Released this past November, the list is based on data collected from the Web of Science and highlights some of the world’s most influential scientific minds by naming the researchers whose publications over the previous decade have included a high number of Highly Cited Papers placing them among the top 1% most-cited.
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We wish to congratulate all of the researchers named and especially our authors on this amazing accomplishment! We are happy and proud to share in their success!
IntechOpen is proud to announce that 179 of our authors have made the Clarivate™ Highly Cited Researchers List for 2020, ranking them among the top 1% most-cited.
\n\n
Throughout the years, the list has named a total of 252 IntechOpen authors as Highly Cited. Of those researchers, 69 have been featured on the list multiple times.
\n\n\n\n
Released this past November, the list is based on data collected from the Web of Science and highlights some of the world’s most influential scientific minds by naming the researchers whose publications over the previous decade have included a high number of Highly Cited Papers placing them among the top 1% most-cited.
\n\n
We wish to congratulate all of the researchers named and especially our authors on this amazing accomplishment! We are happy and proud to share in their success!
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1. Introduction
The use of nasal cavity as a route of administration of drugs, specifically systemically acting drugs that pose a delivery challenge, have become an area of great interest to the pharmaceutical companies in the past decade. The physiology of the nasal cavity allows for variety of drug delivery possibilities and destinations which include local, systemic, vaccine, and access to the central nervous system (CNS)[1]
Anatomically, the nasal cavity can be divided into three functional regions (Figure 1):
Vestibular region having an area of 10 to 20 sq.cm and is situated just inside the nostrils. It is covered with stratified, keratinised and squamous epithelium.
Respiratory region having an area of about 130 sq.cm and occupies majority of the nasal cavity and consists of three turbinates namely inferior, middle and superior.
Olfactory region has an area of about 10 - 20 sq.cm. It is located in the roof of the nasal cavity and on the upper part of the nasal septum. It contains the receptors for the sense of smell. Local delivery of drugs in the nasal cavity can be used to treat allergies, congestion and infection. Systemic delivery of the drugs can be used for crisis treatments during a rapid onset of symptoms, daily administration of drugs for long-term treatment of disorders or delivery of peptides or proteins that may be difficult to administer. The nasal cavity can also be used to deliver vaccines including antigens (whole cells, split cells, and surface antigens) and DNA vaccines [1]. The nasal cavity also allows access to the CNS, thus allowing drugs to circumvent the blood-brain barrier (BBB) [1]. It has been suggested that there is free communication between the nasal submucosal interstitial space and the olfactory perinueronal space, which appears to be continuous with a subarachnoid extension that surrounds the olfactory nerve [2].
Figure 1.
Nasal Anatomy and Physiology
The pharmaceutical companies are increasingly marketing drugs as nasal formulations, drugs such as sumatriptan, estradiol, buserelin, and calcitonin, all which have shown to have faster onset of action, improved bioavailability, and a better delivery method [3].
There are a number of advantages in using nasal cavity for administration of drugs. Some of the advantages are: avoidance of the gastrointestinal tract along with hepatic first pass metabolism, increased absorption and bioavailability of small and larger drug molecules 4. Furthermore, drugs that have low oral bioavailability have been shown to be successfully delivered systemically using the nasal route; studies have suggested that the nasal route is a great alternative to parenteral route for delivery of protein and peptide drugs [4]. Also due to direct delivery of drugs to the systemic circulation, the onset of pharmacological action is rapid [5].
Administration of lower drug doses through the nasal route, may lead to lower side effects. The convenient delivery of drugs via the nasal route, especially in long-term therapies has proven to increase patience compliance compared to parenteral and injection methods [4]. Lipophilic drugs generally have no trouble being absorbed through the nasal cavity. In fact, the bioavailability of lipophilic drugs been shown to be very close to those of intravenous injection (100% bioavailability), for instance, fentanyl has been shown to have an 80% bioavailability for nasal administration [1].
Even though the nasal cavity has a large surface area along with extensive blood supply, it has been shown that the permeability of the nasal mucosa is low for polar molecules. The limiting-factor for nasal absorption of polar drugs such as peptides and proteins is epithelial membrane permeability. Drugs with molecular weights lower than 1000Da can generally pass the epithelial membrane via transcellular route, receptor mediated transport, vesicular transport, use of concentration gradient force [6], or travelling in the paracellular route through the tight junction between the cells. In fact tight junctions seem to have finite permeability to molecules with molecular radii less than or equal 3.6 A and are essentially impermeable to those with molecular radii greater than or equal to 15 A [7]. Despite the advantages of nasal drug delivery, some of the drugs may also cause inconvenience due to potential for nasal irritation. Pathological conditions such as cold and allergies may alter nasal bioavailability significantly, which can have an effect on the intended pharmacological action [8].
Another factor that plays an imperative role in low membrane transport of nasally administered drug therapeutics is rapid drug clearance by the mucociliary clearance mechanism. This problem is common with drugs that are not easily absorbed across the nasal membrane. It has been shown that drugs that do not readily cross the nasal membrane, whether liquid or power form are removed from the nasal cavity in 15-20 min [9]. Mucociliary clearance tends to decrease the residence time of the administered drug. This problem can be overcome using formulation strategies. Novel delivery platforms based on polymeric drug carriers along with variety of methods that can be used to improve the absorption of drugs through the nasal route will be discussed in the following paper. These delivery systems work by attaching themselves to the mucus layer and thus preventing clearance of the drug delivery system. Some of these delivery systems are still experimental, whereas others have advanced to clinical use. Figure 2 summarizes the various mechanisms involved in mucoadhesion of the main drug carriers discussed in this chapter.
Figure 2.
Mechanisms of mucoadhesion by lectins (A), Thiomers (B), Alginate Poly ethylene glycol acrylate (C).
2. Lectins
Lectins are classified as a group of structurally diverse proteins [10] that are found in plants as well as in the animal kingdom. They are also found in some microorganisms [11]. Lectins have the capability to identify and bind to specific sugar moieties. The sugar-binding moiety of most lectins is only a small part of the lectin, i.e., a major portion of lectin is not involved in the recognition and binding to the receptor[12]. Lectins also cause agglutination due to their ability to cross link sugar containing macromolecules. Primarily they identify only specific sugars like mannose, glucose, galactose, N-acetyl-glucosamine, N-acetyl galactosmaine, furose and N-acetyl neuramic acid [13]. The various lectins which have shown specific binding to the mucosa include lectins extracted from Ulex europaeus I, soybean, peanut and Lens culinarius. The use of wheat germ agglutinin has been on the rise due to its least immunogenic reactions, amongst available lectins [2]. Lectins have the ability to stay on the cell surface or become internalized via a process called endocytosis if the adhesion is receptor mediated. In this manner lectins offer twin functionality of not only allowing target specific attachment but also a means of delivering the drug through a controlled process to the cells by active cell mediated drug uptake [1]. Lectins have potential to be used in Nasal Drug Delivery, especially where internalization of the drug encapsulated nanoparticles is of particular importance such as DNA delivery[14]. Inspite of lectins offering significant advantages, it is worth noting that such polymers suffer at least in part from premature inactivation by shed off mucus. This phenomenon has been reported to be advantageous, given that the mucus layer provides an initial yet fully reversible binding site followed by distribution of lectin-mediated drug delivery systems to the cell layer[15].
There are three types of lectins - classified based on their molecular structure:
Merolectins: lectins which have one carbohydrate recognising domain [1].
Hololectins: lectins which have two or more carbohydrate recognising domains [1].
Chimerolectins: lectins with additional unrelated domains [1].
Lectins are involved in various biological processes: cell-to-cell recognition and communication, particularly in the mammalian immune system (transendothelial migration), adhesion and attack of infectious agents on host cells, and clearance of glycoproteins from the blood circulation [16]. Lectins are used in conjugation with other mucoadhesive polymers as drug delivery vehicles to the brain or systemic circulation through the nasal cavity. It was observed that negligible penetration of nanoparticles takes place between cells in the nasal epithelium when administered on their own. Secondly, mucociliary clearance reduced the residence time of the particles in the nasal cavity (particles cleared within the nose every 15 to 20min, thus, resulting in incomplete absorption of the formulation. Also it was found that, unmodified nanoparticles distributed in the nasal cavity without selectivity. This resulted in poor brain targeting efficiency of the formulation. To deal with these problems, novel lectin-modified nanoparticles were constructed. The lectin used was wheat germ agglutinin (WGA), which specifically binds to N-acetyl-D-glucosamine and sialic acid moieties, both of which were abundantly observed in the nasal cavity especially in the olfactory mucosa [17].
Factors like low ciliary irritation and high permeability among other considerations favour the potential use of lectins for nasal drug delivery [18]. Studies in animals concluded that lectins have minimal acute irritancy and can be thus be used for further in vivo studies[19]. However, many lectins are toxic or immunogenic especially those obtained from Ricinus communis,\n\t\t\t\tPhaseolus vulgaris and Lycopersicon esculentum and Canavalia ensiformis[5].There is a probability that lectins promote the production of antibodies which could lead to the blockage of lectin-based delivery vehicles. These antibodies may also expose patients to the risk of systemic anaphylaxis on successive exposure. But, by using truncated varieties of lectin molecules as mucoadhesives this potential risk of toxicity may be triumphed over [20].
Synopsis of the studies on the use of Lectins in formulations for nasal drug delivery
3. Thiomers
Thiomers are mucoadhesive polymers that have side chains carrying thiols which lead to formation of covalent bonds between the cystiene groups in the mucus and the polymer by thiol/disulphide exchange reactions or simple oxidation process. These bonds are also known as disulphide bridges. These bridges sometimes improve mucoadhesion by 100 folds. They also have permeability enhancing effect and ability to control the rate at which drugs are released. This property and increased mucoadhesion leads to higher residence time of the drugs administered in combination with thiomers hence improving their bioavailability [23]. Thiomers are also used in combination with other polymers like chitosan, poly acrylic acid, etc. Due to immobilization of thiol groups, mucoadhesive properties of these polymers are increased by 140 folds and 20 folds respectively [12]. Thus, thiomers are one of the most mucoadhesive polymers known at the present [24]. Thiomers enhance the permeability of drugs with the potential advantage of not being absorbed through the nasal mucosa compared to low molecular weight permeation enhancers. Thus their permeation enhancing effects can be maintained over a longer period of time while excluding systemic toxic effects.[25] Thiomers tend to cause reversible opening of the tight junctions with glutathione as permeation mediator [26]. Thiolated polymers display in situ gelling properties due to the oxidation of thiol groups at physiological pH-values, which results in the formation of inter- and intramolecular disulfide bonds[12]. This increases the viscosity of the formulation coupled with extensive crosslinking due to formation of disulphide bonds with the nasal mucosa, which increases the residence time of the formulation tremendously [27].
Other studies on thiomer combinations with other polymers by Bernkop-Schnurch led to formation of thiolated polycarbophil which increases the uptake of Leu-enkephalin from the nasal mucosa by 82 folds, thus a promising excipient for delivery of Leu-enkephalin through the nasal mucosa[28]. In another study, thiolated polyacrylate microparticles were generated for the nasal delivery of human growth hormone (hGH). The intranasal administration of this microparticulate formulation to rats resulted in a relative bioavailability of 8.11 ± 2.15% that represents a 3-fold improvement compared to microparticles comprising the corresponding unmodified polymer[29].
The nasal route is an attractive alternative to parenteral delivery for a number of therapeutic peptides such as calcitonin, insulin, desmopressin, buserelin and octreotide. However, membrane permeability is low for nasally administered peptides leading to low bioavailabilities, a short local residence time at the site of absorption and a high metabolic turnover in the epithelium. The three major approaches to increase the bioavailability of intranasally administered peptide drugs are (i) the use of permeation enhancers, (ii) incorporation of enzyme inhibitors and (iii) increasing local drug residence time using mucoadhesive polymers. Thiomers are capable of combining most of these strategies. Therefore, thiomers can be used as multifunctional vehicles for systemic nasal peptide delivery[30]. Due to their high molecular mass, thiomers are not absorbed from the nasal mucosa thus systemic toxic effects can be excluded. Ciliary Beat Frequency (CBF) studies with human nasal epithelium cells show that thiomers do not cause any alteration or impact on CBF. Thiomers have also been found in various studies to not cause any irritation to mucosal cells[31]. Table 2 summarizes nasal drug delivery studies with thiomers.
Mucoadhesive Polymer
Dosage Formulation
Active Ingredient
Reference
Thiomer (polycarbophil-cysteine)
Gel
Leu-enkephalin
Bernkop-Schnürch A et al.[28]
Thiomer (polycarbophil-cysteine /glutathione gel)
Gel
Human growth Hormone
Leitner VM et al.[32]
Thiomer (polycarbophil-cysteine)
Microparticles
phosphorothioate antisense oligonucleotide
Vetter A et al[33]
Thiolated chitosan
Microparticles
insulin
Krauland AH et al[34]
Table 2.
Use of thiomers in mucoadhesive nasal formulations for systemic delivery
4. Alginate poly-ethylene glycol acrylate
Alginate Polyethylene glycol Acrylate is also known by the acronym Alginate-PEGAc. It has an alginate backbone with acrylated polyethylenglycol groups attached to it. This polymer meshes the properties of alginates (strength, simplicity and gelation) with characteristics specific to the acrylate functionality of PEG like mucoadhesion. PEG’s have the ability to penetrate the mucus surface while the acrylate group of the polymer reacts with the sulphide group of glycoproteins present in the mucus. This results in a strong interaction between the mucus and the polymer [35]. It is expected to be cross-linkable by two different paths: chemically via the acrylate end groups and physically through the alginate backbone [36]. Alginate is a mucoadhesive polysaccharide of 1 → 4 linked α-l-glucuronic acid and β-d-mannuronic acid which binds to the glycoproteins in the mucus through carboxyl–hydroxyl interactions [37]. It is anionic in nature. It is known to undergo ionic sol to gel transition (gelation) upon interaction with multivalent ions such as Ca2+, Fe2+ [38], thus reducing its adhesion to mucosal tissues [39]. On the other hand Poly-Ethylene Glycol (PEG) is an FDA approved polymer. It is non-toxic, non-immunogenic and non-antigenic. It has high solubility in water and rapid in vivo clearance. It also has the ability to form hydrogen bonds with sugar moieties on glycosylated proteins. This causes PEG to form strong bonds with mucus leading to increased mucoadhesion [25].
Poly Acrylic Acid forms hydrogen bonds between its carboxylic acid groups and sialic acid-carboxylic acid groups present in the mucus [40]. The most recent method for synthesis of Alginate PEG-Ac is a two stage procedure. First the synthesis of alginate thiol takes place. In the second stage, a Michael type addition reaction takes place where a nucleophilic addition between PEG-Diacrylate and alginate backbone occurs conjugating the two [25].
Modification of Alginates with addition of acrylic acid is done to optimize its shortcomings such as erosion in neutral pH. Addition of acrylic acid controls the release rate of drugs and also improves its adhesive properties [29]. Also it has been found that at physiological pH of 7.4 both poly acrylic acid and sialic acid undergo ionization, thus repelling each other. This leads to rapid removal of this polymer-based drug delivery system. Addition of PEG results in H-bonding with PAA enhancing the viscosity of the resulting drug delivery vehicle. Addition of PEG to the polymer increases the viscosity of the resulting polymer complex retarding disintegration and removal of the polymer from the mucosal surface thus increasing mucoadhesion [30]. The combination of the three functional moieties of Alginate Polyethylene glycol Acrylate leads to an improved novel polymer that can be used mucoadhesive nasal drug delivery.
5. Poloxamer (Pluronics)
There is a great interest in Poloxamer based formulations. A number of reviews have been published describing in detail poloxamer formulations like gels, poloxamer-coated nanoparticles, o/w and w/o emulsions, and solid polymer blends [41]. Poloxamers are made up of non-ionic difunctional triblock[42] copolymers containing a centrally located hydrophobic polypropylene oxide between hydrophilic polyethylene oxides [43, 44]. Aqueous solutions of poloxamers are extremely stable in the presence of acids, alkalis and metal ions. These polymers are readily soluble in aqueous, polar and non-polar organic solvents. Hence, they are widely preferred choice as excipients in formulations [45]. Poloxamers are said to contain thermoreversible property and will convert from a liquid to a gel at body temperature, thus, causing in situ gelation at the site of interest [1] preventing the drug to be removed from the nasal cavity due to mucociliary clearance. This vastly improves the bioavailability of the drug administered. The formation of the gel can be explained as follows. When the poloxamer is cooled, the hydration layer surrounds the poloxamer molecule and hydrophobic portions are separated due to hydrogen bonding. As the temperature increases, desolvation of the hydrophilic chains occurs as the result of breakage of hydrogen bonds. This results into hydrophobic interactions amongst the polypropylene oxide domains and gel gets formed. Hydroxyl groups of the copolymer become more accessible due to hydration[46]. Thus, desolvation caused by increase in temperature and subsequently micellization results in formation of a more closely packed viscous gel [47] Various combinations of poloxamers and other mucoadhesive polymers like polycarbophil and polyethylene oxide have been found to be more advantageous since their combination tends to reduce the gelation temperature of poloxamer. This can help in making a polymer that can gel at the temperature observed in the nasal mucosa[5]. Poloxamers are also known as Pluronics. Pluronics have also been chemically combined with poly(acrylic acid)s like Dihydroxyphenylalanine (DOPA)[31] to produce systems with enhanced adhesion and retention in the nasal cavity.
One of the most promising poloxamer is Poloxamer 407 (Pluronic F127) because of its low toxicity, high solubility, bioadhesion characteristics, and acceptability as drug delivery vehicle [48]. Some of the other investigated combination of poloxamers are polymer pluronic PF127 along with benzalkonium chloride which helped decreased the gelation onset temperature. This combination was prepared for the nasal delivery of Vitamin B12[49]. In another study, poloxamer 407 was combined with a mucoadhesive polymer or polyethylene glycol. The combination allowed the manipulation of the temperature at which the conversion of sol to gel would take place as well as decreasing and increasing the in vitro release of the drug respectively[50]. But work still needs to be done on reducing irritability which is one of the major limitations of these formulations[51]. Controlled release nasal formulations of propranolol have been made using a combination of poloxamers and other mucoadhesive polymers for such as Carbopol 934P. By controlling the release of the drug and by increasing its residence time in the nasal cavity, there was a significant increase in bioavailability of the drug[52]. Poloxamer properties are said to be affected by addition of various additives. Concentration can greatly affect the thermodynamic properties of poloxamer. Water soluble additives also affect the thermodynamic properties. The range at which gelation occurs increases with polymer concentration, whereas addition of sorbitol and PEG 15000 narrows the gel range. Significant enthalpy change occurs in gels containing sorbitol and PEG, indicative of interactions with the polymer during the phase transitions. As the concentration of the polymer increases, the aqueous gels display non-Newtonian characteristics. The hydrophobic interaction of Benzalkonium Chloride and pluronic produces a gel with higher viscosity. Addition of PEG 15000 helps achieve desired gelation characteristics for increased drug loading and use of desired formulation additives [41]. Poloxamers at low concentrations, when dispersed in liquid exist individually as monomolecular micelles. As the concentration of the pluronic in the system increases, it forms multi-molecular aggregates[53]. Different aggregate forms of poloxamers are seen depending on the molecular weight, solvent composition, and temperature[54]. Micellar behavior changes with changes in solvent composition and temperature. Various salts and additives like surfactants, polymers, cosolvents have marked effect on the micellar properties, clouding and solubilization characteristics of pluronic solutions[55]. Salts in the order of Na3PO4 > Na2SO4 > NaCl have been found to lower the critical micellar temperature significantly[56]. Pluronic block copolymers are amongst the most potent drug targeting systems. Recent research on pluronics has generated new findings indicating immuno-modulation and cytotoxicity-promoting properties of Poloxamer 407 revealing significant pharmacological interest. Human trials are in progress based on these results [57]. Along with these new findings and favourable properties, poloxamers have generated immense interest as one of the most promising novel mucoadhesive drug delivery systems. Table 3 shows most of the published studies involving nasal drug delivery with this polymer.
6. Future prospects
Although several novel strategies are currently used for nasal drug delivery using bio-and muco-adhesion strategies, the potential exists to improve these methods using other strategies such as nanoparticles, bacterial adhesion, altered amino acid sequence, and antibody mechanism. A graphic representation of these methods is shown in Figure 3. Each of these methods is discussed below.
Figure 3.
Potential future novel strategies for muco-/bio-adhesive drug delivery using Mucoadhesive Nanoparticles (A), Bacterial Adhesion (B), Altered Amino Acid Sequence (C) and Antibody mechanism (D).
Application of Poloxamer (pluronics) in formulations for nasal drug delivery
7. Mucoadhesive nanoparticles
Nanoparticles generally vary in size from 10-1000nm. Biodegradable nanoparticles have been used frequently as drug delivery vehicles due to its better encapsulation efficiency, control release and less toxic properties[70]. They offer enhanced biocompatibility, superior drug/vaccine encapsulation, and convenient release profiles for a number of drugs, vaccines and biomolecules to be used in a variety of applications in the field of medicine[71]. The average pore size of viscoelastic mucus is around 150 ± 50 nm. Thus, formulations of mucoadhesive nanopolymers can lead to effective drug delivery to the target site. Commonly used materials for formulating nanoparticles are poly(lactide-co-glycolide) (PLGA) and Pluronics [55]. PEG coatings have been widely used in the development of polymeric drug carriers, including particles composed of biodegradable polyesters and polyanhydrides. PEG coatings reduce aggregation and enhance the blood circulation times of biodegradable nanoparticles designed for drug delivery[72]. Nanoparticles up to 200 nm in diameter that are coated with a dense layer of non-mucoadhesive PEG polymers, including drug carriers composed entirely of Generally Regarded As Safe(GRAS) components, readily penetrate nasal mucus. The development of polymeric particles with improved sinus mucus penetration capability should encourage the commercial development of new generations of nanoparticle-based intranasal drug delivery systems [46].
8. Bacterial adhesion
Non-denatured bacterial cell envelopes, also known as bacterial ghosts, are produced as a result of plasmid-encoded lysis gene E of bacteriophage in gram-negative bacteria[73]. Due to its hydrophobic nature, gene E product integrates into the inner membrane, resulting in fusion of inner and outer membrane. This leads to the formation of a trans-membrane tunnel[74]. The generated trans-membrane tunnel ranges between 40-80 nm in diameter, through which all cytoplasmic contents are expelled[75]. It is imperative to note that the process of Protein E-specific lysis does not result in physical or chemical denaturation of bacterial surface structures. The bacterial ghosts have been suggested to be a great alternative method for inactivated non-living whole-cell vaccination [76]. Depending on the site-directed sequences included in the fusion, a variety of foreign proteins can be expressed within or on the cell envelop of bacterial ghosts [77]. The advantage of using bacterial ghosts is, bacterial ghosts can be produced in large quantities, do not require the cold-chain-storage system, and are stable for a long time. Further, the size of the foreign protein insert can be very large (>600 amino acids) thus allowing the presence of multiple epitopes simultaneously[78].
The attachment of synthetic or natural macromolecules to mucus or epithelial surface is defined as bioadhesion. Bacteria are capable of adhering to the epithelium surface with aid of fimbriae, which are long, lectin-like proteins found on the surface of many bacterial strains[79]. There is a correlation between the pathogenicity of bacteria and the presence of fimbriae, thus, the adhesion of bacteria to epithelial surfaces can be used as an efficient method of efficient drug-delivery[80].
Bacterial ghosts have been shown to display bio-recognitive abilities which allow their attachment to different surfaces of numerous body tissues depending on the species chosen[81]. Many of these bacterial ghosts are able to bind to surfaces due to the presence of long fimbriae which facilitate the penetration of the mucus covering epithelial tissues[65]. Thus, as a result of the properties of fimbriae a bioadhesive drug delivery system has been developed by using the ghost bacteria with a therapeutic agent coupled to E. coli K99 fimbriae[62]. This strategy may be applied to nasal drug delivery with the intention of reducing mucociliary clearance.
9. Altered amino acid sequence and antibodies
Certain amino acid sequences can be used to promote binding of drug molecules to specific cell surface glycoproteins due to the amino acids having complementary sequences present to these glycoproteins[82]. In certain disease conditions the sequence of glycoproteins is altered. This altered state can be used as a target by complementary amino acid sequences by attaching them to a drug delivery device [66]. Antibodies can be produced against selected molecules present on mucosal surfaces. Due to their high specificity, antibodies can be a rational choice as a polymeric ligand for designing site-specific mucoadhesives. This approach can be useful for targeting drugs to tumour tissues[66] or even normal cells.
10. Conclusion
There is no question that the nasal route has a great potential for systemic drug delivery. The physiology of the nasal cavity creates a variety of opportunities for drug companies to develop local and systemic drugs. As nose- to- brain delivery makes it possible to by-pass the blood-brain-barrier for certain drugs; administration of drugs via this route for treatment of neurological diseases presents exciting opportunities. Despite the advantages of nasal drug delivery, the absorption and permeability of polar drugs through the nasal mucosa remains a challenge. The mucociliary clearance system compounds the problem by limiting how long the drug stays in the nasal cavity for absorption to take place. Hence several strategies have been developed to enable the drug molecules to attach onto the mucus or epithelial layer, thus preventing them from being cleared from the nasal cavity. The application of lectins, thiomers, alginate poly-ethylene glycol acrylate and poloxamers were discussed in this chapter. These polymers are not the only polymers used for nasal delivery. However, they are among the least reviewed polymers for systemic drug delivery via the nasal route. Other bioadhesive strategies including nanoparticles, bacterial adhesion, altered sequence and antibody strategies can further improve the bioavailability of polar drug molecules delivered via the nasal route. However, a lot of work remains to be done in this area.
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Agu",authors:[{id:"149674",title:"Dr.",name:"Remigius",middleName:null,surname:"Agu",fullName:"Remigius Agu",slug:"remigius-agu",email:"remigius.agu@dal.ca",position:null,institution:null},{id:"149675",title:"Ms.",name:"Utkarshini",middleName:null,surname:"Anand",fullName:"Utkarshini Anand",slug:"utkarshini-anand",email:"U.Anand@Dal.Ca",position:null,institution:null},{id:"149676",title:"Mr.",name:"Tiam",middleName:null,surname:"Feridooni",fullName:"Tiam Feridooni",slug:"tiam-feridooni",email:"tiam.feridooni@gmail.com",position:null,institution:null}],sections:[{id:"sec_1",title:"1. Introduction",level:"1"},{id:"sec_2",title:"2. Lectins",level:"1"},{id:"sec_3",title:"3. Thiomers",level:"1"},{id:"sec_4",title:"4. Alginate poly-ethylene glycol acrylate",level:"1"},{id:"sec_5",title:"5. Poloxamer (Pluronics)",level:"1"},{id:"sec_6",title:"6. Future prospects",level:"1"},{id:"sec_7",title:"7. Mucoadhesive nanoparticles",level:"1"},{id:"sec_8",title:"8. 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A. Onifade, B.H. Olaseinde and T. 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Yadav",authors:[{id:"169328",title:"Dr.",name:"Utpal",middleName:null,surname:"Bhadra",fullName:"Utpal Bhadra",slug:"utpal-bhadra"}]},{id:"46941",title:"Pharmacokinetic Properties and Safety of Cadmium-Containing Quantum Dots as Drug Delivery Systems",slug:"pharmacokinetic-properties-and-safety-of-cadmium-containing-quantum-dots-as-drug-delivery-systems",signatures:"Lourdes Rodriguez-Fragoso, Ivonne Gutiérrez-Sancha, Patricia\nRodríguez-Fragoso, Anahí Rodríguez-López and Jorge Reyes-\nEsparza",authors:[{id:"141589",title:"Prof.",name:"Lourdes",middleName:null,surname:"Rodriguez-Fragoso",fullName:"Lourdes Rodriguez-Fragoso",slug:"lourdes-rodriguez-fragoso"}]},{id:"45772",title:"Anticipating Market Introduction of Nanotechnology-Enabled Drug Delivery Systems",slug:"anticipating-market-introduction-of-nanotechnology-enabled-drug-delivery-systems",signatures:"Haico Te Kulve",authors:[{id:"169327",title:"Dr.",name:"Haico",middleName:null,surname:"Te Kulve",fullName:"Haico Te Kulve",slug:"haico-te-kulve"}]},{id:"46864",title:"Current Status and Future Scope for Nanomaterials in Drug Delivery",slug:"current-status-and-future-scope-for-nanomaterials-in-drug-delivery",signatures:"Biswajit Mukherjee, Niladri Shekhar Dey, Ruma Maji, Priyanka\nBhowmik, Pranab Jyoti Das and Paramita Paul",authors:[{id:"73326",title:"Prof.",name:"Biswajit",middleName:null,surname:"Mukherjee",fullName:"Biswajit Mukherjee",slug:"biswajit-mukherjee"}]}]}]},onlineFirst:{chapter:{type:"chapter",id:"69809",title:"Use of Waste Foundry Sand (WFS) as Filler in Hot-Mixed Asphalt Concrete",doi:"10.5772/intechopen.89715",slug:"use-of-waste-foundry-sand-wfs-as-filler-in-hot-mixed-asphalt-concrete",body:'
1. Introduction
Industries annually generate millions of metric tons of solid by-products, and most of these materials have been landfilled at considerable cost since. Modern society has been developing beneficial reuse of industrial by-products in a variety of applications [1, 2, 3]. Recycling of waste construction materials saves natural resources, saves energy, reduces solid waste, reduces air and water pollutants and reduces greenhouse gases [4, 5]. The transportation, construction and environmental industries have the greatest potential for reuse because they use vast quantities of earthen materials annually. Replacement of natural soils, aggregates and cements with solid industrial by-products is highly desirable [1, 2].
The steel industry produces a myriad of metal components for industrial chains such as the automobile industry, which in turn generates mineral discarded sand moulds (waste foundry sand/WFS) that end up occupying large volumes in landfills [6]. The major portion of the WFS is considered as non-hazardous waste and is currently deposited in a special WFS landfill that is remote from areas of settlement [7, 8, 9, 10].
The metal casting industry annually discards about 10% of foundry sand for production, i.e. approximately an estimated 9–10 million tons of WFS each year, in the USA [5, 10, 11]. Generally speaking, approximately 1 ton of foundry sand is needed to produce 1 ton of metal casting [8, 12]. WFS can be used as an alternative material (fine aggregate in asphalt mixtures) in highway constructions allowing the increasing of the lifespan of landfills [13].
This work analyses the physical and mechanical behaviour of asphalt mixtures, using the WFS as a mineral filler in asphalt concrete, in 5% (in mass) of maximum replacement to conventional Portland cement (CP). The waste was obtained from an industry located in the free-trade zone of Manaus city, Amazon State, Brazil. The results showed that the addition of industrial WFS in asphalt mixture resulted in adequate performance of the mixtures.
2. Literature review
Waste foundry sand is generated by industries that use sands, binders and additives to form moulds and cores for castings. Sands are chosen for several reasons; they are readily available everywhere, inexpensive, highly refractory and readily bonded by clays or other inorganic and organic materials [8, 9, 14]. The mould forms the outside of the castings; the core forms the internal shape. When the part to be made has deep recesses or hollow portions, sand cores must be provided in the mould [3]. The material to be used to form moulds and cores in a foundry should have cohesiveness and porosity properties at the same time. Adding binder (bentonite, resins, cement, sodium silicate and oils) will improve the cohesiveness of the sand grains but will tend to reduce porosity. Additives are those materials which are added to the bonded sands to improve properties, either during the moulding process or during the casting process or both [8]. The moulding processes which involve sand are (1) green sand moulding (or clay-bonded sand, [12]), (2) chemically bonded process and (3) shell moulding process [3, 5, 8, 9]. The most commonly used process is green sand moulding [15]. Green sand is composed of four major materials. Sand comprises 85–95% of the green sand mixture. Most often the sand is inert silica, but olivine and zircon sand are also used [8, 15, 16, 17]. Approximately, 4–10% of the mixture is made of some form of clay, e.g. bentonite. The clay acts as a binder for the green sand and provides strength and plasticity. Combustible additives like sea coal, cereal, fuel oil and wood flour typically make up from 2 to 10% of the green sand mixture. The final additive of green sand is water which is usually added in small percentages (2–5% by weight) [5, 8]. Chemically bonded sands are those that use furan, phenolic urethane and acid cured no-bake systems, as well as alkyd and phenolic urethane cold box processes. Shell moulding uses a mixture of sand and thermosetting resin (usually phenol formaldehyde) to form the mould [8, 17].
The physical, chemical and mechanical characteristics of virgin sand make it a popular material for construction engineering, but after several reuses in moulds and cores, it becomes WFS [7]. The grain size distribution of WFS is quite uniform, with a majority of the sizes (85–95%) falling within a narrow range between 0.6 and 0.15 mm, and 5–12% is smaller than 0.075 mm [5, 8, 10] or between 1 and 16.5% [14]. According to Tikalsky et al. [17], more than 80% of the particles by mass are concentrated by size between 0.15 and 0.70 mm, compared to 0.30–4.75 mm for conventional fine aggregate. Most of the WFS materials reported are found to be medium to fine sand. WFS have been found to be too fine to satisfy the specifications for general fine aggregate [8, 10, 12]. WFS has uniform equidimensional subangular to rounded grains, and a few has rounded grains [8, 10, 17, 18].
For density and unit weight, the values found for the WFS were very close to conventional aggregate [13]. The bulk specific gravities reported in the literature on WFS ranged from 1.985 to 2.722 [8, 17]. In most of the cases WFS have been reported to be almost dry. The moisture content as received for WFS were reported to be in the range of 0.0–4.85% [8, 17, 18]. Concerning absorption, the values are relatively higher than those obtained for the natural aggregate, due to the presence of organic matter [6, 8]. The percentage absorption values on WFS samples have been reported to vary between 0.3 and 6.2% [3, 8, 17].
Over the past three decades, there have been several studies around the world on the use of WFS in engineering works, in different areas: base and subbase layers of highway construction [19, 20, 21], embankments [22, 23], hydraulic barriers [24], asphalt mixtures [3, 7, 16, 25, 26], etc.
Highway subbase layers using WFS have been shown to resist winter conditions (freeze–thaw cycles) better than specimens of reference materials [5, 17, 19]. If a subbase layer stabilised with WFS is compacted in field at dry of optimum content then it will have an increase in its strength [19, 20, 27].
It has been mentioned in the literature that the fines of WFS affect the properties of asphalt concrete negatively [7, 28]. The amount of WFS used in an asphalt mixture depends largely on the amount of fines in the WFS [5, 12, 14, 29]. Studies have recommended that WFS should replace successfully as much as 15% (in mass) of the conventional sand (fine) content in asphalt concrete [3, 9]; 8–10, 10–20 and 10%, respectively, in engineering practice in Pennsylvania, Michigan and Tennessee States [5]; 35% [30]; 15% [26]; 10% [7, 13]; 15% [10, 31]; 35% [27, 32]; and 15–30% [14].
Concerning physical characteristics, the densities of the mixtures decreased as the percentage of WFS in the asphalt concrete increased [7, 9, 10, 12, 13, 17, 32]. Percentage of air voids and voids in the mineral aggregate (VMA) were found to increase with blending of increased quantities of WFS [8, 9]. The optimum asphalt content (4.9–6.8%) for HMA mixtures containing various amounts of foundry sand is comparable to the content of mixes not containing foundry sand [14, 17]. The OAC increases with increase in the WFS percentage [13], although Miller et al. [14] found lower values for mixtures containing WFS, in relation to control ones. According to this author, the mixtures obtain the higher percentage of OAC with the WFS with the higher amount of particles passing the #200 sieve. This happens due to the fineness properties of material and increase of surface area [10, 32].
Regarding the mechanical characteristics, the Marshall stability of the asphalt concrete samples containing WFS decreases as the quantity of WFS is increased [3, 6, 7, 8, 10, 12, 29, 32]. The flow values of mixtures decreased with increasing percentage of WFS in the asphalt concrete mixtures [7, 8, 9, 10, 13]. The indirect tensile strengths of the asphalt cement mixtures decreased as the percentage of WFS material was increased [7, 8, 9, 10, 12, 13, 32]. However, Abdulsattar and Mohammed [25] found that all the WFS mixtures that they analysed showed higher tensile strength than the control mixture. According to Tikalsky et al. [17], the level of air voids and saturation greatly influenced the indirect tension values.
In relation to moisture susceptibility, WFS has little effect on top-down fatigue cracking resistance and moisture susceptibility of the mixtures [32]. When WFS replacement is higher than 15%, asphalt mix may become more sensitive to moisture damage (i.e. stripping) due to the presence of silica [10, 27]. WFS, on average, decreases the unconditioned tensile strength and thus the durability of asphalt mixtures; on the other hand, WFS do not necessarily increase or decrease a mixture’s rutting potential but do improve fatigue performance [17].
3. Materials and methods
3.1 Origin of materials
The experimental procedure of this research contemplates the dosage and physical and mechanical tests on five hot-mixed asphalt concrete (HMAC) mixtures using the conventional Portland cement filler (as reference) and four other mixtures using WFS, replacing the cement gradually in proportions of 25%. This residue was produced by the foundry industrial process of a company located in free-trade zone of Manaus city, Amazon State, Brazil, which produces clutch assembly lines (pressure and friction plates, discs, outer housing, etc.) for the motorcycle industry. Figure 1a shows one of the several kinds of pieces that are produced in that industry, while Figure 1b presents the WFS studied. The annual production of WFS in that industry was about 1500 tons in 2014 (SUFRAMA, 2016). The coarse aggregate (natural pebble) came from the “Japurá” River (an Amazon River affluent) riverbeds and was extracted by dredging, but it was acquired in the local market. The fine aggregate (clean sand) came from mining extraction in the vicinity of the city (about 30–50 km), but it was acquired in the local market as well. The mineral filler used was Portland cement II-Z-32 type. Finally, asphalt cement (AC) 50/70 grading was used, produced by the oil refinery of Manaus (REMAN). The materials used in this research and their respective origins are listed in Table 1.
Figure 1.
(a) A piece (to be deburred) produced at the trade zone of Manaus city industry. (b) WFS to be tested.
Material
Origin
Sand
Market of Manaus
Pebble
Market of Manaus
Portland cement (PC) II-Z-32 (mineral filler)
Market of Manaus
Asphalt cement (AC) (50/70 grading)
Oil refinery of Manaus (REMAN)
Waste foundry sand (WFS)
Industry of free-trade zone of Manaus
Table 1.
Provenance of HMAC component materials.
3.2 Characterisation of materials
All mineral aggregates used in the asphalt mixtures were tested according to the standards described in Table 2, mainly by the Brazilian highway standards, which are most similar to known international standards. In relation to the asphalt cement (AC—50/70 penetrating grading), it was submitted to complete characterisation according to standards shown in Table 3.
Material
Brazilian standard
Title
Acceptance parameters (Brazilian standard)
Similar international standard
Pebble
NBR NM 53/2009
Coarse aggregate—determination of the bulk specific gravity, apparent specific gravity and water absorption
Greater than 0.88 and 2.00 g/cm3; less than 18%, respectively
ASTM-T-85
Pebble
NBR NM 51/2001
Coarse aggregate—test method for resistance to degradation by Los Angeles machine
Less than 50%
AASHTO-T-96
Pebble, Sand, Fillers
NBR NM 248/2003
Aggregates—sieve analysis of fine and coarse aggregates
Within granulometric range
ASTM-C136/C136M-14
Pebble
NBR 12583/1992
Coarse aggregate—coating to bituminous binder
Qualitative test (visual analysis)
—
Sand
NBR NM 52/2009
Fine aggregate—determination of the bulk specific gravity and apparent specific gravity
Greater than 1.60 and 2.60 g/cm3, respectively
ASTM-C128–01
Fillers
NBR NM 23/2001
Portland cement and other powdered materials—determination of density
Greater than 3.00 g/cm3
ASTM-C188–09
WFS
NBR 16137/2010
Non-destructive testing—material identification by spot test, X-ray fluorescence spectrometry and optical emission spectrometry
Properties of asphalt cement (AC—50/70 penetrating grading) used in the mixtures.
In order to avoid the presence of impurities, the residue was washed in sieves Nos. 200, 300 and 400, before subjected to characterisation tests and used in asphalt mixtures. The WFS filler was subjected to chemical analysis (XRF) made by an X-Ray spectrometer equipment (720 energy dispersive, Shimadzu), through drying and subsequently pressing the sample in a disc form. The equipment can perform analyses from sodium to uranium, has a rhodium tube and is cooling by liquid nitrogen. Besides that, the WFS filler was also submitted to the X-Ray diffraction (XRD) in order to be characterised its crystalline phases. The equipment used in the analysis was the D8 Focus-Bruker diffractometer, with monochromatic cuprum radiation (CuKα, λ = 1.5418 Å), operating at 35 kV and 40 mA. A laser particle size analyser was used to determine with precision the particle size of both mineral fillers (PC and WFS).
3.3 Dosage method of the SMA mixtures
Since the tests were performed 10 years ago, asphalt concrete studies were developed through the traditional Marshall method and not by current Superior Performing Asphalt Pavements (Superpave) methodology. After the characterisation of all components of asphalt concrete, the materials were classified in the “C” granulometric range limits of Brazilian highway specifications following the Marshall dosage method, as shown in Figure 2. The curves obtained fitted in the area defined by the two curve limits of the “C” range, minimum and maximum. After fixing the particle size distribution of aggregates of the mixture, the probable optimum asphalt content (OAC) was estimated by the expression derived from the work of Duriez (1950) based on the specific surface of the aggregates:
Figure 2.
XRD analysis for WFS filler.
S=0.17G+0.33g+2.30A+12a+135f100E1
where S is the specific surface area of aggregate (m2/kg), G is the percentage retained on sieve 9.5 mm, g is the percentage passing on sieve #9.5 mm e retained on sieve 4.8 mm, A is the percentage passing on sieve #4.8 mm e retained on sieve 0.3 mm, a is the percentage passing on sieve #0.3 mm e retained on sieve 0.074 mm and f is the percentage passing on sieve 0.074 mm.
Then, the probable OAC was calculated, using the following expression:
Tca=mS5E2
where Tca is the OAC in relation to the mass of the aggregates (%) and m is the richness modulus of AC, varying from 3.75 (wearing course with high stiffness) to 4.00 (wearing course with low stiffness).
If the mean bulk specific gravity of the total aggregate is less than 2.60 or greater than 2.70, then the content obtained in the previous item should be corrected by the following expression:
Tca′=2,65TcaδamE3
where T′ca is the corrected OAC in relation to the mass of the aggregates (%) and δam is the mean bulk specific gravity of the total aggregate.
Finally, the OAC is calculated in relation to the entire mixture:
Pca=100Tca100+TcaorPca=100Tca′100+Tca′E4
where Pca is the final value of OAC in relation to the total mixture (%).
From that OAC value were adopted two points below it (each 0.5%) and two points above it (each 0.5%).
3.4 Production of SMA samples in the laboratory
Five HMAC mixtures were analysed whose grain size proportions are shown inTable 4. The mixture 1 was used as reference, for 100% of Portland cement as mineral filler. The other mixtures used WFS as mineral filler, replacing Portland cement in gradual proportions each 25%. At the end, the results were compared between the mixtures with and without WFS according to the physical and mechanical tests performed.
Oxide
SiO2
Al2O3
SO3
Fe2O3
Content (%)
93.68
3.97
1.66
0.41
Table 4.
Composition of oxides present in WFS filler.
The experimental procedures were defined as follows, for each mixture [33]: (i) determination of the AC working temperatures from Saybolt-Furol viscosity test in the range of 85 ± 10 and 140 ± 15 SSF for mixing and compaction, respectively; (ii) the components (aggregates + AC) were mixed at a temperature of 146°C for approximately 2 min; (iii) the mix was placed in the Marshall mould and compacted mechanically with 75 blows on each side of the specimen; (iv) the specimen were left at rest for 24 h at room temperature; (v) after that, the specimens were left in a water bath at 60°C for 2 h; (vi) finally, they were placed in the compression mould and submitted to compression in order to determine the rupture load and flow value. Thus, all physical and mechanical parameters of HMAC mixtures were determined by the Marshall method.
From Eq. 4, an initial OAC value of 6.15% for mixture 1 was adopted, with m = 3.75. Nevertheless, the mixture showed excessive fluid, with AC in excess. Hence, OAC = 4.5% was considered. It is noteworthy that three specimens were cast for each AC content to find the final OAC of each the mixture (mixtures 1–5), whose range varied from 3.5 to 5.5%, at each interval of 0.5%. Figure 3a presents the results of OAC for each mixture.
Figure 3.
Marshall physical and mechanical characteristics of studied mixtures: (a) optimum asphalt content, (b) bulk specific gravity, (c) air void volume, (d) asphalt-void ratio, (e) Marshall stability and (f) flow value.
3.5 Physical and mechanical properties of SMA mixtures
After the tests, the Marshall parameters of the mixtures were determined: bulk specific gravity (BSG), theoretical maximum specific gravity (TMG), air void volume (AVV), voids in the mineral aggregate (VMA), voids filled with asphalt (VFA), asphalt-void ratio (AVR), Marshall stability (STA) and flow value (FLV). The optimum contents of AC adopted were those with an AVV value of 4%.
Three samples with cylindrical forms were moulded for the determination of the static indirect tensile strength (ITS) by diametrical compression for each type of mixture, at each OAC. The ITS individual value was obtained through the expression
σt=TπrhE5
where σt is the individual static ITS (kPa), T is the static rupture load (kN), r is the sample radius (m) and h is the sample height (m).
Three samples were moulded for determining the resilient modulus (RM) of each mixture. This mixture was then placed in the mould and compacted mechanically with 75 blows on each side of the sample. Then, the specimen were submitted to a repeatedly vertical compression load F at a maximum stress level less than or equal to 20% of the ITS. The RM adopted was the arithmetical mean value determined at 300, 400 and 500 load application F.
Hence, the value of the RM was determined by the expression [33]
RM=Fδh×09976μ+02692E6
where RM is the individual resilient modulus (MPa), F is the cyclic vertical load diametrically applied on specimen (N), δ is the elastic strain recorded for 200, 400 and 500 load applications (mm), h is the sample height (mm) and μ is Poisson’s ratio.
The fatigue test was performed to define the number of loading repetitions as a function of controlled stresses in diametrical compression samples with the load applied at a frequency of 1 Hz, with 0.10 s of repeated loading duration through the same resilient modulus equipment, increasing in tensile strain until the specimen is completely disrupted at a constant temperature of 25°C. The fatigue curve was determined in seven stress levels (7.5, 10, 15, 20, 25, 30 and 40% of the static ITS) with two specimens per level. The fatigue resistance was evaluated according to the fatigue curves generated by testing, which introduces the relationship between fatigue strength and fatigue life. The fatigue equation in this study was calculated using the formula given in the following equation [34]:
logNf=n×logσf+kE7
where Nf is the fatigue life (in cycles) and σf is the fatigue stress (MPa), i.e. the tension stress applied during the test. The equation provides a linear relationship between them using a bilogarithmic scale, in which “n” is the gradient and “k” is the intercept.
The study of permanent deformation was made using the static creep test applying a static and continuous compression load on a specimen moulded according to the Marshall methodology. The specimen was placed in the axial position and then was subjected to an applied tension of 0.1 MPa, distributed over the entire contact surface of the specimen for a period of 60 min at a temperature of 40°C. The permanent deformations were measured continuously along that time, and then the specimen was discharged, waiting for 15 min for the stabilisation of the viscous deformations, which were measured continuously too. The total strain (Dt) after the recovery period can be obtained as:
Dt=∆h75hoE8
where Δh75 is the specimen height change after the final recovery period, i.e. 75 min after the start of the test load (mm), and ho is the specimen initial height taken in the axial direction of loading (mm). Table 5 shows the mechanical tests performed on HMAC mixtures, while Figure 4 presents all tests carried out on components and mixtures.
Brazilian standard
Title
Acceptance parameter (Brazilian standard)
Similar international standard
DNER-ME 043/1995
Asphalt mixtures—Marshall test
OAC ≥ 6% STA ≥ 5 kN 3% < AVV < 5%
ASTM D5581-07a
NBR 16018/2011
Asphalt mixture—stiffness determination by repeated load indirect tension test
—
ASTM D4123–82
NBR 15087/2012
Asphalt mixtures—determination of tensile strength by diametrical compression
≥0.65 MPa
ASTM D 6931–17
DNER-ME (provisional standard)/2017
Hot-mixed asphalt concrete—fatigue under repeated loading, constant tension, using the indirect tension test
—
FHWA-Protocol P07/2001
—
Standard test methods for tensile, compressive and flexural creep and creep rupture of plastics
Dt ≤ 0.02 mm/mm in 75 min
ASTM D 2990–09
Table 5.
Mechanical characterisation tests carried out on HMAC mixtures.
Figure 4.
Flowchart of the laboratory tests.
4. Results and discussion
4.1 Characterisation of materials
Figure 2 indicates the result of XRD analysis for WFS filler. As shown in the figure, WFS is essentially formed by quartz mineral, as expected. Table 4 shows the composition of the main oxides present in the WFS filler obtained by XRF analysis. The high percentage of silica confirms the XRD analysis of the material [8, 16, 17].Table 6 indicates the physical characteristics of the aggregates. WFS aggregate apparent specific gravity of WFS is very close to conventional aggregates (pebble and sand) [7, 9, 10, 13] each other except for PC. Pebble had a Los Angeles abrasion loss below the maximum allowed by the Brazilian standard, which is 50%. The WFS had 76.25% of its particle sizes passing at #200 sieve and are slightly larger than that of Portland cement, i.e. it is too fine to replace part of the fine aggregate of the asphalt mixes [8, 10, 12], thus demonstrating that the residue could only replace part or total filler fraction.
Aggregate
Apparent specific gravity (g/cm3)
Absorption (%)
Los Angeles abrasion loss (%)
d90 (mm)
d50 (mm)
d10 (mm)
Pebble
2.66
1.92
40.0
12.0
7.0
2.5
Sand
2.63
—
—
1.5
0.35
0.12
Filler (PC)
3.03
—
—
0.063
0.020
0.004
Filler (WFS)
2.65
—
—
0.133
0.040
0.004
Table 6.
Physical characteristics of aggregates.
Notes: d90, d50 and d10 are the particle size for which 90, 50 and 10% of the all particles, in mass, are finer than it.
Table 7 shows the resulting granulometric composition of the mineral aggregates with and without the addition of WFS. It is observed that all the mixtures were composed with the same amount of aggregates, varying only the proportion between the two types of the filler fraction. Conventional mixture 1 used PC exclusively, while mixture 2 used WFS as filler exclusively. The other mixtures had variations between permutations of PC and WFS proportions. The grain size distribution of the mineral aggregates, the “C” range maximum and minimum limits of the Brazilian highway specification and the resulting aggregates of mixtures 1 and 2 are shown in Figure 5.
Aggregate
Mixture designation
1 (%)
2 (%)
3 (%)
4 (%)
5 (%)
Pebble
62.0
62.0
62.0
62.0
62.0
Sand
33.0
33.0
33.0
33.0
33.0
Filler (cement)
5.0
0.0
3.75
2.5
1.25
Filler (WFS)
0.0
5.0
1.250
2.5
3.75
% Total
100.0
100.0
100.0
100.0
100.0
Table 7.
Granulometric composition of mineral aggregate mixtures with and without WFS addition.
Figure 5.
Grain size distribution and limit curves of mineral aggregates.
4.2 Physical characteristics of mixtures
Figure 3 shows the main physical parameters of the mixtures, obtained through the Marshall methodology. OAC values of the mixtures containing WFS are comparable to the control in mixture 1 [14, 17]. Mixture 1 obtained the lowest OAC (4.5%), whereas mixtures with WFS had little bit higher OAC values, whose contents increased as WFS proportions were increased too [13]. This reason probably is due to the absorption characteristics of this residue, and not due to the grain size [10, 32], since CP has larger particle size and therefore smaller surface area and thus should consume less AC, at the same proportion of WFS.
It was observed that all five mixtures met the Brazilian standards regarding the physical Marshall parameters (OAC, AVV, VMA and AVR). Mixture 1 had a higher GMB values than all other mixtures with WFS and was therefore the densest. The other mixtures maintained a slight decrease of this parameter, when the proportion of WFS in the mixture was increased [7, 9, 13]. Mixture 2 (100% WFS filler) had the highest amount of AVV and the second largest AVR among all mixtures. AVV values increased when WFS content were increased in the mixtures [8, 9, 10, 32].
4.3 Mechanical characteristics of mixtures
High amounts of AVV and AVR tend to negatively influence STA and FLV values, given the viscous characteristic of AC. Thus, mixture 1 showed the best performance, with the highest STA and lowest FLV values. Among the mixtures using WFS, mixture 5 (one fourth WFS + three fourths PC) was the one that presented the highest value of GMB, thus being the densest, and also presented the highest value of STA; however, it had the highest FLV value too. The FLV values of the WFS blends were higher than the PC blends, which characterises a higher AC consumption of these blends. In summary, the use of WFS decreased the stability of blends [6, 8, 10, 12, 32] while increasing their fluency. This latter is in disagreement with that observed by the author cited previously. Even so, all mixtures showed STA values higher than the minimum required (>5 kN).
There was a certain tendency that static ITS values will decrease as WFS content increased [7, 9, 10, 13, 32]. Mixtures 3 and 5 presented higher values of this parameter than control mixture 1 [25]. All asphalt mixtures presented values above the minimum value of the Brazilian standard (>0.65 MPa). This is a good indication for durability of the mixtures since fatigue life is a function of ITS. There was not an apparent correlation between AVV and static ITS values (Figure 6).
Figure 6.
Mechanical characteristics of studied mixtures: (a) static indirect tensile strength, (b) resilient modulus, (c) RM/ITS ratio and (d) total strain (static creep).
The use of WFS decreased the RM values. Mixture 1 presented the highest value, followed by mixture 2. In Brazil, the relationship between RM and static ITS (RM/ITS) has been used as an analysis parameter to evaluate the behaviour of asphalt mixtures related to fatigue life. As a rule, mixtures with RM/ITS ratio around 3000 exhibit good structural behaviour because they allow the use of thinner asphalt wearing layers for the same fatigue life; that is, they characterise mixtures that are not susceptible to early development of permanent deformations because they are not rigid enough. In this sense, mixture 3 was the only one that met this criterion. On the other hand, the conventional mixture 1 presented the highest value of this ratio, thus indicating a more rigid behaviour.
Figure 7 shows the comparison between asphalt mixtures in relation to the stress-controlled fatigue test. For the acquisition of fatigue curves, the average value of the RM and the static ITS of each mixture were used. Between Mixtures 1 and 4, the best-fitting straight lines were very close to each other, with a parallelism between the line slopes, and both mixtures can be considered to have practically the same fatigue life. Mixture 2 presented the shortest fatigue life, while mixture 5 presented the longest fatigue life, standing out among the others. For applied stress differences up to 0.4 MPa, Mixtures 1, 2 and 4 behave similarly.
Figure 7.
Fatigue life for the mixtures with and without WFS content.
It should be noted that mixture 5 presented the second best ITS result and the second closest value of the RM/ITS ratio around 3000, thus justifying the use of this parameter as a quantitative indicator of fatigue life of asphalt mixtures. The fatigue life test on mixture 3 was not performed.
Regarding the permanent deformation, Mixtures 2 and 3 presented lower values than mixture 1, while mixture 5 presented the highest value among the others. There was no direct relationship with AVV, since, of all of them, mixture 5 presented the lowest value of voids. Mixture 3 presented the lowest value of permanent deformation, confirming again the good indicative of the RM/ITS ratio around 3000 in predicting the behaviour of asphalt mixtures for fatigue and permanent deformations. All mixtures presented permanent deformation values below the conventional criterion of 0.020 mm/mm and do not have the tendency to be susceptible to premature permanent deformations.
5. Conclusions
This work analysed five asphalt mixtures, one using 100% CP as a filler and the other four using WFS, with a maximum proportion of 5% (by weight) of the total aggregate. The WFS residue used consisted of almost 94% silica, without organic compounds, with apparent specific gravity similar to clean sand and slightly coarser than CP.
All mixtures with WFS residue presented physical and mechanical parameters within the Brazilian standards, following the Marshall methodology, although with lower STA and higher FLV values. The use of WFS increased static ITS values, while decreased MR values. The mixtures with WFS showed total permanent deformation values less than 2% after 75 min of the test. The RM/ITS ratio around 3000 proved to be a good indication of mixtures with better performance against fatigue life and permanent deformation.
Finally, the use of WFS as a mineral filer in asphalt mixtures proved to be adequate, meeting the criteria of Brazilian standards in physical and mechanical tests.
Acknowledgments
The authors would like to thank Prof. Dr. Laura Maria Goretti da Mota, from Pavement Laboratory of COPPE/Federal University of Rio de Janeiro (UFRJ), for some laboratorial tests carried out in that place. This work was supported by the CNPq [grant number 620244/2008-9]; FAPEAM [scholarship].
\n',keywords:"waste foundry sand (WFS), mineral filler, asphalt mixture, fatigue life, static creep, resilient modulus, static indirect tensile strength, Marshall stability",chapterPDFUrl:"https://cdn.intechopen.com/pdfs/69809.pdf",chapterXML:"https://mts.intechopen.com/source/xml/69809.xml",downloadPdfUrl:"/chapter/pdf-download/69809",previewPdfUrl:"/chapter/pdf-preview/69809",totalDownloads:319,totalViews:0,totalCrossrefCites:0,dateSubmitted:"May 21st 2019",dateReviewed:"September 13th 2019",datePrePublished:"October 29th 2019",datePublished:null,dateFinished:null,readingETA:"0",abstract:"The environmental issue has become a topic of relevant discussion in modern society, given the current awareness that construction inputs are finite, and a large amount of waste can be reused as a building material in engineering works. The products used in foundry industry can be non ferrous and ferrous and the residue produced by this last one is not potentially hazardous to human health. The waste foundry sand (WFS) fits this reuse and can be employed in asphalt mixtures, in partial or complete replacement of the conventional filler, i.e. Portland cement (PC). In this sense, this work analyses five asphalt mixtures, one using 100% CP (reference mixture) as filler, and the other four using WFS in proportions of 25-100%, every 25% of the total amount, in 5% (in mass) of the maximum replacement. The mixtures were physically and mechanically characterised according to the Marshall methodology and subsequently submitted to the tests of static indirect tensile strength (static ITS), resilient modulus (RM), repeated-load indirect fatigue (fatigue life) and unconfined static creep. The results of the tests showed that all mixtures with WFS residue presented physical and mechanical parameters within Brazilian standards following the Marshall methodology.",reviewType:"peer-reviewed",bibtexUrl:"/chapter/bibtex/69809",risUrl:"/chapter/ris/69809",signatures:"Nilton de Souza Campelo, Karine Jussara Sá da Costa, Raimundo Kennedy Vieira and Adalena Kennedy Vieira",book:{id:"8436",title:"Sandy Materials in Civil Engineering",subtitle:"Usage and Management",fullTitle:"Sandy Materials in Civil Engineering - Usage and Management",slug:"sandy-materials-in-civil-engineering-usage-and-management",publishedDate:"July 22nd 2020",bookSignature:"Saeed Nemati and Farzaneh Tahmoorian",coverURL:"https://cdn.intechopen.com/books/images_new/8436.jpg",licenceType:"CC BY 3.0",editedByType:"Edited by",editors:[{id:"296316",title:"Dr.",name:"Saeed",middleName:null,surname:"Nemati",slug:"saeed-nemati",fullName:"Saeed Nemati"}],productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"}},authors:null,sections:[{id:"sec_1",title:"1. Introduction",level:"1"},{id:"sec_2",title:"2. Literature review",level:"1"},{id:"sec_3",title:"3. Materials and methods",level:"1"},{id:"sec_3_2",title:"3.1 Origin of materials",level:"2"},{id:"sec_4_2",title:"3.2 Characterisation of materials",level:"2"},{id:"sec_5_2",title:"3.3 Dosage method of the SMA mixtures",level:"2"},{id:"sec_6_2",title:"3.4 Production of SMA samples in the laboratory",level:"2"},{id:"sec_7_2",title:"3.5 Physical and mechanical properties of SMA mixtures",level:"2"},{id:"sec_9",title:"4. Results and discussion",level:"1"},{id:"sec_9_2",title:"4.1 Characterisation of materials",level:"2"},{id:"sec_10_2",title:"4.2 Physical characteristics of mixtures",level:"2"},{id:"sec_11_2",title:"4.3 Mechanical characteristics of mixtures",level:"2"},{id:"sec_13",title:"5. Conclusions",level:"1"},{id:"sec_14",title:"Acknowledgments",level:"1"}],chapterReferences:[{id:"B1",body:'Abichou T, Edil TB, Benson CH, Bahia H. 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Recycling foundry sand in road construction–field assessment. Construction and Building Materials. 2014;61:69-78. DOI: 10.1016/j.conbuildmat.2014.02.055'},{id:"B22",body:'Fox PJ, Mast DG. Geotechn1cal performance of highway embankment constructed using waste foundry sand (Final Report). School of Civil Engineering, Purdue University, West Lafayette, Ind., Project No. C-36-36Z, FHWA/IN/JTRP-98/1; 1998'},{id:"B23",body:'Partridge BK, Fox PJ, Alleman JE, Mast DG. Field demonstration of highway embankment construction using waste foundry sand. Transportation research record 1670. Transportation Research Board. Washington, DC; 1999;1670(1):98-105. DOI: 10.3141/1670-13'},{id:"B24",body:'Abichou T, Benson C, Edil T. Foundry green sand as hydraulic barriers: Field study. Journal of Geotechnical and Geoenvironmental Engineering. 2002;128(3):206-215'},{id:"B25",body:'Abdulsattar ZA, Mohammed EA. Effect of waste foundry sand on indirect tensile strength of asphalt mixture. Journal of Engineering and Sustainable Development. 2018;22(4):116-123. DOI: 10.31272/jeasd.2018.4.9'},{id:"B26",body:'Coutinho B, Furlan AP, Fabbri GTP. Evaluation of the reuse of foundry sand as aggregate in dense asphalt mixtures. In: Proceedings of the International Symposium on Pavement Recycling (ISPR ‘05), ISPR; 14-16 March 2005; São Paulo/SP, Brazil; 2005'},{id:"B27",body:'Winkler ES, Bol’shakov AA. Characterization of foundry sand waste. Center for Energy Efficiency and Renewable Energy, University of Massachusetts at Amherst, Chelsea Center for Recycling and Economic Development, Technical Research Program; 2000'},{id:"B28",body:'Shah V, Aijaz A, Naidu K, Francis S, Kayam PK. Waste aggregate in concrete pavement—A review. International Journal of Latest Engineering Research and Applications (IJLERA). 2016;1(9):44-50'},{id:"B29",body:'Abichou T, Benson CH, Edil TB. Beneficial reuse of foundry by-products. In: Environmental Geotechnical Report 99-1. 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