction of large-scale

components. In extrusion printing, the (alternative) cementitious material must be pumped

through a hose and into the 3D printer, and this is where rheology comes into play. The
functionality and overall possibility of these 3D-printer materials are directly dependent on the

workability and rheology of the paste that is being pumped through and extruded [6].

There is a dilemma here: keeping the viscosity low enough to flow through the hose, but

high enough to keep its shape when printed. This means that the mixture must be thixotropic in

nature, where it has a low viscosity during flow and high yield stress after extrusion [6]. The area

of thixotropy depends on the ratio of fly ash to slag in relevant mixtures [3]. In one study by

Panda et. al [4], the inclusion of up to 10% silica fume (SF) in fly ash-based geopolymer blends

for extrusion 3D printing was effective at limiting the yield stress and viscosity in the

freshly-mixed state, making extrusion smoother, but also succeeded in creating a freeform 3D

part. However, the effects of additives in geopolymer blends are highly dependent on inherent

composition factors and various polycondensation reactions [4]. Hence, there is a need to

understand how these reactions during activation affect the temporal evolution of the rheological

performance of these materials.

Powder-based 3D printing is usually used for smaller building components, such as

panels, that are made and then assembled on-site. In this printing process, the nozzle deposits

binder liquid into a powder bed. Geopolymer-based materials have shown the ability to replace

the commercially-available materials conventionally used in powder-based printers.

Additionally, a post-processing method can be used to increase the strength enough to be suitable

for some construction applications [6].

Combining Raman Spectroscopy and Rheology

Phase transitions and critical rheological changes, such as glass transition and heat

deflection temperature, greatly affect any extrusion process [7]. Transition temperatures are
especially relevant to organic polymer dispersion binders [8] and polymer-modified cement [9].

Rheological testing methods can identify these transitions, but results often rely on empirical

assumptions and there is a lack of connection to the atomic structure of the cementitious binder.

Raman spectroscopy can be used in combination with rheological testing simultaneously to

provide information about the chemical composition and structure of the cementitious binder. In

order to capture data from both the rheological testing and the Raman spectroscopy

simultaneously, a quartz glass plate can be used as a platform for the sample being rheologically

measured. A Raman fiber probe can then acquire Raman spectra without any silica background

from the quartz plate [10]. Although this rheo-Raman shows promising results in a study by

Napp et. al [10], there is little to no research specifically available on simultaneous rheo-Raman

analysis of ACMs.

Figure 2. Experimental setup for rheo-Raman testing [8]

Surface Chemistry, Kinetics, and Rheology

Monitoring particle surface charge (zeta potential) in conjunction with measuring pH and

heat changes during the early stages of reaction between slag and alkali-activating solution can

give insight into how surface chemistry is connected to rheology. In a study by Kashani et. al
[11] using sodium and potassium hydroxide silicate solutions to activate blast furnace slag, it was

shown that both the formation of solid products and the yield stress increase with higher reaction

rate. Although pH did not show a direct influence on the chemistry of the paste, there is a direct

relationship between dosage of activators and zeta potential. Zeta potential is measured by

measuring the movement of colloidal particles under the influence of an applied electric field.

Zeta potential measurements are used to monitor changes in electric double layer forces with

varying pH and electrolytic environment, as these factors determine the location and charges on

the particle surface. The yield stress has been shown to depend on the square of the zeta

potential. This relationship differs depending on the type of slag and activators. A zeta potential

further from neutrality often indicates a lower yield stress by increasing the repulsion within the

electric double layer; on the other hand, higher dosage of silicate activator shows some attraction

within the double layer. Specific inter-particle interactions and gelation are both influenced by

which activator is chosen [11].

Potential Future Work

Looking forward, more research can be pursued with simulation to discover empirical

models of stress vs strain, depending on activators used [3]. Machine learning could eventually

be implemented here to use training data from test runs of different shear stress vs. shear strain

rate models for various AAMs in order to derive a more comprehensive or integrated model(s) as

a function of composition [12]. More robust formulations are required to improve the rheological

and mechanical requirements of AAMs; this would involve more in-depth research on organic

and inorganic plasticizers to optimize workability. In order for research to continue progressing

on this topic, we need to overall better understand the effects of shrinkage risk of AAMs and
inconsistency of raw materials and activators [3]. There is also a need for the development of

empirical equations to describe the effect of fibers and additives on rheological properties,

similarly to the Bingham, modified Bingham, and H-B equations for shear stress and shear strain

rate [3]. There is also some work to be done in research on more additives beyond PVA fibers

and attapulgite nano-clay, such as PP and nano-graphite particles [4].

More research can be done on post-processing methods to further increase strength of

geopolymer-based 3D-printed materials enough to make them suitable for even more

construction applications [6]. Researchers may have to further examine shear history and surface

chemistry. There is a definite need for research in the rheo-Raman analysis of ACMs and AAMs,

as there is very little established work in this area and there may be a lot to gain from

simultaneous analysis of chemical composition, transitional rheological points, and shear stress,

shear strain rate, and viscosity measurements [10]. More in-depth research is needed to

understand the chemical reaction mechanisms that occur to cause changes in inter-particle forces

within the cement [11]. This will open up more of an understanding to how the zeta potential,

activator type, and activator dosage affect its rheological properties.

References:

[1] Bechthold, Martin, and James C. Weaver. “Materials Science and Architecture.” Nature

Reviews Materials, vol. 2, no. 12, 2017. Crossref, doi:10.1038/natrevmats.2017.82.

[2] Rao, N. Venkat, et al. “The Future of Civil Engineering with the Influence and Impact of

Nanotechnology on Properties of Materials.” Procedia Materials Science, vol. 10, 2015, pp.

111–15. Crossref, doi:10.1016/j.mspro.2015.06.032.

[3] Lu, Cuifang, et al. “Rheology of Alkali-Activated Materials: A Review.” Cement and

Concrete Composites, 2021, p. 104061. Crossref, doi:10.1016/j.cemconcomp.2021.104061.

[4] Panda, Biranchi, et al. “Investigation of the Rheology and Strength of Geopolymer Mixtures

for Extrusion-Based 3D Printing.” Cement and Concrete Composites, vol. 94, 2018, pp. 307–14.

Crossref, doi:10.1016/j.cemconcomp.2018.10.002.

[5] Chougan, Mehdi, et al. “Investigation of Additive Incorporation on Rheological,

Microstructural and Mechanical Properties of 3D Printable Alkali-Activated Materials.”

Materials & Design, vol. 202, 2021, p. 109574. Crossref, doi:10.1016/j.matdes.2021.109574.

[6] Xia, Ming, and Jay Sanjayan. “Method of Formulating Geopolymer for 3D Printing for

Construction Applications.” Materials & Design, vol. 110, 2016, pp. 382–90. Crossref,

doi:10.1016/j.matdes.2016.07.136.

[7] Bors, John. “Comparing and Explaining Polymers in Concrete Construction, Protection and

Repair.” ChemCo Systems, 2020,

info.chemcosystems.com/blog/comparing-and-explaining-polymers-in-concrete-construction-pro

tection-and-repair.

[8] Jansen, D., et al. “The Influence of the Glass Transition Temperature (Tg) of Polymers on

Early OPC Hydration: A Complete Study of the Heat Flow, Phase Evolution, and Pore Solution

Chemistry.” Materials and Structures, vol. 52, no. 6, 2019. Crossref,

doi:10.1617/s11527-019-1435-9.

[9] Nasvik, Joe. “UNDERSTANDING POLYMERS IN CONCRETE.” Concrete Construction,

2001, www.concreteconstruction.net/how-to/materials/understanding-polymers-in-concrete_o.
[10] Napp, Katharina E., et. al. “Combined Raman Spectroscopy and Rheology for

Characterizing.” Spectroscopy, vol. 34, no. 9, 2019, pp. 38–43,

www.spectroscopyonline.com/view/combined-raman-spectroscopy-and-rheology-characterizing.

[11] Kashani, Alireza, et al. “The Interrelationship between Surface Chemistry and Rheology in

Alkali Activated Slag Paste.” Construction and Building Materials, vol. 65, 2014, pp. 583–91.

Crossref, doi:10.1016/j.conbuildmat.2014.04.127.

[12] “Machine Learning: What It Is and Why It Matters.” SAS, 2020,

www.sas.com/en_us/insights/analytics/machine-learning.html#:%7E:text=Machine%20learning

%20is%20a%20method,decisions%20with%20minimal%20human%20intervention.