Chemical composition of fly ash (FA) and blast furnace slag (GBFS).
\r\n\t
",isbn:"978-1-83881-920-0",printIsbn:"978-1-83881-919-4",pdfIsbn:"978-1-83881-933-0",doi:null,price:0,priceEur:0,priceUsd:0,slug:null,numberOfPages:0,isOpenForSubmission:!1,hash:"c1999f94cbb4a0340032feb750236ffa",bookSignature:"Prof. Zamzuri Idris",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/9656.jpg",keywords:"Paediatric Brain Injury, Adult Brain Injury, Brain Swelling, Immune Response, Brainwaves, Endocrine, Neuromonitoring, Intensive Care, Hypothermia, Neuroimaging, Brain-computer Interface, Robotic Rehabilitation",numberOfDownloads:1131,numberOfWosCitations:0,numberOfCrossrefCitations:0,numberOfDimensionsCitations:0,numberOfTotalCitations:0,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"June 2nd 2020",dateEndSecondStepPublish:"September 9th 2020",dateEndThirdStepPublish:"November 8th 2020",dateEndFourthStepPublish:"January 27th 2021",dateEndFifthStepPublish:"March 28th 2021",remainingDaysToSecondStep:"7 months",secondStepPassed:!0,currentStepOfPublishingProcess:5,editedByType:null,kuFlag:!1,biosketch:"Dr. Idris is acting as the Head of the Committee in Malaysia Neurosurgical Teaching and Education, Head for the Local Neurosurgical Association of Malaysia, Member for the Society for Brain Mapping and Therapeutics USA, for the European Society for Stereotactic and Functional Neurosurgery. He has graduated from the University of Wales College of Medicine Cardiff, then pursued his postgraduate career at Universiti Sains Malaysia. He completed his fellowship program at the University of Gent, Belgium.",coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"73844",title:"Prof.",name:"Zamzuri",middleName:null,surname:"Idris",slug:"zamzuri-idris",fullName:"Zamzuri Idris",profilePictureURL:"https://mts.intechopen.com/storage/users/73844/images/system/73844.png",biography:"Prof Dr Zamzuri Idris had graduated from University of Wales College of Medicine Cardiff UK in 1994, then pursued his postgraduate career in Neurosurgery locally at Universiti Sains Malaysia. In 2007, he completed his fellowship programme in Gent Belgium under Prof J. Caemaert in Neuroendoscopy and Prof D. Van Roost in Functional Neurosurgery. He is currently the Head of Neuroscience Department and holds various important posts related to Neurosurgery, Neurosciences and Scientific Society. He is currently acting as the Head of the Committee in Malaysia Neurosurgical Teaching and Education, Head for the Local Neurosurgical-Board Examination and an Executive Committee Member for Neurosurgical Association of Malaysia, Member for the Society for Brain Mapping and Therapeutics USA, for the European Society for Stereotactic and Functional Neurosurgery (ESSFN) and for the Asia Pacific Low Grade Glioma Network. His major interests are in brain trauma, minimally invasive neurosurgery (neuroendoscopy), precision radiation therapy, epilepsy, brain mapping, brain stimulation, brainwaves and lately in Quantum Brain. 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About 4.2 GJ energy is required to produce 1 metric ton PC, resulting approximately in 0.8–1.0 metric ton of CO2 release into the atmosphere [2]. A second problem besides CO2 emissions is connected with the negative ecological and health impact of red and brown mud ponds in the manufacture of aluminium-containing high-alkaline waste water rich in NaOH. Landfilling of this hazardous waste raises other problems due to the high concentrations of heavy metals and the variety in chemical composition depending to a large extent on the season and weather conditions. The main task of the current research is the development of less energy-intensive but more ecological cements. One solution is the production of innovative cement binders like alkali-activated cements, geopolymers and hybrid alkaline cements with Portland clinker addition [3, 4]. The hybrid alkaline cements have various compositions of alkali-activated aluminosilicates with low Portland clinker content [5]. In spite of the low clinker content, the hybrid binders can obtain useful early-age mechanical strengths [6]. Hybrid cements take advantage of the material properties of a cement and ordinary geopolymer with the resulting benefit on the acquired properties, so that hybrid cement can replace in large quantities energy-intensive PC [7]. The novel hybrid cement H-Cement is produced on the base of industrial by-products and wastes according to the patent application [8]. The content of clinker is always under 30 wt%. A typical feature for H-Cement binding phase formation is the combined effect of hydraulic properties of Portland clinker, pozzolanic properties of fly ashes, latent hydraulic properties of granulated blast furnace slag (GBFS) and geopolymeric properties coming from the alkaline inorganic polycondensing reactions of aluminosilicate materials. Such inorganic material is activated by addition of alkaline waste water separated from the caustic red mud ponds and Na2SO4 obtained from alkaline waste water neutralization by H2SO4. In the presence of these alkaline agents, the pH value of cement mixture is increased. This results in fly ash (FA) and GBFS dissolution leading to final geopolymerization effect. At the same time, Ca(OH)2 addition coming from Portland clinker hydration promotes the binding reactions of fly ash and GBFS. H-Cement is characterized by lower early strength and hydration heat but higher long-term strengths. H-Cement possesses high chemical resistance against aggressive action of sulphate, magnesium, chloride and acidic waters [9]. When autoclaving at an elevated temperature and pressure, H-Cement provided volume stability and strength increase in concrete with steel slag replacing a natural aggregate as opposed to PC concrete with steel slag which was disintegrated after the test [10].
The production of H-Cement does not require additional heat treatment. It is cured in the same way as traditional cements and owns the certificate of conformity [11] issued on the base of SK Technical Assessment [12]. H-Cement is a sustainable cement which, due to its material composition, does not meet the categorization of cements according to STN EN 197-1 [13].
This article shows that one possible solution for innovative binders with improved durability and decreased energy requirements is the production of hybrid cement. It is demonstrated that:
H-Cement is suitable for production of ready-mixed concrete strength classes up to C30/37.
Shrinkage-reducing and alkali-silica reaction (ASR)-mitigating character of H-Cement is especially relevant because it prevents propagation of shrinkage or expansive cracking during the service life of the concrete.
H-Cement is specified after 5-year impact of 5% wt. sodium sulphate solution by the same sulphate resistance with the sulphate-resistant CEM I 42.5 R-SR O with C3A = 0.
H-Cement is suitable for making concrete with mostly landfilled steel slag when replacing a natural aggregate.
The novel H-Cement and CEM I/42.5 R as a reference were tested. Both are produced by the cement plant Považská cementáreň, a. s., Ladce in Slovakia; H-Cement is according to internal standard. The cement was used in combination with river aggregates of 0/4, 4/8 and 8/16 mm fraction from Jelka (Slovakia). For the tests with steel slag, the river aggregate was completely replaced by the slag of the same fraction. All river aggregate properties met the requirements of STN EN 12620+A1 [14]. The compatibility of H-Cement was verified with seven types of plasticizers [15]. The concrete without admixture was examined as a reference. The shrinkage-reducing ability was confirmed on the concrete made from H-Cement, PC and selected blended systems [15]. The H-Cement suitability for mitigating alkali-silica reaction was verified on the cement mortars by the procedure reported in STN 721179 [16] (the related ASTM Standards: C289-03 for Chemical method; ASTM C1293-08b for length change of concrete). Resistance to sulphate and higher temperature/pressure attack was verified by own methodologies [10, 17].
Specimens of ready-mixed concrete were made according to STN EN 12390-2 [18]. Fresh concrete was compacted on a vibration table (40 Hz) for 60 s and casted into 150 mm cubes or 100 × 100 × 400 mm prisms. Casting of the specimens for verification of specific properties of H-Cement is reported separately for each experiment, either shrinkage-reducing or ASR-mitigating property, sulphate resistance and volume stability of steel slag concrete.
The moulds were stored at more than 95% relative humidity of air (abbreviated as RH) at (20 ± 1)°C for the first 24 h, and then the concrete specimens were cured according to the test. A method of treating the specimens for special properties verification is given separately for each test.
Both cements were tested for chemical composition by STN EN 196-2 [19]; the Bogue mineral composition was also determined. Standard consistency, initial and final setting, and soundness were verified by STN EN 196-3+A1 [20] and hydration heat by STN EN 196-8 [21]. After 2-, 28- or 90-day cure, flexural and compressive strengths of the mortars with cement-to-sand ratio 1:3 by weight were obtained according to STN EN 196-1 [22]. H-Cement is sensitive to excess of water; the PC and H-Cement mortars therefore differ in water-to-cement ratios.
The consistency of fresh concrete was estimated by slump by STN EN 12350-2, volume density by STN EN 12350-6 and air content in the fresh mixture by STN EN 12350-7 [23, 24, 25]. Concrete specimens were tested for cube compressive strengths [26], compressive strengths of the edges of prisms of standard size [27] and dynamic elasticity modulus [28].
Cement CEM I 42.5 R (PC) produced by Považská cementáreň, a. s., Ladce cement plant (PCLA) and C3A-free sulphate-resistant CEM I 42.5 R-SR O (SRC) produced by Lafarge Zementwerke GmbH, Mannersdorf (Austria) according to STN EN 197-1, both as reference, were chosen for the investigation. H-Cement was tested as the verified sample.
Mortars with cement-to-sand ratio of 1:3 by weight adjusted on the constant consistency of 140 ± 1 mm were prepared as prismatic specimens of size 40× 40× 160 mm. All specimens were kept for 5-year exposure in 5% wt. sodium sulphate (Na2SO4) solution and water as reference medium after 28-day water curing (BC) at (20 ± 1)°C. The tests of chemical resistance were conducted by own methodology of “partially accelerated test” based on keeping the mortars in strongly over-concentrated aggressive solution for a sufficient long time. The aggressive storage was specified by the following way: each 1 cm2 of the exposed area of prism must be in permanent contact with at least of 10 cm3 of 5% wt. Na2SO4 [33802.8 mg aggressive SO42− per 1 litre solution]. The sulphate solution and reference water were refreshed every 30 days within 90 days of testing, every 45 days between 90 and 365 days and every 60 days up to 5 years of exposure, respectively.
Consistency, density and fresh air content of the mortars were determined according to relevant STN EN Standards. The mortars were continuously tested for length changes, dynamic modules of elasticity (DME) and periodically flexural and compressive strength. After destructive tests the microstructure and pore structure were identified by X-ray diffraction (XRD), thermogravimetry-differential thermal analysis (TG-DTA), mercury intrusion porosimetry (MIP) and scanning electron microscopy (SEM) techniques. The ground material was sieved through a 0.063 mm mesh to receive the powder suitable for testing. For the X-ray diffraction, the Philips diffractometer was used in a 2Θ range of 5–65°. CuKα radiation and Ni filter were applied. Thermal analysis was performed on the Netzsch apparatus STA 449 F3 Jupiter in air at heating rate 10°C/min. Basic parameters of the pore structure were identified by MIP using the high-pressure porosimeter Quantachrome PoreMaster 60 GT using small mortar fragments for testing. The JEOL 7500F was used to study microstructure by scanning electron microscopy. Chemical composition, with special emphasis on the bound SO3 content, was estimated by STN EN 196-2 [19].
Two types of binders (PC and H-Cement as HC) were chosen to prepare concrete based on steel slag. The Sika® ViscoCrete®-225 powder superplasticizer was used to improve the consistency of the fresh concrete mixture. It provides water reduction, excellent fluidity and cohesion, together with a self-compacting effect. Tap water from the water supply system was used as the mixing water.
Two mixes designated as HC concrete and PC concrete were used within the scope of the experimental research.
HC concrete contained 0/8 mm steel slag fraction as filler, 380 kg of H-Cement, 241 kg of water, Sika superplasticizer in the amount of 0.5% of the cement weight and a retardant additive (Retardal 540) in the amount of 0.4% of the cement weight.
PC concrete contained 0/8 mm steel slag fraction as filler, 380 kg of CEM I 42,5 N, 241 kg of water and Sika superplasticizer in the amount of 0.5% of the cement weight. No retardant admixture was used.
The production of the specimens used to test the properties of fresh and hardened concrete based on steel slag was carried out in two stages. The first stage involved the production of the specimens for testing cube strength after 3, 7, 14, 21, 28 and 90 days of age. The second stage involved the production of the specimens for the comparison of cube and prism strengths after 28 days of curing.
The following properties of hardened concrete were tested: cube and prism concrete strengths. The durability of the concrete based on steel slag was tested in the conditions of a higher temperature and pressure. Determination of the volume changes of the concrete was carried out in a 540-l laboratory autoclave at the maximum saturated steam pressure of 1.2 MPa and a maximum temperature of 189°C. Cubes of 150 mm were used as the test specimens. The temperatures and pressures in the testing laboratory autoclave were set by this way to determine the volume changes of the concrete based on the steel slag as aggregate [10].
Chemical composition of main constituents of H-Cement (HC) and Portland cement (PC) clinker are listed in Tables 1 and 2. Table 3 confirms that H-Cement shows different chemical and mineral compositions compared to PC. Both hydrated cements differ in typical characteristic values as stated in Table 4. The results suggest that hybrid cement can be used prospectively in concrete for the same purposes as the blended cements of lower-strength classes, e.g., CEM III–V, probably CEM II/B-S according to STN EN 197-1, preferably in massive constructions due to low hydration heat and aggressively exposed media because of low Portland clinker (and therefore C3A) content.
% wt. | CaO | SiO2 | Al2O3 | Fe2O3 | MgO | SO3 | K2O | Na2O | L.O.I |
---|---|---|---|---|---|---|---|---|---|
FA | 3.36 | 51.42 | 26.93 | 7.27 | 2.10 | 0.87 | 3.28 | 0.17 | 1.84 |
GBFS | 39.24 | 40.13 | 7.19 | 0.27 | 10.04 | 1.50 | 0.52 | 0.31 | 1.10 |
Chemical composition of fly ash (FA) and blast furnace slag (GBFS).
Abbreviations: FA, fly ash; GBFS, granulated blast furnace slag; LOI, loss on ignition.
% wt. | CaO | SiO2 | Al2O3 | Fe2O3 | MgO | SO3 | K2O | Na2O | P2O5 |
---|---|---|---|---|---|---|---|---|---|
Clinker | 64.4 | 20.80 | 4.80 | 3.08 | 1.45 | 0.47 | 1.05 | 0.28 | 0.49 |
C3S | C2S | C3A | C4AF | Free CaO | Arcanite | Periclase | |||
65.1 | 10.60 | 8.40 | 9.72 | 1.40 | 0.82 | 0.58 |
Chemical and mineralogical composition of Portland clinker.
% wt. | CaO | SiO2 | Al2O3 | Fe2O3 | MgO | Na2O | Na2O | SO3 | TiO2 |
---|---|---|---|---|---|---|---|---|---|
HC | 30.73 | 48.57 | 20.13 | 6.81 | 2.13 | 2.51 | 3.22 | 4.67 | 1.14 |
C3S | C2S | C3A | C4AF | Q | ARC | ANH | PER | ||
33.66 | 11.75 | 11.54 | 6.64 | 28.34 | 1.30 | 1.18 | 0.50 | ||
PC | CaO | SiO2 | Al2O3 | Fe2O3 | MgO | K2O | SO3 | P2O5 | Cl− |
64.09 | 21.54 | 4.07 | 2.64 | 1.24 | 1.05 | 3.37 | 0.34 | 0.07 | |
C3S | C2S | C3A | C4AF | ARC | G | BAS | PER | Cc | |
61.63 | 7.18 | 7.86 | 8.72 | 1.39 | 4.22 | 3.57 | 0.51 | 3.34 |
Chemical and mineralogical composition of HC and PC.
Abbreviations: Q, quartz; ARC, arcanite; ANH, anhydrite; PER, periclase; G, gypsum; BAS, bassanite; Cc, calcite.
Technical parameters | Unit | HC | PC |
---|---|---|---|
Initial setting time | Minute | 200 ± 20 | 190 ± 20 |
Final setting time | Minute | 300 ± 40 | 250 ± 30 |
Standard consistency | % | 32 ± 2.0 | 29.1 ± 1.8 |
2-day compressive strength | MPa | 17.5 ± 3.0 w/c = 0.4* | 33.7 ± 2.0 w/c = 0.5 |
28-day compressive strength | MPa | 36.5 ± 4.0 w/c = 0.4 | 59.2 ± 1.6 w/c = 0.5 |
90-day compressive strength | MPa | 41.5 ± 3.0 w/c = 0.4 | 63.1 ± 1.9 w/c = 0.5 |
2-day flexural strength | MPa | 3.5 ± 0.5 w/c = 0.4 | 6.4 ± 0.4 w/c = 0.5 |
28-day flexural strength | MPa | 4.4 ± 0.4 w/c = 0.4 | 8.9 ± 0.4 w/c = 0.5 |
90-day flexural strength | MPa | 9.0 ± 0.3 w/c = 0.4 | 9.3 ± 0.3 w/c = 0.5 |
Le Chatelier (soundness) | mm | 0.5 | 0.01 |
Content of CrVI | ppm | 1.0 | 1.23 |
Content of C3A | % wt. | 2.0 ± 0.5 | 7.5 ± 0.8 |
Hydration heat | J/g | 185 | 359 |
Comparison of characteristic values of H-cement and reference PC.
Too plastic consistency at w/c = 0.5.
H-Cement consists essentially in a blend of materials containing 20–30% wt. Portland clinker and 70–80% alkaline cement, in turn a combination of fly ash, granulated blast furnace slag and alkaline sulphates.
The cube compressive strengths of ready-mixed concretes of C8/10 to C30/37 strength class for reaching a slump of 100–150 mm (slump class S3 according to [23]) without the use of plasticizers are listed in Table 5. The consistency and cube compressive strength of ready-mixed concretes prepared with different plasticizers with slump values ≥220mm [slump class S5] are reported in Table 6. Laboratory-made ready-mixed concrete specimens were prepared with the following types of plasticizers coming from various producers: M1, no admixture; M2, lignosulfonate; M3, modified polycarboxylate (<22% polycarboxylate content); M4, polycarboxylate (30% water-reducing effect); M5, modified polycarboxylate (more than 22% polycarboxylate content); M6, polycarboxylate (35% water-reducing effect); M7, melamine; and M8, lignosulfonate modified by polycarboxylate.
Concrete strength class | Cube compressive strength (MPa) | ||
---|---|---|---|
2 days | 7 days | 28 days | |
C8/10 | 4.8 | 10.4 | 16.0 |
C12/15 | 5.7 | 11.4 | 18.7 |
C16/20 | 6.9 | 14.6 | 22.2 |
C20/25 | 8.0 | 16.8 | 25.0 |
C30/37 | 14.6 | 29.4 | 42.6 |
Ready-mixed concrete compositions with H-Cement at slump S3.
Concrete mixture | Entrapped air (% vol.) | Slump (mm) | Cube compressive strength (MPa) | ||||
---|---|---|---|---|---|---|---|
After mixing | After mixing | After 60 min | 2 days | 28 days | 56 days | 90 days | |
M1 | 1.2 | 220 | 120 | 11.0 | 23.6 | 24.8 | 26.3 |
M2 | 2.1 | 220 | 130 | 11.0 | 25.0 | 27.1 | 28.4 |
M3 | 1.7 | 220 | 60 | 10.6 | 21.8 | 22.5 | 22.6 |
M4 | 1.6 | 220 | 70 | 9.3 | 21.2 | 22.5 | 22.7 |
M5 | 1.7 | 220 | 110 | 10.1 | 23.6 | 26.6 | 25.4 |
M6 | 1.4 | 220 | 170 | 8.6 | 22.6 | 24.1 | 23.7 |
M7 | 2.3 | 220 | 40 | 7.1 | 24.0 | 24.6 | 29.9 |
M8 | 1.3 | 220 | 190 | 9.4 | 22.2 | 21.1 | 24.6 |
Properties of fresh ready-mixed concrete mixtures C20/25 with different kinds of plasticizers.
The results show that H-Cement is suitable for the production of ready-mixed concrete between C8/10 and C30/37 strength classes [29]. Workability of the concretes made from H-Cement is dependent on the specific plasticizer type being used. Admixtures based on a lignosulfonate and a combined lignosulfonate/polycarboxylate mixture are found best to ensure the workability of fresh concrete mixtures and also after the elapsed 60 min.
The concretes were prepared from the cement mixture made of two cements, HC and PC, in the selected ratios (expressed as % wt.) as reported in Table 7. The specimens were stored in water at (20 ± 1)°C and in air at (20 ± 1)°C with 60% RH and at (40 ± 1)°C with an average RH of 15% in order to minimize the length changes within the 90-day period of curing. The concretes were prepared with a constant water-to-cement ratio of 0.475 according to the proportion: 400 kg/m3 of cement (PCHC 1.00 or HCPC 1.00) or cement blend, 190 l of water and dried river aggregates—0/4 mm, 630 kg; 4/8 mm, 390 kg; and 8/16 mm, 775 kg from Jelka (Slovakia). No admixture was used at the concrete production to preclude its influence on the measured length changes. The measurements were performed on the prisms 100 × 100 × 400 mm having a length comparator according to STN 731320 [30] (the related ASTM Standard: C157/C157M-08) and are illustrated in Figures 1 and 2. Mechanical properties of the specimens are listed in Table 8.
Cement mixture in concrete | Content of cements (% wt.) | Curing regime | |
---|---|---|---|
HC | PC | ||
PCHC 1.00 | 0 | 100 | In water at 20°C and in air at 20 and 40°C |
PCHC 0.95 | 5 | 95 | In water at 20°C |
PCHC 0.90 | 10 | 90 | |
PCHC 0.85 | 15 | 85 | |
HCPC 0.50 | 50 | 50 | In water at 20°C and in air at 20 and 40°C |
HCPC 0.85 | 85 | 15 | In air at 20 and 40°C |
HCPC 0.90 | 90 | 10 | |
HCPC 0.95 | 95 | 5 | |
HCPC 1.00 | 100 | 0 | In water at 20°C and in air at 20 and 40°C |
Content of cements in the concrete mixtures with w/c = 0.475.
Length changes of concrete stored 90 days at 20°C and 60% RH.
Length changes of concrete stored 90 days at 40°C and 15% RH.
Concrete mixture | HC (% wt.) | Curing | 28-day basic curing | 90-day curing | ||
---|---|---|---|---|---|---|
Compressive strength (MPa) | DME (GPa) | Prism strength (MPa) | ||||
Flexural | Compressive | |||||
HCPC 1.00 | 100 | W20 | 27.2 | 46.6 | 5.4 | 34.2 |
A20 | 27. 6 | 41.7 | 2.4 | 32.3 | ||
A40 | 28.7 | 36.7 | 2.3 | 30.6 | ||
HCPC 0.95 | 95 | A20 | 29.3 | 41.4 | 2.8 | 32.9 |
A40 | 30.0 | 36.7 | 2.4 | 31.8 | ||
HCPC 0.90 | 90 | A20 | 31.3 | 41.3 | 2.9 | 34.8 |
A40 | 32.0 | 36.6 | 2.5 | 33.0 | ||
HCPC 0.85 | 85 | A20 | 32.4 | 41.4 | 3.0 | 37.2 |
A40 | 33.2 | 36.6 | 2.6 | 34.7 | ||
HCPC 0.50 | 50 | W20 | 35.7 | 50.3 | 5.5 | 49.1 |
A20 | 38.1 | 41.2 | 3.3 | 41.0 | ||
A40 | 38.5 | 36.5 | 3.2 | 38.5 | ||
PCHC 0.85 | 15 | W20 | 40.5 | 55.1 | 5.5 | 50.6 |
PCHC 0.90 | 10 | W20 | 40.5 | 55.9 | 5.5 | 50.7 |
PCHC 0.95 | 5 | W20 | 41.0 | 56.6 | 5.5 | 51.4 |
PCHC 1.00 | 0 | W20 | 41.6 | 56.6 | 5.6 | 54.5 |
A20 | 40.2 | 39.3 | 3.7 | 42.0 | ||
A40 | 39.1 | 33.4 | 3.8 | 39.0 |
Mechanical properties of the concretes made from a mixture of HC and PC stored for 90 days in water at 20°C (W20), in air at 20°C/60% RH (A20) and at 40°C/15% RH (A40) after 28-day basic curing.
Abbreviations: W20, water at 20°C; A20, air at 20°C; A40, air at 40°C; DME, dynamic modulus of elasticity; BC, basic curing specified by 1-day cure in the chamber at (20 ± 1)°C at 100% RH air and 27-day curing in water at (20 ± 1)°C.
The results show that H-Cement has reduced shrinkage. All concretes slightly expand when permanently cured in water. H-Cement concrete (HC concrete) expands by 21.6% less than PC concrete after 90-day immersion in water. The shrinkage of HC concrete exposed for 90 days in 20°C/60% RH air cure and 40°C/15% RH air cure is about 48 and 58% smaller than that of PC concrete. The shrinkage-reducing effect is also recorded by the blended systems.
Depending on its cement blend composition and curing regime, however, blending HC with PC contributes to raising the compressive strength values compared to plain HC concrete. The 90-day compressive strength of HCPC 1.00 (100% wt. HC), HCPC 0.50 (50% wt. of both cements) and PCHC 1.00 (100% wt. PC) in 20 and 40°C air cure is 32.3 and 30.6 MPa, 41.0 and 38.5 MPa and 42.0 and 39.0 MPa, respectively.
The andesite aggregate with a proven susceptibility to ASR according to the criteria for evaluation of the chemical test according to STN 721179 [16] was used for the tests. The alkali content expressed as Na2O equivalent in both cements was estimated. From this content, the amount of NaOH required to achieve the desired Na2O eq. (1.30 + 0.05)% wt. by the standard was calculated. The tap water was enriched with a calculated amount of NaOH during laboratory production of the mortars. Prediction criteria of andesite aggregate susceptibility to ASR are given in Table 9. The composition of mortars for 6-month length change test cured at 20 and 40°C/100% RH moist air took into account the requirements of the above standard. Length changes are illustrated in Figure 3.
Aggregate | Loss of alkalinity R (mmol/l) | Molar concentration of SiO2 S (mmol/l) | Criterion for R value in [16] | Criterion for S value in [16] | Assumption that aggregate contains reactive forms of SiO2 |
---|---|---|---|---|---|
Andesite | 132.42 | 400.04 | R > 70 | S > R | Yes |
Prediction of andesite susceptibility to ASR by the chemical test.
Length changes of the mortars with the ASR aggregate andesite.
The results show that H-Cement is characterized by ASR-mitigating property. H-Cement mortar (abbreviated as HC 20 and HC 40), in contrast with PC (abbreviated as PC 20 and PC 40), clearly reduces the expansion markedly below the maximum allowable standard limit [16] of 0.1% (<1%) regardless of the long-term treatment. ASR-mitigating effect under maximum allowable limit of 0.1% (<1%) is confirmed also for the blended cement consisting of 70% wt. PC and 30% wt. HC (abbreviated as HM 20 and HM 40 in Figure 3).
The contemplated cause of ASR mitigation is the presence of alkali-activated pozzolans in the substitution of up to 80% by weight of the PC clinker, which could prevent the expansion [31]. The cause of ASR is a complicated problem and is still not fully understood. In this research focused on the need for industry, the achieved effect was investigated, and its cause is not studied in detail.
Basic physical properties and standard strengths are summarized in Table 10. HC compared to PC is characterized by low C3A content. Such composition predisposes such cement to be chemically more resistant than PC. Properties of fresh mortars are listed in Table 11. HC mortar compared to both reference is characterized by the higher specific surface area and standardized density. In spite of that fact, water-to-cement ratio of HC mortar is 0.42 compared to 0.5 of PC mortar when both are adjusted on the same consistency of 140 ± 1 mm. H-Cement shows plasticity effect in the mortar; however, it is unable to reach the strength level of both reference mortars, as reported in Table 10. The second reference mortar was prepared from C3A-free industrially made Portland cement (abbreviated as SR). HC and PC mortars were adjusted on the same consistency; that of SR differs. SR and PC were produced with the same w/c ratio of 0.5.
Cement kind | C3A content (% wt.) | Specific surface area (m2/kg) | Standard density (% wt.) | Initial and final set (min) | Compressive strength (MPa) | Flexural strength (MPa) | ||
---|---|---|---|---|---|---|---|---|
2 days | 28 days | 2 days | 28 days | |||||
HC | 1.95 | 696.8 | 33.0 | 230/285 | 14.9 | 39.0 | 4.1 | 7.8 |
SR | 0.03 | 354.9 | 27.2 | 185/225 | 26.2 | 52.8 | 4.7 | 8.4 |
PC | 14.31 | 344.7 | 25.8 | 220/285 | 26.5 | 56.5 | 5.4 | 8.5 |
Basic properties of the cements.
Mortar | Consistency (mm) | Bulk density (kg/m3) | Air content (% vol.) | w/c |
---|---|---|---|---|
HC mortar | 141 | 2200 | 5.2 | 0.42 |
SR mortar | 186 | 2210 | 6.3 | 0.50 |
PC mortar | 142 | 2240 | 4.7 | 0.50 |
Properties of fresh mortars.
Chemical composition of PC and HC mortar after 28-day basic curing in water at (20 ± 1)°C is listed in Table 12.
Constituent | PC mortar (% wt.) | HC mortar (% wt.) |
---|---|---|
Ignition loss | 9.43 | 6.79 |
SiO2 | 64.69 | 71.50 |
CaO | 18.07 | 6.38 |
Al2O3 | 1.86 | 7.91 |
Fe2O3 | 1.17 | 2.28 |
MgO | 3.54 | 3.37 |
SO3 | 0.98 | 1.17 |
Cl− | 0.03 | 0.02 |
Na2O eq. | 0.09 | 0.41 |
Differences in chemical composition of PC and HC mortar after basic curing.
The cements confirm a substantial difference, especially in CaO content, also evident in Al2O3 and detectable in Na2O eq. amounts. Low CaO in hybrid cement is a prerequisite for the increased chemical resistance. Higher levels of Al2O3 and Na2O eq., as opposed to PC mortar, induce the occurrence of the alkali-activated binder based on pozzolanic components as an inorganic polymer characterized by a binder potential alongside the minor portion of hydrated PC clinker.
Dynamic modulus of elasticity (DME) of mortars after 5 years of exposure in the sulphate and water environment is shown in Figure 4. No evident changes were observed in 5% wt. Na2SO4 for HC and SR mortar, while drops in DME values are found for PC mortar, slightly after 2-year exposure and dramatically after 3-year attack. Elasticity modules at the water curing remain approximately the same.
Changes in DME of mortars in 5% Na2SO4 solution and water over time.
The effect of sulphate action on the expansion of the mortars is depicted in Figure 5. The HC and SR mortar show negligible expansion in sulphate exposure. PC mortar is specified by negligible length changes underwater, while evident expansion is observed in the sodium sulphate.
Length changes of mortars in 5% Na2SO4 solution and water over time (1 mm/m = 1%) = 0.1%.
Flexural and compressive strength of PC mortar is 9.0 and 63.9 MPa after 4-year curing in water; contrary evident destruction is observed in the sodium sulphate. Determination of the strength was therefore impossible. Excellent resistance of H-Cement to sulphate attack is demonstrated by 5-year strength of HC mortar. Data in Table 13 show that only a slight decrease in flexural and compressive strength is observed between reference water and aggressive sulphate exposure.
HC mortar kept in | Strength (MPa) | |
---|---|---|
Flexural | Compressive | |
Reference water | 9.1 | 47.1 |
Aggressive 5% Na2SO4 | 6.7 | 44.8 |
HC mortar strength characteristics at 5-year age from the production in 2012.
The structural integrity of SR and HC mortar is not disturbed, despite the found slight differences between the 5-year strength parameters. The observed HC mortar’s sulphate resistance is determined by the material composition of H-Cement that is not sensitive to sulphate attack as well as CEM I 42.5 R-SR 0 but not for the same reason. The cause of high sulphate resistance of H-Cement is explained later.
It is approved in Table 14 that PC mortar is characterized by extremely high bound SO3 and ignition loss values after 4-year exposure in 5% wt. Na2SO4 opposite to HC and SR mortar. The CaO content is dramatically reduced in sulphate exposure as compared to that of HC and SR mortar. HC mortar behaves in the sodium sulphate as well as SR mortar; even the difference between the SO3 bound in HC mortar in sulphate and water exposure is smaller than that in SR mortar.
Constituent | Contents of the constituents (% wt.) | |||||
---|---|---|---|---|---|---|
PC mortar | SR mortar | HC mortar | ||||
28-day BC + 4 years in H2O | 28-day BC + 4 years in Na2SO4 | 28-day BC + 5 years in H2O | 28-day BC + 5 years in Na2SO4 | 28-day BC + 5 years in H2O | 28-day BC + 5 years in Na2SO4 | |
Ignition loss | 10.75 | 22.97 | 16.97 | 19.15 | 7.65 | 10.81 |
SiO2 | 60.81 | 50.63 | 45.85 | 42.98 | 68.65 | 55.67 |
CaO | 22.90 | 7.52 | 30.82 | 28.19 | 7.50 | 10.00 |
Al2O3 | 0.75 | 0.67 | 1.83 | 1.83 | 9.17 | 13.38 |
Fe2O3 | 1.40 | 1.22 | 2.53 | 2.51 | 2.72 | 3.87 |
MgO | 1.82 | 2.26 | 0.77 | 0.82 | 1.05 | 1.36 |
SO3 | 1.19 | 14.31 | 1.01 | 4.21 | 1.66 | 1.75 |
Cl− | 0.03 | 0.02 | 0.03 | 0.03 | 0.01 | 0.01 |
Na2O eq. | 0.06 | 0.05 | 0.10 | 0.22 | 1.51 | 2.46 |
Chemical composition of PC mortar after 4 years and HC and SR mortar after 5 years of exposure in aggressive 5% Na2SO4 and reference water.
Qualitative and quantitative differences in mineral and phase composition of PC and HC mortar after 28-day basic curing (BC) in (20 ± 1)°C water are recognized in Figures 6–9. The basic feature of the difference in the mineral composition of both mortars lies in the absence of portlandite Ca(OH)2 in the mortar with the hybrid cement. Hydrated hybrid cement without the developed Ca(OH)2 assumes a realistic chemical resistance in terms of sulphate resistance.
Mineral composition of PC mortar after 28-day basic curing in water.
Mineral composition of HC mortar after 28-day basic curing in water.
TG-DTA plots of PC mortar after 28-day basic curing in water.
TG-DTA plots of HC mortar after 28-day basic curing in water.
The results of thermal analysis confirmed that H-Cement generates a hydrated phase without the formation of crystalline Ca(OH)2. This fact can decisively improve the increase in resistance to sulphate aggressiveness.
Mineral and phase compositions of the long-term exposed mortars are given in Figures 10–14. PC mortar in water contains quartz SiO2 (Q) from the standardized sand and calcium hydroxide Ca(OH)2 (CH) as a reaction product of cement hydration, also calcite CaCO3 (Cc) as minor mineral. The high content of gypsum CaSO4.2H2O (G) and, to a less extent, more voluminous ettringite 3CaO.Al2O3.3.CaSO4.32H2O (E) are detected in 4-year-old PC mortar exposed to 5% wt. Na2SO4 solution. Contrary, 5-year-old SR mortar shows a reduced content of CH in the sodium sulphate compared to water exposure and only a slight indication of the presence of CaSO4.2H2O arising as a reaction product of sulphate attack. HC mortar records in the same time negligible differences in mineral composition. The presence of CH and any reaction products of sulphate attack (G and E) are not confirmed; a negligible share of the marginal sodium thiosulfate pentahydrate Na2S2O3.5H2O (SH) and mirabillite Na2SO4.10H2O (MI) is detected. Both of the latter minerals would be considered as reaction products of sulphate attack, however, with no negative impact on degradation of the mortar. TG-DTA plot confirms the presence of reaction products of sulphate attack in PC mortar by endotherm with maximum peak at 160°C (Figure 13), compared to HC mortar (Figure 14). The presence of CH was not recognized in HC mortar in water and Na2SO4 exposure. The minimum presence of calcite CaCO3 (Cc) is also negligible in terms of mortar damage.
XRD patterns of PC mortar after 4 years in 5% wt. sodium sulphate and water.
XRD patterns of SR mortar after 5 years in 5% wt. sodium sulphate and water.
XRD patterns of HC mortar after 5 years in 5% wt. sodium sulphate and water.
TG-DTA plots of PC mortar stored 4 years in 5% wt. sodium sulphate and water.
TG-DTA plots of HC mortar after 5 years in 5% wt. sodium sulphate and water.
Basic parameters of the pore structure of the mortars are considered in Table 15.
Mortar | SSAP (m2/g) | VTP (cm3/g) | MTP (nm) | MMP (nm) | TP (%) | K (m/s) |
---|---|---|---|---|---|---|
PC | 5.32 | 0.100 | 252.00 | 84.65 | 19.39 | 3.3 × 10−10 |
SR | 2.90 | 0.55 | 55.40 | 28.51 | 11.95 | 2.2 × 10−12 |
HC | 11.17 | 0.100 | 31.46 | 19.91 | 19.67 | 8.0 × 10−11 |
Basic pore structure parameters of PC mortar after 4-year immersion as well as SR and HC mortar after 5-year exposure in aggressive 5% Na2SO4.
Abbreviations: SSAP, specific surface area of total open pores; VTP, volume of total open pores (1.82–0.534 nm); MTP, total pore median radius; MMP, micropore median radius (1.82–5250 nm); TP, total open porosity (1.82–0.534 nm); K, permeability coefficient (calculated from the MIP results).
PC mortar is characterized by evident coarsening of the pore structure after 4 years of exposure to the sodium sulphate. This finding is proven by one order of increased permeability in contrast to water treatment. HC and SR mortars show no significant differences in the pore structure parameters after 5 years of exposure.
The insignificant detrimental effect of 5-year sulphate attack on HC and SR mortar is also proven by the permeability values, which remain for each mortar the same in both exposure conditions (reference water vs. aggressive sulphate), while that of PC mortar is increased by one order even after 4-year exposure to sulphate attack.
Visual and microscopy observations support the previous finding that sulphate resistance of H-Cement is the same with that of the sulphate-resistant Portland cement. Visual observations prove that 5-year-old HC mortar is characterized by well-preserved structural integrity, while PC mortar is considerably destroyed in the sodium sulphate after 4 years of exposure (Figure 15).
Destroyed integrity of PC mortar after 4 years of aggressive attack with sodium sulphate (left) and intact state of H-cement after 5 years of aggressive attack of 5% wt. Na2SO4 (right).
The gypsum and ettringite presence is confirmed in PC mortar after 4-year exposure in the sodium sulphate, while the same reaction products are not detected in HC and SR mortar after 5-year exposure in Na2SO4 (Figure 16). The property of high non-permeability, which is a consequence of the formed hydrate phase character, is a basic condition for the high chemical resistance of a mortar and, in the conveyed meaning of the word, also a concrete made of the same binder system as that which occurred in 5-year-old HC mortar.
SEM image of SR mortar (left) and HC mortar (right) after 5 years of exposure in sodium sulphate (10,000× magnification).
Degradation of the hydrate phase of cement-based composite by sulphate attack is characterized by the formation of gypsum CaSO4.H2O(CSH2) together with ettringite (CaO)3(Al2O3)(CaSO4)3.32H2O(C6AS3H32). Gypsum is formed by the reaction of sulphate ions with Ca(OH)2 or calcium silicate hydrate (C-S-H):
The formed gypsum binds to tricalcium aluminate (C3A), in particular to ettringite, but also monosulphate (CaO)3(Al2O3)(CaSO4)12H2O(C4ASH12) is secondary generated:
Ettringite formation is also accompanied by another minor reaction:
Reaction products of sulphate attack (gypsum and ettringite) are high-volume salts that cause destructive expansion of hydrated cement matrix. The tested H-Cement is specified by the major portion of the cement-less inorganic polymer (80% wt.) and the minor portion of the PC clinker (20% wt.). It contains a little C3A and when hydrated no Ca(OH)2. Therefore, just the composition of H-Cement is the cause of its high sulphate resistance because degradation processes, as described by Eqs. (1)–(5), cannot be applied with H-Cement use. Sulphate resistance of H-Cement is therefore regarded the same as sulphate-resistant CEM I 42.5 R-SR 0.
The temperatures and pressures in the testing laboratory autoclave were set according to the autoclave curves presented in Figure 17 in order to determine the volume changes of the concrete based on steel slag. The properties of the steel slag used for experimental research are shown in Tables 16 and 17. Figure 18 shows a gradual increase in the cube strength of concretes based on H-Cement and steel slag (HC concrete) as the aggregate compared with that consisting of PC with steel slag (PC concrete). HC concrete reports a smaller increase in strength, which equals that of PC concrete after 90 days of exposure in water. The characteristic concrete strength after 90 days in the case of the HC concrete and PC concrete is approximately the same, 38 MPa.
Temperature-pressure conditions and concrete autoclaving time.
Bulk density of grains | 3.742 Mg m−3 |
Bulk density of grains after drying in a dryer | 3.439 Mg m−3 |
Bulk density of grains saturated with water and surface dried | 3.520 Mg m−3 |
WA24 water absorption | 2.34% |
Values of bulk density and absorption power of steel slag with the fraction of 0/8 mm.
Constituent | Unit | Result | Uncertainty | Element | Unit | Result |
---|---|---|---|---|---|---|
Na2O | % wt. | 0.46 | ±0.10 | V | mg/kg | 570 |
MgO | % wt. | 10.2 | ±1.2 | Cr | mg/kg | 3900 |
Al2O3 | % wt. | 2.43 | ±0.27 | Ni | mg/kg | 25 |
SiO2 | % wt. | 13.7 | ±1.3 | Cu | mg/kg | 38 |
P2O5 | % wt. | 0.91 | ±0.09 | Zn | mg/kg | 63 |
SO3 | % wt. | 0.50 | ±0.06 | Sr | mg/kg | 130 |
K2O | % wt. | <0.003 | Zr | mg/kg | 140 | |
CaO | % wt. | 38 | ±2 | Nb | mg/kg | 67 |
TiO2 | % wt. | 0.29 | ±0.02 | Mo | mg/kg | 36 |
MnO | % wt. | 3.02 | ±0.13 | Ba | mg/kg | 200 |
Fe total | % wt. | 22 | Ta | mg/kg | 110 | |
CaO free | % wt. | 2.34 | ±0.24 | W | mg/kg | 86 |
— | — | — | — | Loss by annealing | % wt. | −0.74 |
Results of chemical analysis of steel slag.
Average values of cube strengths from the first stage of the experiment.
The gradual increase in the cube strength of concretes based on H-Cement is caused by the fact that the hybrid cement generates lower hydration heat during the initial hydration and thus makes it possible to reduce the volume changes during setting and hardening of the concrete mixture based on steel slag.
Table 18 compares the average values of cube strengths after 28 and 90 days and prism strengths after 28 days from the first and second stages of the experiment.
Age of concrete | HC concrete (MPa) | PC concrete (MPa) | ||
---|---|---|---|---|
First stage | Second stage | First stage | Second stage | |
Cube 28 days | 29.1 | 27.9 | 34.6 | 29.2 |
Cube 90 days | 38.4 | 33.4 | 38.0 | 31.5 |
Prism 28 days | 29.0 | 25.0 | 31.2 | 32.1 |
Comparison of cube and prism strengths after 28 and 90 days from the first and second stage of the experiment.
When comparing the results of the cube strength from the first and second stage of the experiment, the next partial observations may be drawn:
After 28 days, HC concrete shows a lower strength by 1.2 MPa (4.1%).
After 28 days, PC concrete shows a lower strength by 5.4 MPa (15.6%).
After 90 days, HC concrete shows a lower strength by 5.0 MPa (13.0%).
After 90 days, PC concrete shows a lower strength by 6.5 MPa (17.1%).
It is therefore evident that:
The difference between the prism strength of HC concrete is 4 MPa (13.8%).
The difference in prism strength of PC concrete is 0.9 MPa (2.8%).
The results of durability tests of the concrete based on steel slag showed the suitability of H-Cement as a binder for the production of the concrete based on steel slag in an environment with a higher temperature and pressure. The above-stated fact is well-confirmed by Figure 19, where the comparison of test specimens after the autoclaving process is shown. The PC concrete with steel slag as aggregate was disintegrated into rubbles, while that composed of H-Cement remained compact and without any apparent damage. The autoclaving process (see Figure 17) of concrete containing steel slag and CEM I (PC concrete) resulted in a disruption of the cement compound due to shrinkage with increasing temperature. The autoclaving process accelerated the calcium disintegration and the magnesium disintegration of steel slag, which is associated with volume changes. This process has caused the disintegration of the test specimens. The autoclaving process of concrete containing steel slag and H-Cement (HC concrete) has eliminated the volume changes of the steel slag (calcium and magnesium expansion). There was no disruption of the cement compound and the contact zones between the grain of steel slag and the cement compound. This is confirmed by an increase in the concrete strength after the autoclaving process from 29.1 to 43.0 MPa (increase by 32%).
View on (a) HC concrete and (b) PC concrete after autoclaving.
From the results of our experimental investigation, it is possible to formulate the following conclusions:
H-Cement with the composition that is found to be outside of the EN 197-1 can be used similarly to traditional cements of medium-strength classes like 32.5R and 42.5N and for high long-term flexural strength. No kind of additional heat treatment during early and later hydration is needed.
H-Cement is suitable for use in ready-mixed concrete up to C30/37 strength class with a variety of plasticizers, which are compatible with it in the same way as traditional cements. Lignosulfonate-based and combined lignosulfonate-polycarboxylate plasticizers have been found to be the best in terms of workability of fresh mixtures standing for 60 min.
H-Cement has under the conditions tested shrinkage-reducing properties. Shrinkage-reducing effect is also recorded in cement blends at replacement level of H-Cement by 5–15% wt. PC. No shrinkage-reducing admixture is necessary in concrete when H-Cement is used.
H-Cement has under the conditions tested ASR-mitigating property. The expansion of concrete is also suppressed when using cement blend with replacement level of PC by 30% wt. H-Cement.
High sulphate resistance of H-Cement is the result of a special composition; sulphate resistance of H-Cement was found by a 5-year test, the same with that of sulphate-resistant CEM I 42.5 R-SR 0.
H-Cement is suitable for use in concrete with 100% replacement of natural aggregate by the artificial steel slag aggregate. No detrimental processes leading to disintegration of such concrete exposed to high temperature and pressure were recognized.
The financial support of this research project based on the contract related to the utility properties and durability of developed new cement kinds by the Považská cementáreň, a. s., cement plant, Ladce (Slovakia), is greatly appreciated.
The authors do not register any conflict of interest.
Malaria remains a serious public health problem in several developing countries. Globally, there are about 3.2 billion people at risk of malaria and 435,000 malaria-related deaths, most of which happening in West Africa [1, 2]. Malaria is a complicated disease caused by the genus
A wide deployment of malaria control tools in the past few decades have significantly reduced malaria morbidity and mortality worldwide. The number of countries with fewer than 100 clinical malaria cases increased from six to 27. Countries including Iran, Malaysia, Timor-Leste Belize, Cabo Verde, China, and El Salvador reported zero malaria cases in 2019 and malaria cases dropped by 90% in the Greater Mekong subregion (GMS) [7]. However, in the last five to seven years, there has been a resurgence of malaria in several African countries, raising the questions of whether and why current control mechanisms are failing. A number of factors has limited malaria control and elimination efforts. First,
Knowledge of the evolution and genetic variation of the
Compared to other eukaryotic organisms, whole genome sequencing (WGS) showed that the genome of
In comparison, conserved genes are genes that have not been altered. They contribute to important biological processes and fitness [25]. Information of conserved genes allow us to infer phylogenetic relatedness and trace the genetic origin of different lineages, determine new targets for therapeutic treatment, and serve as a guide when determining functions of unknown genes [18]. The processes that determine the polymorphisms of the parasitic genome include both selective pressures and recombination frequencies. Selective pressures on conserved genes allow certain important genes to remain unmodified for normal metabolic activities, whereas polymorphic genes diversify through frequent recombination allow for better evasion of antimalarial drug treatments and escape detection from diagnostic tests [26]. For example, the
One of the challenges to malaria elimination is the burden of submicroscopic asymptomatic infections that contribute to malaria transmission [7]. The gold standard for malaria diagnosis is microscopy [32]. Microscopy can differentiate malaria species and quantify parasite density, but only has a detection threshold of 10 to 50 parasites μl of blood (approximately 0.001% parasitemia, assuming an erythrocyte count of 5 × 106 cells μl) [33]. However, it requires well trained microscopists and is labor-intensive and time-consuming [32]. Previous studies have reported higher prevalence of asymptomatic parasitemia (6–7 times higher) using PCR compared to microscopy [5]. Nested PCR of the
Rapid Diagnostic Test (RDT) is a lateral flow immunochromatographic test that can detect the presence of
ELISA is an enzyme-linked immunosorbent assay that is used to detect antigens and antibodies by utilizing a highly specific antibody–antigen interaction and their bonding affinity to proteins on a solid surface [50]. Samples, including and positive and negative controls are inserted on a 96 well plate which enables the possibility to analyze multiple samples simultaneously, then samples get incubated and detection of the signal is generated directly or indirectly via secondary tag on the specific antibody [51]. ELISA can be very efficient diagnostic tool for
One of the current diagnostic tests in development is an antibody-based lateral flow immunoassay (LFIA). Unlike ELISA that requires repeated incubation and washing steps, LFIA is considered to be a simple, user-friendly and cost-effective method for front-line diagnosis [54]. LFIA is versatile enough to detect target genes in sample matrices including whole blood, saliva, and urine. This method is primarily applied to detecting gametocytes in malaria-infected samples. Gametocytes are the sexual form of the parasite that gets transmitted to the mosquito host. They play a very important role in malaria transmission, and can contribute to up to 80% [55] of the infectious reservoirs. Previous studies have shown that infections with parasitemia as low as 4 gametocytes/μl can sustain transmission [56]. LFIA targets
The combination of PCR-based assays and sequencing technologies have revolutionized malaria diagnosis since their introduction in the early 2000s. Various gene targets have be used to monitor genetic and/or mutational changes in the parasites that cause the disease. PCR is a very common technique used in malaria diagnoses in laboratory settings. The main advantage of this technique is that it enables us to identify individuals with low parasitemia (Table 1). There are multiple versions of this technique including nested conventional PCR, real-time quantitative PCR and reverse transcriptase PCR. Nested PCR is the easiest and least expensive methods among the others. It only requires a thermocycler, set of primers, reagents and visualization after gel electrophoresis. It is mostly a qualitative method as it is fairly difficult to estimate parasite density on a agarose gel. Unlike conventional PCR that uses gel electrophoresis to visualize PCR products, real-time PCR or qPCR detects and quantifies the amount of amplified DNA usually by SYBR green or a fluorogenic probe designed based on a target gene segment (TaqMan). The standard cycle threshold (Ct) value is inversely proportional to the amount of target DNA in the sample [66] and allows estimation of parasite density even in submicroscopic samples. Different from nested and qPCRs, reverse transcriptase PCR uses RNA as template and transcribes RNA into complementary DNA. This method has been widely used to detect and quantify gametocyte density in malaria samples. Though PCR-based methods are undoubtedly more sensitive than microscopic diagnosis, the level of sensitivity is highly dependent on the gene targets (Table 1).
Type | Target | Sensitivity (%) | Specificity (%) | Application | Detection Limit | Refs |
---|---|---|---|---|---|---|
RDT | 57 | 99 | Field | 50–100 parasites/μL of blood | [35] | |
RDT | 58 | 93 | Field | 50–100 parasites/μL of blood | [35] | |
PCR | 64 | 92 | Laboratory | 0.5–5 parasites/μL of blood | [60] | |
PCR | — | — | Laboratory | 0.6–2 parasites/μL blood | [60] | |
PCR | 81 | 49 | Laboratory | 6–24 parasites in 200 μL whole blood | [61] | |
PCR | — | — | Laboratory | 12–30 parasites in 200 μL whole blood | [62] | |
PCR | — | — | Laboratory | 0.3 mature females/μL blood | [63] | |
ELISA | 69.9 | 100 | Laboratory | 3 parasites/μL blood | [53, 64] | |
LFIA | — | — | Laboratory | 0.02 gametocytes/μl blood | [58] | |
SERS | Hemozoin | — | — | Laboratory | 30 parasites/μL of blood | [65] |
Existing malaria diagnostic tests and their respective performance.
— Denotes that the sensitivity or specificity is not reported.
The
The cytochrome c oxidase III (
The recently discovered Telomere Associated Repetitive Element 2 (
The
Raman spectroscopy is a relatively novel technique that can be used to diagnose the presence of
Extensive level of genetic diversity observed in
In regions in high malaria endemicity, individuals typically harbor multiple
Molecular inversion probes (MIPs) are another deep sequencing technique that targets several short gene regions across the genome. MIPs are single stranded DNA molecules that contain flanking regions of the targeted gene regions up to several hundred base pairs long [83]. MIPs can hybridize with the target sequence and undergo gap filling ligation to form circular DNA. The target sequence will also contain adaptors and barcodes to be further amplified by PCR [83]. The advantages of this technique include low rate of errors, small amount of DNA samples, high throughput, and cost-effective for several hundreds of samples. It is scalable to the number of targeted gene regions and samples, requires minimal costs in terms of reagents and labor, and allows efficient capture of DNA extracted from dried blood spots [84]. The latter advantage would make large-scale population studies feasible. MIPs have been used for monitoring SNP mutations associated with drug resistance, such as
Anti-malarial | Chloroquine | Amodiaquine | Sulfadoxine | Pyrimethamine | Artemisinin |
---|---|---|---|---|---|
Gene | Crt | Mdr1 | Dhps | Dhfr | K13 |
Mutation(s) | K76T | N86Y, Y184F | A437G, K540E | N51I, C59R, S108N | M476I, Y493H, R539T, I543T, C580Y |
Gene mutations associated with antimalarial drug resistance.
Genetic information of
Name of Vaccine | Type of Vaccine | Target of Vaccine | Malarial Life Cycle Stage | Phase of Vaccine | Efficacy | Refs |
---|---|---|---|---|---|---|
RTS,S/AS01E | Recombinant protein vaccine | Circumsporozoite protein (CSP) | Pre-Erythrocytic | Phase III | 35.2% in Children 20.3% in Infants | [94] |
Live, radiation- attenuated vaccine | Sporozoite (SPZ) | Pre-Erythrocytic | Phase III | Homologous challenge: 64% Heterologous challenge: 83% | [102] | |
Recombinant protein vaccine | Liver-stage antigen 1 ( | Pre-Erythrocytic | Phase I | Efficacy has yet to be found in humans | [105] | |
Subunit based Vaccine | MSP1 | Erythrocytic | Phase I | Efficacy has yet to be found in humans | [110] | |
Recombinant protein vaccine? | Erythrocytic | Phase II | Efficacy has yet to be found in humans | [125] | ||
R21 Vaccine | Recombinant protein vaccines | Illicit a higher anti-CSP antibody count | Erythrocytic | Phase I/IIa | Efficacy has yet to be found in humans | [92] |
Potential new target | Transmission Blocking Vaccine | None | Efficacy has yet to be found in humans | [123] | ||
Recombinant conjugated vaccines | Antibodies against the | Transmission Blocking Vaccine | Phase I | Efficacy has yet to be found in humans | [120] | |
Potential new target | Glutamic acid rich protein | Erythrocytic | None | Efficacy has yet to be found in humans | [115] | |
Potential new target | Induce strain-transcending neutralizing antibodies against blood-stage | Erythrocytic | Phase I/II | Efficacy has yet to be found in humans | [116] |
Overview of current vaccines candidates against
Pre-erythrocytic vaccines aim to kill infected hepatocytes and prevent sporozoites from reaching the liver [91]. There are various gene targets currently being investigated and in clinical trials.
RTS,S/AS01E is a well-known pre-erythrocytic vaccine that has successfully completed phase III of clinical testing. It is currently distributed by World Health Organization (WHO) in Malawi, Ghana, and Kenya to further investigate vaccine efficacy [92]. RTS,S is a vaccine that targets circumsporozoite proteins (CSP) from
Liver surface antigen (LSA) is another pre-erythrocytic vaccine target. LSA is essential for the survival of the parasites during the late liver schizogony stage [105]. Schizonts are asexual stage of
Erythrocytic vaccines aim to kill and terminate the asexual reproduction and invasion of the parasite within red blood cells (RBC). Infected individuals typically experience symptoms when the parasites invade a threshold number of RBCs and disrupt their normal functions. Preventing the parasites developed into blood stage will inhibit progression of malaria symptoms such as chills, aches, and fevers.
Merozoite surface protein 1 (MSP1) is one of the targets used for erythrocytic vaccine. MSP1 is a glycosylphosphatidylinositol-anchored protein found in abundance on the surface of the merozoites [109]. MSP1 plays an important role in the invasion of erythrocytes as it binds and recruits other peripheral merozoite surface proteins to form a complex [109]. MSP1 starts off as a precursor of about 196 kDa and then cleave into four subunits before invading the erythrocytes [110]. The four subunits are held non-covalently forming a complex attached to the merozoite’s GPI anchor [110]. Once the MSP1 complex is formed, it binds with the receptors on erythrocytes and activates a spectrin-binding function to enter the erythrocytes [110]. MSP1 has been shown to elicit both humoral (IgM and IgG antibodies) and cell-mediated immune responses (memory T cells) that lasted about 6 months after immunization [110]. These results are promising as MSP1 vaccine will also activate antibodies for complement fixation, induce opsonizing antibodies, and initiate secretion of reactive oxygen species by other immune cells [110]. To date, MSP1 vaccine is in phase I clinical trial. Further investigation is needed to evaluate efficacy.
The erythrocytic vaccine based on Apical Membrane Antigen 1 (AMA1) is currently in phase II clinical trial [111]. The AMA1 protein is approximately 83 kDa and can be found in both the merozoite and sporozoite stages of
The
TBV aims to prevent and kill the sexual stages of the
WHO aims to achieve malaria elimination in at least 35 countries, reduce incidence and mortality rates by 90%, and prevent resurgence in malaria-free countries by 2030. This ambitious goal has been challenged by the emergence and spread of antimalarial resistance, inaccurate diagnostic testing, asymptomatic transmission, and lack of effective vaccines [126]. Information of the
We thank our colleagues at the University of North Carolina at Charlotte and the University of Ghana for the inspiration and discussion that lead to the conceptualization of this paper. We also thank the reviewers for their insightful comments.
The authors declare no conflict of interest.
Conceptualization, C.C.D. and E.L.; resources, D.A.J. and E.L.; writing—original draft preparation, C.C.D., C.T.F., J.H., and E.L.; writing—review and editing, C.C.D., C.T.F., L.E.A, Y.A.A., D.A.J., and and E.L.; funding acquisition, E.L. All authors have read and agreed to the published version of the manuscript.
This research was funded by NIH/NIAID, grant number R15 AI138002.
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