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Lignocellulosic nanomaterials for construction and building applications
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Lignocellulosic nanomaterials for construction and building applications
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Wei Chen Lum*, Seng Hua Lee†, Zakiah Ahmad*, Juliana Abdul Halip‡ Kit Ling Chin† Institute for Infrastructure Engineering and Sustainability Management, Universiti Teknologi MARA, Shah Alam, Malaysia* Institute of Tropical Forestry and Forest Products, Universiti Putra Malaysia, Serdang, Malaysia† Faculty of Technology Management and Business, Universiti Tun Hussien Onn, Parit Raja, Malaysia‡
1 Introduction Nanomaterial, as its name implies, is extremely minutes particles. The International Organization for Standardization (ISO) defined nanomaterial as a material having any external dimension or internal structure in the length range of 1–100 nm [1]. Lignocellulose or lignocellulosic biomass is plant dry matter composed of carbohydrate polymers, namely cellulose and hemicellulose, and a polyphenolic polymer, which is lignin [2]. Therefore, lignocellulosic nanomaterial refers to materials derived from lignocellulosic biomass, for example, nanocellulose, nanohemicellulose, and nanolignin. The first extraction procedure of nanocellulose was reported by Ranby [3] and was first made by Ranby [4] at the Uppsala University before the field has quieted down for more than 40 years. However, the interest on nanocellulose has been rekindled in the last 20 years seeing the continuously increment in researches around the world [5]. The statement was supported by the data compiled by Garcia et al. [6] who reported that the annual average of publications on the mentioned topic was less than 500 documents/year up to 2000. This amount increased more than twofolds in the years between 2005 and 2010, which recorded an annual average publication of 1000–1500 documents/year. From 2010 onwards, the figures reached a whopping 2500 documents/year. The trend of the researches in this particular field also sees a drastic change from preparation and characterization studies toward application of these nanostructures in different fields. Lately, mitigation of greenhouse gas emissions emittance is a matter of the utmost importance. It could be achieved by either increase the application of Industrial Applications of Nanomaterials. https://doi.org/10.1016/B978-0-12-815749-7.00015-3 # 2019 Elsevier Inc. All rights reserved.
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lightweight building materials that are environmentally friendly, derived from renewable sources and recyclable or through the usage of novel materials with improved insulation properties that are able to reduce the energy consumption during the lifetime service of a building. Because of that, a number of nanoparticles have been used in imparting better properties to the construction and building materials in the past few years. Carbon nanotubes have been used in concrete and ceramics for better mechanical and thermal properties. Silicon dioxide (SiO2) nanoparticles have been used in window for fire proofing as well as antireflection while titanium dioxide (TiO2) has been applied for rapid hydration of concrete. For steel, copper (Cu) nanoparticles have been applied to attain weld ability and formability as well as to gain corrosion-resistance properties. In coating or painting, nanosilver was often used to bestow biocidal properties to the coated materials [7]. Apart from that, a by-product from kaolin called kaolinite has also been used to produce ultra-highperformance concrete (UHPC) where higher compression, tensile, and flexural strength have been reported [8]. However, this chapter focused only on the lignocellulosic nanomaterials and their applications in construction and building sector.
2 Types of lignocellulosic nanomaterials Lignocellulosic materials constituted by three main cell wall component, namely hemicellulose, cellulose, and lignin. Each component contributes differently to the strength properties of the lignocellulosic materials. In concrete terms, hemicellulose is the bonding agent or cross-linking material between cellulose and lignin. Cellulose acts as reinforcement that contributes to tension forces and lignin for compression forces [8a]. Nanocellulose exists in a number of forms, which generally can be classified into two subcategories: (1) short and needle-shaped nanocrystalline cellulose (NCC)/cellulose nanocrystals (CNCs) which sometimes called as nanowhiskers (CNWs) or NCC and (2) nanofibrillated cellulose/slender cellulose nanofibers (CNFs) [9, 10]. In addition to these two subcategories, bacterial nanocellulose (BNC) is another main subcategory of nanocellulose [11]. Nanocellulose possesses synergetic effect of the key properties of cellulose and the characteristics of the nanoscale. Cellulose nanomaterials are capable of being versatile in a variety of applications owing to its high surface-area-to-volume ratio. For example, cellulose nanomaterials can be used as reinforcement of polymers due to its high mechanical properties and aspect ratio [12]. In the recent years, availability of huge volumes of cellulose nanomaterials has opened up the possibility of these materials to be used in various application areas. According to Moon et al. [12], cellulose nanomaterials can act as additive to adhesive, paper-based products, drilling fluids, cement-based materials, food coatings, transparent-flexible electronics, catalysis support structure, and biomedical applications. Lignin is the most abundant by-products of the paper industry as well as the second most abundant natural aromatic polymer which can be found on earth.
3 Application of lignocellulosic nanomaterials in construction
FIG. 1 The three structural units of lignin [14]. (Reproduced with permission from Elsevier.)
The three-dimensional (3D) and highly cross-linked of lignin macromolecule can be broken down into three monomers which are coniferyl alcohol, synapyl alcohol, and p-coumaryl alcohol. The monomers are connected together mainly by ether linkages and condensed linkages. The final structure of lignin is composed of three units: (1) guauacyl (G-type), (2) synringyl (S-type), and (3) p-hydroxylphenol propane (p-H-type) [13, 14]. The three structural units of lignin are illustrated in Fig. 1. The ratio of these units existed in the structure of lignin depends on the origin of the lignin (softwood, hardwood, and grass) and also the delignification process applied [15, 16]. The lignin nanoparticles (LNP) synthesized can be used in various application. Lignin-based nanomaterials offer numerous benefits when compared to conventional synthetic materials. Lignin-based nanomaterials are biodegradable, carbon dioxide neutral, available abundantly from industrial byproducts, relative low cost, and environmentally friendly besides also having antioxidant, antimicrobial, and stabilizer properties [17–19].
3 Application of lignocellulosic nanomaterials in construction and building materials Building materials represent a variety of materials that are used for construction purposes including wood and timber, fired bricks and clay blocks, steel, concrete, cement composites, etc. Construction and building materials can be simply classified as structural and nonstructural materials. Concrete, wood, and steel are three of the main structural materials while nonstructural materials including glass, plastics, insulator, and adhesives [20]. Nanomaterials can be applied in the production of construction and building materials. Nanomaterials are able to enhance the properties of construction and building materials by acting as a reinforcement to the concrete and steel [20]. When it comes to the application in the construction and building materials, nanotechnology offers several advantages such as sturdier and stronger but relatively lighter structural composites, cementitious materials with superior properties, thermal and sound insulators with lower thermal transfer rate, and better sound
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absorption capability [7]. According to Zhu et al. [21], nanomaterials have been applied in the construction sectors aiming to increase the strength and durability of construction materials and components while reducing pollution at the same time. Table 1 listed the nanomaterials derived from various lignocellulosic sources and its uses in the construction and building materials.
3.1 Concrete and cement composite During the production process of concrete and cement, environmental issues such as high energy consumption and emittance of carbon dioxide are highly undesirable. Application of nanotechnology has alleviated the aforementioned matters where new concrete and cement with enhanced properties was produced by the addition of nanoparticles [36]. Nanomaterials are believed to be able to improve the strength of conventional concrete by exerting superior filler effect that increase the bulk properties and therefore resulted in denser concrete. Several drawbacks such as microvoid, porosity, and deterioration caused by alkali silica can be negated by the addition of nanomaterials [37]. In the production of cement, CNCs have the ability
Table 1 Nanomaterials derived from various lignocellulosic biomass sources and its uses in the construction and building materials. Biomass source
Nanomaterial
Green algae (Cladophora sp)
Cellulose nanofiber
Softwood pulp
Nanocellulose fiber gel
Bacteria (Gluconacetobacter xylinus)
Bacterial nanocellulose powder, gel and
Application and finding Reinforcement in concrete. Flexural stress of the concrete mortar was enhanced by almost 3 times after reinforcement with algal cellulose nanofiber while commercial cellulose resulted in negative effects in the flexural stress of the concrete mortar Reinforcement in cement composites Improved flexural strength and energy absorption property of cement paste Reinforcement in fibercement composites Bending and internal
Reference [22]
[23]
[24]
3 Application of lignocellulosic nanomaterials in construction
Table 1 Nanomaterials derived from various lignocellulosic biomass sources and its uses in the construction and building materials. Continued Biomass source
Nanomaterial coated onto bagasse fibers
Bacterial cellulose extracted from nata-de-coco
Bacterial nanocellulose
Balsa tree (Ochromapyramidale Cav)
Nanofibrillar cellulose
Rachis of date palm tree (Phoenix dactylifera L.)
Nanofibrillar cellulose
Application and finding bonding strength of the fiber-cement composites reinforced with bacterial nanocellulose was improved and the highest fracture toughness was recorded in the composites made with bacterial nanocellulosecoated bagasse fibers Reinforcement in soy polyol-based polyurethanes nanocomposites Higher flexural strength and modulus was achieved in bacterial cellulose reinforced polyurethanes nanocomposites Balsa wood fibers— castor bean cake— glycerol matrix composites Production of green composite is feasible and the addition of nanofibrillar cellulose increased the flexural modulus of the resultant composites when the density of the composites remained constant Hybrid composites aerogels monolith made with combinations of cellulose microfibers, cellulose nanofibers and nanozeolites Hybrid materials with super thermal insulating properties was produced by adding nanozeolites to cellulose nanofibers
Reference
[25]
[26]
[27]
Continued
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Table 1 Nanomaterials derived from various lignocellulosic biomass sources and its uses in the construction and building materials. Continued Biomass source
Nanomaterial
Bamboo pulp
Nanofibrillated cellulose and cellulosic pulp
Raw jute fibers
Nanocellulose fiber
Waste jute fibers
Nanocellulose suspension
By-products from pulp and paper industries
Lignin nanoparticles— Lignosulfonate
Application and finding Reinforcement of the extruded cementbased materials In the hybrid composites the nanofibrillated cellulose improved the mechanical behavior compared to the composite without nanofiber Reinforcement in natural rubber nanocomposite Enhanced Young’s modulus and tensile strength of the nanocomposite Coating for woven jute fabric to produce green epoxy composites Epoxy composite reinforced with nanocellulose-coated woven jute revealed better tensile modulus, flexural properties and fracture toughness but lower tensile strength Substitution of phenol in the synthesis of phenolformaldehyde (PF) wood adhesive Bio-resin for wood composite with higher shear strength and modulus of elasticity was produced by using lignosulfonate during PF resin synthesis. The bioresin produced also demonstrated better thermal properties
Reference [28]
[29]
[30]
[31] [32]
3 Application of lignocellulosic nanomaterials in construction
Table 1 Nanomaterials derived from various lignocellulosic biomass sources and its uses in the construction and building materials. Continued Biomass source
Nanomaterial
Sugarcane bagasse
Lignin acetate
Giant reed (Arundo donax L.)
Lignin nanoparticles (LNP)
Kraft pulping process
Kraft lignin
Application and finding Water resistance surface coating Water absorption tests showed the coated substrates had significantly lower a weight increase compared to the untreated substrate Reinforcement of Polymethyl methacrylate (PMMA) nanocomposites Thermogravimetric analysis (TGA) test showed that LNP visibly improved the thermal stability of PMMA. The hardness of the PMMA also increased and fulfilled the required hardness values for industrial applications such as building materials Thermoplastic ligninbased nanocomposites Results shows that lignin-based nanocomposite not only exhibited enhanced toughness and ultimate elongation compared to homopolymers, but also showed 10 times higher toughness and 4 times better ultimate elongation than the corresponding lignin/ polymer blend system
Reference [33]
[34]
[35]
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as superplasticizer to promote a more uniform particle distribution and subsequently resulted in stronger material. Lignocellulosic nanomaterials have been used by several researchers in improving the concrete and cement composite. Claramunt et al. [38] reinforced cement mortar composites with nanofibrillated cellulose and sisal microfibers and reported that the flexural strength and modulus of elasticity of the composites improved with increasing nanofibrillated pulp content. On the contrary, the nanofibrillated pulp reinforced cement mortar composites have lower toughness or more brittle compared to that of the composites reinforced with sisal microfibers. Onuaguluchi et al. [23] prepared nanocellulose fiber gel from bleached softwood pulp and mixed it with general use limestone cement paste. After the addition of nanocellulose fiber gel, the hydration rate of the cement decreased at the early stage but no negative effect on the 28-day degree of hydration was detected. Enhanced flexural strength and energy absorption property of cement paste was observed even merely 0.1% nanocellulose fiber were added. Da Costa Correia et al. [28] derived nanofibrillated cellulose from bamboo pulp and reinforced it in the cement composite. Comparison was made between the cement composite reinforced with 9% cellulosic pulp with those of reinforced with 8% pulp and 1% nanofibrillated cellulose. In the presence of nanofibrillated cellulose, the mechanical strength of the cement composites improved, which suggested that the content of 1% of nanofibrillated cellulose associated with 8% of pulp was sufficient to form stress transfer bridges in the nano and micro-cracking. On the other hand, accelerated aging did not affect the mechanical performance of both types of cement composite adversely. In addition, the water absorption and apparent void volume of the hybrid composites were no higher than composites without nanofibers at 28 days, although the higher water/cement ratio of the composites with nanofibers. It was due to the fact the high specific surface area of the nanofibrillated cellulose allowed the improvement of the packing of the nanofibers with the particles of the matrix (cement + limestone). In another research, cellulose microfiber and nanofiber enhanced the thermal properties of hybrid composite. Bendahou et al. [27] found that hybrid aerogel biocomposite prepared using cellulose microfibers, CNFs, and nanozeolites exhibited low thermal conductivity value which was 18 mW m 1 K 1. The value was lower than most aerogel materials used as insulating material which has thermal conductivity higher than 20 mW m 1 K 1 as reported by Hrubesh and Pekala [39] and Lu et al. [40]. The substantial reduction in thermal conductivity was achieved by the addition of nanozeolites to CNFs which combined the inter-cellulose films meso-porosity and closed the nanozeolite pores. Considering of the vital characteristics of the nanofibrillated cellulose, which are, worldwide availability, renewable resource and most importantly have a high aspect ratio and specific surface area, nanofibrillated cellulose is considered a promising material to be used as a nanoreinforcement material of the extruded hybrid cement-based biocomposites. Apart from nanofibrillated cellulose derived from various lignocellulosic sources, BNC has also been used as reinforcement in cement and concrete. Mohammadkazemi et al. [24] used BNC extracted from Gluconacetobacter xylinus in the
3 Application of lignocellulosic nanomaterials in construction
forms of powder, gel, and coated onto the bagasse fibers to produce fiber-cement composites. The results revealed that bagasse fibers coated with BNC exhibited increased surface OH groups and contact surface. Fiber-cement composites produced from BNC-coated bagasse fibers showed the best properties among the other forms as the BNC protect the fiber from mineralization by inhibits the penetration of alkali ions. On the other hand, in comparison to the powder form, BNC in gel form displayed better mechanical strength and higher hydration temperature. Recently, marine biomass such as algae has entered people’s vision as a promising source of nanocellulose production. The benefits of marine biomasses over land plants are that they have higher rapid growth rate and are low in natural physicochemical barriers. Therefore, no severe chemical treatment is required to remove their inherently recalcitrant structure in order to enhance the cellulose accessibility [41]. Cengiz et al. [22] used CNF derived from green algae, Cladophora sp., as a reinforcement in concrete. The efficiency of the CNF derived from green algae in the concrete reinforcement was compared with commercial cellulose. Due to its higher aspect ratio, concrete produced by adding algae CNF in concrete mortar exhibited almost three times higher the flexural stress when compared to the concrete made from shorter commercial cellulose. This was possible as a result of improved bonding interface between nanofibers and the cement paste.
3.2 Wood Wood is a prevalently used renewable construction and building material well known for its high strength-to-weight ratio and lower processing energy [42]. Unfortunately, wood in use is dimensionally instable when exposed to moisture and susceptible to the degradation by bio-organisms as well as discoloration caused by the exposure to ultraviolet (UV) light. Application of nanocomposite coating could help to protect and improve the performance and functionality of wood [43]. Apart from acting as reinforcement materials, nanocellulose has also been incorporated into coatings system for wood protection. Generally, incorporation of nanomaterials such as CNC into the coating system could enhance its mechanical properties, hardness, and abrasion resistance [44]. Cataldi et al. [45] compared the effectiveness of nanocellulose- and microcellulose-filled UV-light curable methacrylic-siloxane-cellulose composite coatings in terms of thermal properties, dimensional stability, stiffness, hydrophobicity, and surface hardness on maple wood. The results revealed that nanocellulosefilled coatings are superior in all aspects compared to that of the microcellulose-filled coatings. Veigel et al. [46] incorporated microfibrillated cellulose (MFC) and NCC into waterborne acrylate/polyurethane-based wood coating and was applied on the particleboard covered with beech veneer. Higher scratch resistance and hardness of coated wood but no significant improvement in abrasion resistance was observed. It is interesting to note that MFC works better than NCC in improving the mechanical properties of waterborne wood coating. Similar findings were also reported by Cheng et al. [47] TEMPO-oxidized CNFs were added into waterborne polyurethane
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coating. The improvements were attributed to the good compatibility and strong interfacial adhesion between the waterborne polyurethane coating and TEMPOoxidized CNFs through hydrogen bonding. In addition, a continuous network is formed when the content of the TEMPO-oxidized CNFs exceeds the critical percolation threshold.
3.3 Polymer composites As the public’s awareness toward environmental conservation grew over the years, more and more environmental friendly materials are currently in demand. Dependency on petroleum-based polymers is, therefore, lessen in favor of the synthesis of greener and renewable polymers. However, the thermomechanical performance of renewable polymers is relatively poor compared to the conventional petroleum-based polymers. Polymer composite can be modified with the addition of nanofillers to produce a polymer composite with enhanced properties. A nanocomposite is a multiphase solid material where one of the phases has one, two, or three dimensions of less than 100 nm. Performance of the polymer composites such as mechanical strength, thermal stability, and barrier properties could be improved by the incorporation of nanofillers [48]. Clay minerals, carbon nanotubes, and silica nanoparticles are among the nanofillers that often adopted in improving the physical, mechanical, and thermal properties of polymers [49]. Dufresne et al. [50] was the first to demonstrate the application of cellulose microfibrils from potato tuber cells to improve the properties of polymer composites. Nakagaito and Yano [51] reported mechanical strength enhancement of phenol formaldehyde (PF) resin-based composites reinforced with nanoscale fibrillated cellulose. In a review by Kargarzadeh et al. [52], thermoset polymer composites including epoxy, unsaturated polyester resin, phenol-, melamine-, and ureaformaldehyde resins, and nanocellulose reinforced polyethylene terephthalate (PET) composite have been reviewed and discussed. Although having identified with various advantages such as high physico-mechanical properties, thermoset composites are brittle and easy to crack. Nanocellulose could act as reinforcement for thermoset composites in order to enhance its fracture toughness [52]. Thomas et al. [29] reported that, the increase of nanocellulose content in the natural rubber matrix had resulted in a significant improvement of the mechanical properties of the composite. The modulus of elasticity and tensile strength of material also increased as the nanocellulose content increased. The enhanced mechanical properties can be attributed to the formation of the nanocellulosic networks in the natural rubber matrix. Nanocellulose can also be used as surface coating to improve the material properties. Jabbar [30] found that nanocellulose coating over woven jute composite improved its mechanical properties. In the study, three different concentration (3, 5, and 10 wt%) of nanocellulose coating were applied to jute composite, and the results obtained show enhanced tensile and flexural strength compared to uncoated jute composite. In comparison to the extensively reported nanofibrillated cellulose-based polymer composites, lesser studies were reported on the BNC-based polymer composites.
3 Application of lignocellulosic nanomaterials in construction
This is because nanofibrillated cellulose can be produced in huge quantities in laboratories using a variety of methods. BNC contains only pure cellulose while nanofibrillated cellulose often consists of both cellulose and hemicellulose [53]. Bacterial cellulose nanofibril extracted from nata-de-coco was used by Ozgur Seydibeyoglu et al. [25] as a reinforcement in soy polyol-based polyurethanes nanocomposites. Significantly higher flexural strength and modulus was achieved in bacterial cellulose nanofibril-reinforced polyurethanes nanocomposites even at the loading of less than 0.5 wt%. In addition, the transparency of bacterial cellulose nanofibrilreinforced polyurethanes nanocomposites was not significantly affected as it stays in the same range with the neat polyurethane. On the other hand, in the development of lignin nanocomposites, emphasis should be put on the molecular uniformity of the lignin as it is an important factor that influences the final properties of the composites. The preparation procedure of lignin is, therefore, very vital. Recently, lignin-based nanocomposites have been synthesized by using different grafting strategies. Lignin-based carbon/CePO4 nanocomposites were produced by Li et al. [54] and showed great potential to be utilized in luminescent devices. Hilburg et al. [35] produced lignin-based nanocomposites using synthetic thermoplastic polymers grafted from kraft lignin. The polymers were synthesized with the application of atom transfer radical polymerization (ATRP) and possessed an average particle size of 5 nm. The results reported that, the poly(methyl methacrylate)-grafted samples exhibited ultimate elongation of approximately two times higher compared to that of the polystyrene grafts at high graft density. Both types of grafted nanocomposites possessed 10-times higher toughness values in comparison to that of the corresponding kraft-lignin/polymer blend system. In comparison to the other inorganic nanoparticles-based nanocomposites, lignin grafted with thermoplastic polymers is an inexpensive, renewable, and worthwhile material that bestows unique properties to the resultant nanocomposites. Nano-lignin could be used as partial replacement of carbon black in the production of natural rubber composites. Nano-lignin filled natural rubber composites were successfully produced by Jiang et al. [55] through coprecipitation of colloidal lignin-cationic polyelectrolyte complexes and rubber latex. PF resin is widely used as a binder in wood composite. Various studies have shown that phenol which is the main component in the resin can be substituted with lignin from plants. However, for the proper reaction to take place during resin synthesis, the lignin used will first have to be synthesized into lignosulfonate (LS). Phenol can be substituted with LS at a relatively high level which is about 50 wt%. PF adhesive with the addition of 50% LS displayed better strength performance when compared to conventional pure PF adhesive. With the substitution of phenol with LS, PF resin with cheaper cost can be produced because LS is relatively cheaper than pure phenol. Although PF resin with different level of LS substitution can be synthesized, PF resin with 20% LS replacement showed the highest shear strength in both wet and dry conditions [31]. In another study, Domı´nguez et al. [32] investigated the various properties of lignin-based phenol formaldehyde (LPF) resin containing a 30 wt% of ammonium
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LS (extracted from softwood) such as chemical structure, thermal stability, and rheological behavior. The results obtained in the study confirmed the similarity of the chemical structures of a typical PF resin and the modified lignin-based PF resin. Furthermore, the results also showed that PF resin has a higher reactivity than the LPF while LPF resin has a higher thermal stability. Thermogravimetric analysis (TGA) results showed that the thermal stability of LPF resin was improved in comparison with the commercial resin. This is because LS used during resin formation possesses high thermal stability. The study also suggested that a better mechanical performance could be obtained for the LPF resins than for PF resins based on the viscoelasticity properties found for the LPF resins as a consequence of the increase of their branching. The addition of LSs also modified the rheological behavior of LPF resin, changing its flow behavior from Newtonian to pseudoplastic. Sugarcane bagasse is also a good source of lignin. Lignin extracted can be used to partially replace the phenol in PF resin. In order to obtain an optimal LPF resin for the applications such as in coating and composite materials, thermal and rheological tests were performed with different wt% of lignin substitution into PF resins. Differential scanning calorimetry (DSC) scans exhibited a typical small exothermic peak and a large endothermic peak. The thermal transition (Tg) of the resins was seen between 125°C and 150°C. This transition was clearly evident when the lignin content was increased from 10 to 40 wt%. The increase of lignin content in the PF resin also increased the curing rate and reaction heat. Water absorption tests showed that the lignin-PF resin films were an effective water-barrier coating for cardboard substrates. Coated cardboard substrates (30 wt% lignin PF adhesive) demonstrated a better repellence against water despite having high contact angles. Results from water absorption showed that coated substrate had lower water absorption percentage (40%–72%) compared to the substrate without coating (148%). Therefore, it can be concluded that lignin PF coating offers desirable water resistance and thus better dimensional stability. However, to obtain the favorable LNP to be used in the lignin PF adhesive synthesis, lignin used should undergo purification process with cyclohexane/ethanol mixture. It is because the mixture when comparing to acid precipitation offers a more uniform modification of lignin and thus give a better control of sample structure for the LNP produced [33]. Polymethyl methacrylate (PMMA) sheets which are used as various element in construction and building material can be reinforced with LNP to produce a better nanocomposite material. The reinforced PMMA nanocomposite with added LNP displays a higher thermal resistance and molecular weight over conventional PMMA. This happened owing to the fact that during the polymerization process of the nanocomposite, LNP assists the cross-linking between the monomers present. Results from the study showed that, with the addition of 1 wt% of LNP, the light transmittance at 320 nm achieve only 15.3%, demonstrating a good UV resistance performance. Besides that, the PMMA composite reinforced with LNP showed better thermal stability. The addition of LNP also improved the hardness and scratch resistance of PMMA composite despite showing no obvious improvement on the tensile
4 Challenges and limitations
strength. PMMA-LNP biocomposite can be used in many building applications where the optical and aesthetic properties are important such as the windows used in skyscraper [34].
4 Challenges and limitations Despites having a lot of advantages and benefits, production of these nanomaterials is very costly and energy consuming. Particularly in the developing countries, due to the financial constraints, many developers are still clinging to the traditional building industry. Lack of exposure to the nanotechnology is also one of the main reasons that inhibited the growth of application of nanomaterials in construction and building sector [56]. In many countries, there is no specific standard for design and execution of the construction elements using nanomaterials. Taking LNP as example, LNP have wide range of benefits especially in wood composite adhesive synthesis. Nevertheless, lignin has complex structure and low reactivity and therefore is very difficult to blend with other polymers. As a result, lignin-based resins are generally having weaker adhesion properties and high degree of variability in adhesion performance. Low bond strength was also reported and could be attributed to the existence of the plasticizers or contaminants, some very low molecular weight lignin monomeric units. These impurities are responsible in causing a fluctuated transition temperature. Hence, purification of lignin must be carried out using specific process in order to attain desirable material properties. Besides that, the lack of confidence from users toward its biological impacts is one of the biggest barriers for the development and promotion of lignocellulosic nanomaterials. Similar to the other biodegradable materials, CNC has a life cycle starting from isolation, compounding, product formation, postmanufacturing processing and use, and disposal [57]. All stages pose potential human exposure with inhalation and skin exposure being the main two exposure routes to human. However, there is currently lack of understanding and information to the biological impacts of these lignocellulosic nanomaterials upon exposure. Such information is vital for the future determination of biocompatibility and hazard assessment of the lignocellulosic nanomaterials. Although some preliminary studies on the toxicity of unmodified nanocellulose revealed low-to-minimal adverse health effects from oral or dermal, the health risks associated with nanomaterials remain uncertain. Contradictory results have been reported particularly on the health effects on the respiratory system and cytotoxicity [12]. The absence of the information inevitably restricted the application of these lignocellulosic nanomaterials. In order to enhance the popularity of lignocellulosic nanomaterials and make it more socially acceptable, principles of green chemistry must be strictly adhered. The principles including prevent waste or leaving no waste, safer chemicals, lesser hazardous chemical syntheses, utilization of renewable feedstocks, biodegradable after use, pollution prevention, high energy efficiency must all be taken into consideration to comply with the stringent environmental rules, regulations, and standards. At last,
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in finding a path to facilitate the commercialization of lignocellulosic materials, communications and mindset between researchers and producers must be on the same page. Most of the studies conducted are only focused on solving particular problem and lacking of commercially components and procedures involved is inappropriate for industrial-scale processes. Therefore, exposure of the researchers to the needs of the marketplace and product value chain is a vital future topic.
5 Conclusions Lignocellulosic nanomaterials are the future materials and interesting tools to tailor desired function and performance into construction and building sector. They can be acted as reinforcement into various construction and building materials such as wood, concrete, and cement composite and polymer nanocomposites for properties enhancement. In cement and concrete, incorporation of lignocellulosic nanomaterials such as nanocellulose fiber could improve the bonding interface between nanofibers and the cement paste and subsequently resulted in products with better performance. In wood, nanocellulose could be dispersed into coatings system for wood protection and enhancement of mechanical strength and abrasion resistance. In polymer nanocomposite, mechanical strength could be improved with the lignocellulosic nanomaterials act as nanofiller. Nevertheless, despite owning a number of advantages, the applications of lignocellulosic nanomaterials are still not prevalent in the developing countries mainly due to lack of exposure and financial constraints. Lacking of understanding and information to the biological impacts of these lignocellulosic nanomaterials upon exposure is also another important factor that contributed to the indecisiveness of the consumers. In the future, a comprehensive understanding on the potential threats posed by nanomaterials toward human and environmental health is the matter of the utmost important. The current researches are ambiguous and scattered. Despite some studies revealed that nanomaterials have no detrimental effects to human health, some contrary opinions regarding the potential threats of nanomaterials did prevail among other researchers. Therefore, the biological impacts and its effects on the human health must be addressed in the future for boosting the user’s confidence in the adoption and utilization of these nanomaterials. Apart from that, exposure of the researchers to the needs of the marketplace and product value chain is also a vital future topic.
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[4] B.G. Ranby, Fibrous macromolecular systems. Cellulose and muscle. The colloidal properties of cellulose micelles, Discuss. Faraday Soc. 11 (1951) 158–164. [5] R. Bordes, T. van de Ven, Nanocellulose: what used to be cellulose micelles, Curr. Opin. Colloid Interface Sci. 29 (2017) A1–A2. [6] A. Garcia, A. Gandini, J. Labidi, N. Belgacem, J. Bras, Industrial and crop wastes: a new source for nanocellulose biorefinery, Ind. Crop. Prod. 93 (2016) 26–38. [7] J. Lee, S.H. Mahendra, P.J.J. Alvarez, Nanomaterials in the construction industry: a review of their applications and environmental health and safety considerations, ACS Nano 4 (7) (2010) 3580–3590. [8] M. Morsy, S. Alasyed, M. Aqel, Effect of nano-clay on mechanical properties and microstructures of ordinary Portland cement mortar, Int. J. Civil Environ. Eng. 10 (2010) 21–25. [8a] W.J. Homan, A.J.M. Jorissen, Wood modification developments, Heron 49 (2004) 361–386. [9] H. Kargarzadeh, M. Mariano, D. Gopakumar, I. Ahmad, S. Thomas, A. Dufresne, J. Huang, N. Lin, Advances in cellulose nanomaterials, Cellulose 25 (2018) 2151–2189. [10] R. Mohammadinejad, S. Karimi, S. Iravani, R.S. Varma, Plant-derived nanostructures: types and applications, Green Chem. 18 (1) (2016) 20–52. [11] S. Mondal, Preparation, properties and applications of nanocellulosic materials, Carbohydr. Polym. 163 (2017) 301–316. [12] R.J. Moon, G.T. Schueneman, J. Simonsen, Overview of cellulose nanomaterials, their capabilities and applications, J. Miner. Metals Mater. Soc. 68 (2016) 2383–2394. [13] H. Hatakeyama, T. Hatakeyama, Lignin structure, properties, and applications, in: Biopolymers, Springer Berlin Heidelberg, 2009, pp. 1–63. [14] A. Tejado, C. Pena, J. Labidi, J.M. Echeverria, I. Mondragon, Physico-chemical characterization of lignins from different sources for use in phenol–formaldehyde resin synthesis, Bioresour. Technol. 98 (8) (2007) 1655–1663. [15] P. Benar, A.R. Gonc¸alves, D. Mandelli, U. Schuchardt, Eucalyptus organosolv lignins: study of the hydroxymethylation and use in resols, Bioresour. Technol. 68 (1) (1999) 11–16. [16] M. Wang, M. Leitch, C.C. Xu, Synthesis of phenol–formaldehyde resol resins using organosolv pine lignins, Eur. Polym. J. 45 (12) (2009) 3380–3388. [17] F. Bertini, M. Canetti, A. Cacciamani, G. Elegir, M. Orlandi, L. Zoia, Effect of lignoderivatives on thermal properties and degradation behavior of poly (3-hydroxybutyrate)-based biocomposites, Polym. Degrad. Stab. 97 (10) (2012) 1979–1987. [18] A. Pinkert, D.F. Goeke, K.N. Marsh, S. Pang, Extracting wood lignin without dissolving or degrading cellulose: investigations on the use of food additive-derived ionic liquids, Green Chem. 13 (11) (2011) 3124–3136. [19] Y. Uraki, Y. Sugiyama, K. Koda, S. Kubo, T. Kishimoto, J.F. Kadla, Thermal mobility of β-O-4-type artificial lignin, Biomacromolecules 13 (3) (2012) 867–872. [20] A. Sev, M. Ezel, Nanotechnology innovations for the sustainable buildings of the future, Int. J. Architect. Environ. Eng. 8 (8) (2014) 886–896. [21] W. Zhu, P.J.M. Bartos, J. Gibbs, Application of nanotechnology in construction. Summary of a state-of-the-art report, J. Mater. Struct. 37 (2004) 649–658. [22] A. Cengiz, M. Kaya, N.P. Bayramgil, Flexural stress enhancement of concrete by incorporation of algal cellulose nanofibers, Constr. Build. Mater. 149 (2017) 289–295. [23] O. Onuaguluchi, D.K. Panesar, M. Sain, Properties of nanofibre reinforced cement composites, Constr. Build. Mater. 63 (2014) 119–124. [24] F. Mohammadkazemi, K. Doosthoseini, E. Ganjian, M. Azin, Manufacturing of bacterial nano-cellulose reinforced fiber-cement composites, Constr. Build. Mater. 101 (2015) 958–964.
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[25] M. Ozgur Seydibeyoglu, M. Misra, A. Mohanty, J.J. Blaker, K. Lee, A. Bismarck, M. Kazemizadeh, Green polyurethane nanocomposites from soy polyol and bacterial cellulose, J. Mater. Sci. 48 (2013) 2167–2175. [26] M.M. Nishidate Kumode, G.I. Muniz Bolzon, W.L.E. Magalhaes, S.G. Kestur, Microfibrillated nanocellulose from balsa tree as potential reinforcement in the preparation of ‘green’ composites with castor seed cake, J. Clean. Prod. 149 (2017) 1157–1163. [27] D. Bendahou, A. Bendahou, B. Seantier, Y. Grohens, H. Kaddami, Nano-fibrillated cellulose-zeolites based new hybrid composites aerogels with super thermal insulating properties, Ind. Crop. Prod. 65 (2015) 374–382. [28] V. da Costa Correia, S.F. Santos, R.S. Teixeira, H.S. Junior, Nanofibrillated cellulose and cellulosic pulp for reinforcement of the extruded cement based materials, Constr. Build. Mater. 160 (2018) 376–384. [29] M.G. Thomas, E. Abraham, P. Jyotishkumar, H.J. Maria, L.A. Pothen, S. Thomas, Nanocellulose from jute fibers and their nanocomposites with natural rubber: preparation and characterization, Int. J. Biol. Macromol. 81 (2015) 768–777. [30] A. Jabbar, J. Militky, J. Wiener, B.M. Kale, U. Ali, S. Rwawiire, Nanocellulose coated woven jute/green epoxy composite: characterization of mechanical and dynamic mechanical behavior, Compos. Struct. 161 (2017) 340–349. [31] T. Akhtar, G. Lutfullah, Z. Ullah, Lignonsulfonate-phenolformaldehyrde adhesive: a potential binder for wood panel industries, J. Chem. Soc. Pak. 33 (4) (2011) 535–538. [32] J.C. Domı´nguez, M. Oliet, M.V. Alonso, E. Rojo, F. Rodrı´guez, Structural, thermal and rheological behavior of a bio-based phenolic resin in relation to a commercial resol resin, Ind. Crop. Prod. 42 (2013) 308–314. [33] Y. Park, W.O. Doherty, P.J. Halley, Developing lignin-based resin coatings and composites, Ind. Crop. Prod. 27 (2) (2008) 163–167. [34] W. Yang, M. Rallini, D.Y. Wang, D. Gao, F. Dominici, L. Torre, J.M. Kenny, D. Puglia, Role of lignin nanoparticles in UV resistance, thermal and mechanical performance of PMMA nanocomposites prepared by a combined free-radical graft polymerization/masterbatch procedure, Compos. A: Appl. Sci. Manuf. 107 (2018) 61–69. [35] S.L. Hilburg, A.N. Elder, H. Chung, R.L. Ferebee, M.R. Bockstaller, N.R. Washburn, A universal route towards thermoplastic lignin composites with improved mechanical properties, Polymer 55 (4) (2014) 995–1003. [36] C. Vigneshkumar, Study on nanomaterials and application of nanotechnology and its impact in construction, Discovery 23 (2014) 8–12. [37] M.M. Norhasri, M.S. Hamidah, A.M. Fadzil, Applications of using nano material in concrete: A review, Constr. Build. Mater. 133 (2017) 91–97. [38] J. Claramunt, M. Ardanuy, L.J. Fernandez-Carrasco, Wet/dry cycling durability of cement mortar composites reinforced with micro- and nanoscale cellulose pulps, Bioresources 10 (2015) 3045–3055. [39] L.W. Hrubesh, R.W. Pekala, Thermal properties of organic and inorganic aerogels, J. Mater. Res. 9 (3) (1994) 731–738. [40] X. Lu, R. Caps, J. Fricke, C.T. Alviso, R.W. Pekala, Correlation between structure and thermal conductivity of organic aerogels, J. Non-Cryst. Solids 188 (3) (1995) 226–234. [41] Y.W. Chen, H.W. Lee, J.C. Juan, S.M. Phang, Production of new cellulose nanomaterial from red algae marine biomass Gelidium elegans, Carbohydr. Polym. 151 (2016) 1210–1219. [42] S.H. Lee, Z. Ashaari, W.C. Lum, A.H. Juliana, A.F. Ang, L.P. Tan, K.L. Chin, M. T. Paridah, Thermal treatment of wood using vegetable oils: A review, Constr. Build. Mater. 181 (2018) 408–419.
Further reading
[43] T. Marzi, Nanostructured materials for protection and reinforcement of timber structures: a review and future challenges, Constr. Build. Mater. 97 (2015) 119–130. [44] A. Kaboorani, N. Auclair, B. Riedl, V. Landry, Mechanical properties of UV-cured cellulose nanocrystal (CNC) nanocomposite coating for wood furniture, Prog. Org. Coat. 104 (2017) 91–96. [45] A. Cataldi, C.E. Corcione, M. Frigione, A. Pegoretti, Photocurable resin/nanocellulose composite coatings for wood protection, Prog. Org. Coat. 106 (2017) 128–136. [46] S. Veigel, G. Grull, S. Pinkl, M. Obersriebnig, U. M€ uller, W. Gindl-Altmutter, Improving the mechanical resistance of waterborne wood coatings by adding cellulose nanofibers, React. Funct. Polym. 85 (2014) 214–220. [47] D. Cheng, Y. Wen, X. An, X. Zhu, Y. Ni, TEMPO-oxidized cellulose nanofibers (TOCNs) as a green reinforcement for waterborne polyurethane coating (WPU) on wood, Carbohydr. Polym. 151 (2016) 326–334. [48] K. Majeed, M. Jawaid, A. Hassan, A. Abu Bakar, H.P.S. Abdul Khalil, A.A. Salema, I. Inuwa, Potential materials for food packaging from nanoclay/natural fibres filled hybrid composites, Mater. Des. 46 (2013) 391–410. [49] J. Gonza´lez-Iru´n Rodrı´guez, P. Carreira, a. Garcı´a-Diez, D. Hui, R. Artiaga, L.M. LizMarza´n, Nanofiller effect on the glass transition of a polyurethane, J. Therm. Anal. Calorim. 87 (1) (2007) 45–47. [50] A. Dufresne, D. Dupeyre, M.R. Vignon, Cellulose microfibrils from potato tuber cells: processing and characterization of starch-cellulose microfibril composites, J. Appl. Polym. Sci. 76 (14) (2000) 2080–2092. [51] A.N. Nakagaito, H. Yano, The effect of morphological changes from pulp fiber towards nano-scale fibrillated cellulose on the mechanical properties of high-strength plant fiber based composites, Appl. Phys. A Mater. Sci. Process. 78 (4) (2004) 547–552. [52] H. Kargarzadeh, M. Mariano, J. Huang, N. Lin, I. Ahmad, A. Dufresne, S. Thomas, Recent developments on nanocellulose reinforced polymer nanocomposites: a review, Polymer 132 (2017) 368–393. [53] K. Lee, Y. Aitomaki, L.A. Berglund, K. Oksman, A. Bismarck, On the use of nanocellulose as reinforcement in polymer matrix composites, Compos. Sci. Technol. 105 (2014) 15–27. [54] S.M. Li, S.L. Sun, M.G. Ma, Y.Y. Dong, L.H. Fu, R.C. Sun, F. Xu, Lignin-based carbon/ CePO4 nanocomposites: solvothermal fabrication, characterization, thermal stability, and luminescence, Bioresources 8 (3) (2013) 4155–4170. [55] C. Jiang, H. He, H. Jiang, L. Ma, D.M. Jia, Nano-lignin filled natural rubber composites: preparation and characterization, Express Polym. Lett. 7 (5) (2013) 480–493. [56] A.S. Yousef Mohamed, Nano-innovation in construction, a new era of sustainability, in: Proceedings of International Conference on Environment and Civil Engineering, 24–25 April, Pattaya, 2015. [57] S. Camarero-Espinosa, C. Endes, S. Mueller, A. Petri-Fink, B. Rothen-Rutishauser, C. Weder, M.J.D. Clift, E.J. Foster, Elucidating the potential biological impact of cellulose nanocrystals, Fibers 4 (3) (2016) 21.
Further reading [58] M. Hu, The significance of nanotechnology in architectural design, Future Archit. Res. (2015) 90–96. [59] S. Wong, An overview of nanotechnology in building materials, Canadian Young Scientist J. 2014 (2) (2014) 18–21.
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Lignocellulosic nanomaterials for construction and building applications
15
Wei Chen Lum*, Seng Hua Lee†, Zakiah Ahmad*, Juliana Abdul Halip‡ Kit Ling Chin† Institute for Infrastructure Engineering and Sustainability Management, Universiti Teknologi MARA, Shah Alam, Malaysia* Institute of Tropical Forestry and Forest Products, Universiti Putra Malaysia, Serdang, Malaysia† Faculty of Technology Management and Business, Universiti Tun Hussien Onn, Parit Raja, Malaysia‡
1 Introduction Nanomaterial, as its name implies, is extremely minutes particles. The International Organization for Standardization (ISO) defined nanomaterial as a material having any external dimension or internal structure in the length range of 1–100 nm [1]. Lignocellulose or lignocellulosic biomass is plant dry matter composed of carbohydrate polymers, namely cellulose and hemicellulose, and a polyphenolic polymer, which is lignin [2]. Therefore, lignocellulosic nanomaterial refers to materials derived from lignocellulosic biomass, for example, nanocellulose, nanohemicellulose, and nanolignin. The first extraction procedure of nanocellulose was reported by Ranby [3] and was first made by Ranby [4] at the Uppsala University before the field has quieted down for more than 40 years. However, the interest on nanocellulose has been rekindled in the last 20 years seeing the continuously increment in researches around the world [5]. The statement was supported by the data compiled by Garcia et al. [6] who reported that the annual average of publications on the mentioned topic was less than 500 documents/year up to 2000. This amount increased more than twofolds in the years between 2005 and 2010, which recorded an annual average publication of 1000–1500 documents/year. From 2010 onwards, the figures reached a whopping 2500 documents/year. The trend of the researches in this particular field also sees a drastic change from preparation and characterization studies toward application of these nanostructures in different fields. Lately, mitigation of greenhouse gas emissions emittance is a matter of the utmost importance. It could be achieved by either increase the application of Industrial Applications of Nanomaterials. https://doi.org/10.1016/B978-0-12-815749-7.00015-3 # 2019 Elsevier Inc. All rights reserved.
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lightweight building materials that are environmentally friendly, derived from renewable sources and recyclable or through the usage of novel materials with improved insulation properties that are able to reduce the energy consumption during the lifetime service of a building. Because of that, a number of nanoparticles have been used in imparting better properties to the construction and building materials in the past few years. Carbon nanotubes have been used in concrete and ceramics for better mechanical and thermal properties. Silicon dioxide (SiO2) nanoparticles have been used in window for fire proofing as well as antireflection while titanium dioxide (TiO2) has been applied for rapid hydration of concrete. For steel, copper (Cu) nanoparticles have been applied to attain weld ability and formability as well as to gain corrosion-resistance properties. In coating or painting, nanosilver was often used to bestow biocidal properties to the coated materials [7]. Apart from that, a by-product from kaolin called kaolinite has also been used to produce ultra-highperformance concrete (UHPC) where higher compression, tensile, and flexural strength have been reported [8]. However, this chapter focused only on the lignocellulosic nanomaterials and their applications in construction and building sector.
2 Types of lignocellulosic nanomaterials Lignocellulosic materials constituted by three main cell wall component, namely hemicellulose, cellulose, and lignin. Each component contributes differently to the strength properties of the lignocellulosic materials. In concrete terms, hemicellulose is the bonding agent or cross-linking material between cellulose and lignin. Cellulose acts as reinforcement that contributes to tension forces and lignin for compression forces [8a]. Nanocellulose exists in a number of forms, which generally can be classified into two subcategories: (1) short and needle-shaped nanocrystalline cellulose (NCC)/cellulose nanocrystals (CNCs) which sometimes called as nanowhiskers (CNWs) or NCC and (2) nanofibrillated cellulose/slender cellulose nanofibers (CNFs) [9, 10]. In addition to these two subcategories, bacterial nanocellulose (BNC) is another main subcategory of nanocellulose [11]. Nanocellulose possesses synergetic effect of the key properties of cellulose and the characteristics of the nanoscale. Cellulose nanomaterials are capable of being versatile in a variety of applications owing to its high surface-area-to-volume ratio. For example, cellulose nanomaterials can be used as reinforcement of polymers due to its high mechanical properties and aspect ratio [12]. In the recent years, availability of huge volumes of cellulose nanomaterials has opened up the possibility of these materials to be used in various application areas. According to Moon et al. [12], cellulose nanomaterials can act as additive to adhesive, paper-based products, drilling fluids, cement-based materials, food coatings, transparent-flexible electronics, catalysis support structure, and biomedical applications. Lignin is the most abundant by-products of the paper industry as well as the second most abundant natural aromatic polymer which can be found on earth.
3 Application of lignocellulosic nanomaterials in construction
FIG. 1 The three structural units of lignin [14]. (Reproduced with permission from Elsevier.)
The three-dimensional (3D) and highly cross-linked of lignin macromolecule can be broken down into three monomers which are coniferyl alcohol, synapyl alcohol, and p-coumaryl alcohol. The monomers are connected together mainly by ether linkages and condensed linkages. The final structure of lignin is composed of three units: (1) guauacyl (G-type), (2) synringyl (S-type), and (3) p-hydroxylphenol propane (p-H-type) [13, 14]. The three structural units of lignin are illustrated in Fig. 1. The ratio of these units existed in the structure of lignin depends on the origin of the lignin (softwood, hardwood, and grass) and also the delignification process applied [15, 16]. The lignin nanoparticles (LNP) synthesized can be used in various application. Lignin-based nanomaterials offer numerous benefits when compared to conventional synthetic materials. Lignin-based nanomaterials are biodegradable, carbon dioxide neutral, available abundantly from industrial byproducts, relative low cost, and environmentally friendly besides also having antioxidant, antimicrobial, and stabilizer properties [17–19].
3 Application of lignocellulosic nanomaterials in construction and building materials Building materials represent a variety of materials that are used for construction purposes including wood and timber, fired bricks and clay blocks, steel, concrete, cement composites, etc. Construction and building materials can be simply classified as structural and nonstructural materials. Concrete, wood, and steel are three of the main structural materials while nonstructural materials including glass, plastics, insulator, and adhesives [20]. Nanomaterials can be applied in the production of construction and building materials. Nanomaterials are able to enhance the properties of construction and building materials by acting as a reinforcement to the concrete and steel [20]. When it comes to the application in the construction and building materials, nanotechnology offers several advantages such as sturdier and stronger but relatively lighter structural composites, cementitious materials with superior properties, thermal and sound insulators with lower thermal transfer rate, and better sound
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absorption capability [7]. According to Zhu et al. [21], nanomaterials have been applied in the construction sectors aiming to increase the strength and durability of construction materials and components while reducing pollution at the same time. Table 1 listed the nanomaterials derived from various lignocellulosic sources and its uses in the construction and building materials.
3.1 Concrete and cement composite During the production process of concrete and cement, environmental issues such as high energy consumption and emittance of carbon dioxide are highly undesirable. Application of nanotechnology has alleviated the aforementioned matters where new concrete and cement with enhanced properties was produced by the addition of nanoparticles [36]. Nanomaterials are believed to be able to improve the strength of conventional concrete by exerting superior filler effect that increase the bulk properties and therefore resulted in denser concrete. Several drawbacks such as microvoid, porosity, and deterioration caused by alkali silica can be negated by the addition of nanomaterials [37]. In the production of cement, CNCs have the ability
Table 1 Nanomaterials derived from various lignocellulosic biomass sources and its uses in the construction and building materials. Biomass source
Nanomaterial
Green algae (Cladophora sp)
Cellulose nanofiber
Softwood pulp
Nanocellulose fiber gel
Bacteria (Gluconacetobacter xylinus)
Bacterial nanocellulose powder, gel and
Application and finding Reinforcement in concrete. Flexural stress of the concrete mortar was enhanced by almost 3 times after reinforcement with algal cellulose nanofiber while commercial cellulose resulted in negative effects in the flexural stress of the concrete mortar Reinforcement in cement composites Improved flexural strength and energy absorption property of cement paste Reinforcement in fibercement composites Bending and internal
Reference [22]
[23]
[24]
3 Application of lignocellulosic nanomaterials in construction
Table 1 Nanomaterials derived from various lignocellulosic biomass sources and its uses in the construction and building materials. Continued Biomass source
Nanomaterial coated onto bagasse fibers
Bacterial cellulose extracted from nata-de-coco
Bacterial nanocellulose
Balsa tree (Ochromapyramidale Cav)
Nanofibrillar cellulose
Rachis of date palm tree (Phoenix dactylifera L.)
Nanofibrillar cellulose
Application and finding bonding strength of the fiber-cement composites reinforced with bacterial nanocellulose was improved and the highest fracture toughness was recorded in the composites made with bacterial nanocellulosecoated bagasse fibers Reinforcement in soy polyol-based polyurethanes nanocomposites Higher flexural strength and modulus was achieved in bacterial cellulose reinforced polyurethanes nanocomposites Balsa wood fibers— castor bean cake— glycerol matrix composites Production of green composite is feasible and the addition of nanofibrillar cellulose increased the flexural modulus of the resultant composites when the density of the composites remained constant Hybrid composites aerogels monolith made with combinations of cellulose microfibers, cellulose nanofibers and nanozeolites Hybrid materials with super thermal insulating properties was produced by adding nanozeolites to cellulose nanofibers
Reference
[25]
[26]
[27]
Continued
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Table 1 Nanomaterials derived from various lignocellulosic biomass sources and its uses in the construction and building materials. Continued Biomass source
Nanomaterial
Bamboo pulp
Nanofibrillated cellulose and cellulosic pulp
Raw jute fibers
Nanocellulose fiber
Waste jute fibers
Nanocellulose suspension
By-products from pulp and paper industries
Lignin nanoparticles— Lignosulfonate
Application and finding Reinforcement of the extruded cementbased materials In the hybrid composites the nanofibrillated cellulose improved the mechanical behavior compared to the composite without nanofiber Reinforcement in natural rubber nanocomposite Enhanced Young’s modulus and tensile strength of the nanocomposite Coating for woven jute fabric to produce green epoxy composites Epoxy composite reinforced with nanocellulose-coated woven jute revealed better tensile modulus, flexural properties and fracture toughness but lower tensile strength Substitution of phenol in the synthesis of phenolformaldehyde (PF) wood adhesive Bio-resin for wood composite with higher shear strength and modulus of elasticity was produced by using lignosulfonate during PF resin synthesis. The bioresin produced also demonstrated better thermal properties
Reference [28]
[29]
[30]
[31] [32]
3 Application of lignocellulosic nanomaterials in construction
Table 1 Nanomaterials derived from various lignocellulosic biomass sources and its uses in the construction and building materials. Continued Biomass source
Nanomaterial
Sugarcane bagasse
Lignin acetate
Giant reed (Arundo donax L.)
Lignin nanoparticles (LNP)
Kraft pulping process
Kraft lignin
Application and finding Water resistance surface coating Water absorption tests showed the coated substrates had significantly lower a weight increase compared to the untreated substrate Reinforcement of Polymethyl methacrylate (PMMA) nanocomposites Thermogravimetric analysis (TGA) test showed that LNP visibly improved the thermal stability of PMMA. The hardness of the PMMA also increased and fulfilled the required hardness values for industrial applications such as building materials Thermoplastic ligninbased nanocomposites Results shows that lignin-based nanocomposite not only exhibited enhanced toughness and ultimate elongation compared to homopolymers, but also showed 10 times higher toughness and 4 times better ultimate elongation than the corresponding lignin/ polymer blend system
Reference [33]
[34]
[35]
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as superplasticizer to promote a more uniform particle distribution and subsequently resulted in stronger material. Lignocellulosic nanomaterials have been used by several researchers in improving the concrete and cement composite. Claramunt et al. [38] reinforced cement mortar composites with nanofibrillated cellulose and sisal microfibers and reported that the flexural strength and modulus of elasticity of the composites improved with increasing nanofibrillated pulp content. On the contrary, the nanofibrillated pulp reinforced cement mortar composites have lower toughness or more brittle compared to that of the composites reinforced with sisal microfibers. Onuaguluchi et al. [23] prepared nanocellulose fiber gel from bleached softwood pulp and mixed it with general use limestone cement paste. After the addition of nanocellulose fiber gel, the hydration rate of the cement decreased at the early stage but no negative effect on the 28-day degree of hydration was detected. Enhanced flexural strength and energy absorption property of cement paste was observed even merely 0.1% nanocellulose fiber were added. Da Costa Correia et al. [28] derived nanofibrillated cellulose from bamboo pulp and reinforced it in the cement composite. Comparison was made between the cement composite reinforced with 9% cellulosic pulp with those of reinforced with 8% pulp and 1% nanofibrillated cellulose. In the presence of nanofibrillated cellulose, the mechanical strength of the cement composites improved, which suggested that the content of 1% of nanofibrillated cellulose associated with 8% of pulp was sufficient to form stress transfer bridges in the nano and micro-cracking. On the other hand, accelerated aging did not affect the mechanical performance of both types of cement composite adversely. In addition, the water absorption and apparent void volume of the hybrid composites were no higher than composites without nanofibers at 28 days, although the higher water/cement ratio of the composites with nanofibers. It was due to the fact the high specific surface area of the nanofibrillated cellulose allowed the improvement of the packing of the nanofibers with the particles of the matrix (cement + limestone). In another research, cellulose microfiber and nanofiber enhanced the thermal properties of hybrid composite. Bendahou et al. [27] found that hybrid aerogel biocomposite prepared using cellulose microfibers, CNFs, and nanozeolites exhibited low thermal conductivity value which was 18 mW m 1 K 1. The value was lower than most aerogel materials used as insulating material which has thermal conductivity higher than 20 mW m 1 K 1 as reported by Hrubesh and Pekala [39] and Lu et al. [40]. The substantial reduction in thermal conductivity was achieved by the addition of nanozeolites to CNFs which combined the inter-cellulose films meso-porosity and closed the nanozeolite pores. Considering of the vital characteristics of the nanofibrillated cellulose, which are, worldwide availability, renewable resource and most importantly have a high aspect ratio and specific surface area, nanofibrillated cellulose is considered a promising material to be used as a nanoreinforcement material of the extruded hybrid cement-based biocomposites. Apart from nanofibrillated cellulose derived from various lignocellulosic sources, BNC has also been used as reinforcement in cement and concrete. Mohammadkazemi et al. [24] used BNC extracted from Gluconacetobacter xylinus in the
3 Application of lignocellulosic nanomaterials in construction
forms of powder, gel, and coated onto the bagasse fibers to produce fiber-cement composites. The results revealed that bagasse fibers coated with BNC exhibited increased surface OH groups and contact surface. Fiber-cement composites produced from BNC-coated bagasse fibers showed the best properties among the other forms as the BNC protect the fiber from mineralization by inhibits the penetration of alkali ions. On the other hand, in comparison to the powder form, BNC in gel form displayed better mechanical strength and higher hydration temperature. Recently, marine biomass such as algae has entered people’s vision as a promising source of nanocellulose production. The benefits of marine biomasses over land plants are that they have higher rapid growth rate and are low in natural physicochemical barriers. Therefore, no severe chemical treatment is required to remove their inherently recalcitrant structure in order to enhance the cellulose accessibility [41]. Cengiz et al. [22] used CNF derived from green algae, Cladophora sp., as a reinforcement in concrete. The efficiency of the CNF derived from green algae in the concrete reinforcement was compared with commercial cellulose. Due to its higher aspect ratio, concrete produced by adding algae CNF in concrete mortar exhibited almost three times higher the flexural stress when compared to the concrete made from shorter commercial cellulose. This was possible as a result of improved bonding interface between nanofibers and the cement paste.
3.2 Wood Wood is a prevalently used renewable construction and building material well known for its high strength-to-weight ratio and lower processing energy [42]. Unfortunately, wood in use is dimensionally instable when exposed to moisture and susceptible to the degradation by bio-organisms as well as discoloration caused by the exposure to ultraviolet (UV) light. Application of nanocomposite coating could help to protect and improve the performance and functionality of wood [43]. Apart from acting as reinforcement materials, nanocellulose has also been incorporated into coatings system for wood protection. Generally, incorporation of nanomaterials such as CNC into the coating system could enhance its mechanical properties, hardness, and abrasion resistance [44]. Cataldi et al. [45] compared the effectiveness of nanocellulose- and microcellulose-filled UV-light curable methacrylic-siloxane-cellulose composite coatings in terms of thermal properties, dimensional stability, stiffness, hydrophobicity, and surface hardness on maple wood. The results revealed that nanocellulosefilled coatings are superior in all aspects compared to that of the microcellulose-filled coatings. Veigel et al. [46] incorporated microfibrillated cellulose (MFC) and NCC into waterborne acrylate/polyurethane-based wood coating and was applied on the particleboard covered with beech veneer. Higher scratch resistance and hardness of coated wood but no significant improvement in abrasion resistance was observed. It is interesting to note that MFC works better than NCC in improving the mechanical properties of waterborne wood coating. Similar findings were also reported by Cheng et al. [47] TEMPO-oxidized CNFs were added into waterborne polyurethane
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coating. The improvements were attributed to the good compatibility and strong interfacial adhesion between the waterborne polyurethane coating and TEMPOoxidized CNFs through hydrogen bonding. In addition, a continuous network is formed when the content of the TEMPO-oxidized CNFs exceeds the critical percolation threshold.
3.3 Polymer composites As the public’s awareness toward environmental conservation grew over the years, more and more environmental friendly materials are currently in demand. Dependency on petroleum-based polymers is, therefore, lessen in favor of the synthesis of greener and renewable polymers. However, the thermomechanical performance of renewable polymers is relatively poor compared to the conventional petroleum-based polymers. Polymer composite can be modified with the addition of nanofillers to produce a polymer composite with enhanced properties. A nanocomposite is a multiphase solid material where one of the phases has one, two, or three dimensions of less than 100 nm. Performance of the polymer composites such as mechanical strength, thermal stability, and barrier properties could be improved by the incorporation of nanofillers [48]. Clay minerals, carbon nanotubes, and silica nanoparticles are among the nanofillers that often adopted in improving the physical, mechanical, and thermal properties of polymers [49]. Dufresne et al. [50] was the first to demonstrate the application of cellulose microfibrils from potato tuber cells to improve the properties of polymer composites. Nakagaito and Yano [51] reported mechanical strength enhancement of phenol formaldehyde (PF) resin-based composites reinforced with nanoscale fibrillated cellulose. In a review by Kargarzadeh et al. [52], thermoset polymer composites including epoxy, unsaturated polyester resin, phenol-, melamine-, and ureaformaldehyde resins, and nanocellulose reinforced polyethylene terephthalate (PET) composite have been reviewed and discussed. Although having identified with various advantages such as high physico-mechanical properties, thermoset composites are brittle and easy to crack. Nanocellulose could act as reinforcement for thermoset composites in order to enhance its fracture toughness [52]. Thomas et al. [29] reported that, the increase of nanocellulose content in the natural rubber matrix had resulted in a significant improvement of the mechanical properties of the composite. The modulus of elasticity and tensile strength of material also increased as the nanocellulose content increased. The enhanced mechanical properties can be attributed to the formation of the nanocellulosic networks in the natural rubber matrix. Nanocellulose can also be used as surface coating to improve the material properties. Jabbar [30] found that nanocellulose coating over woven jute composite improved its mechanical properties. In the study, three different concentration (3, 5, and 10 wt%) of nanocellulose coating were applied to jute composite, and the results obtained show enhanced tensile and flexural strength compared to uncoated jute composite. In comparison to the extensively reported nanofibrillated cellulose-based polymer composites, lesser studies were reported on the BNC-based polymer composites.
3 Application of lignocellulosic nanomaterials in construction
This is because nanofibrillated cellulose can be produced in huge quantities in laboratories using a variety of methods. BNC contains only pure cellulose while nanofibrillated cellulose often consists of both cellulose and hemicellulose [53]. Bacterial cellulose nanofibril extracted from nata-de-coco was used by Ozgur Seydibeyoglu et al. [25] as a reinforcement in soy polyol-based polyurethanes nanocomposites. Significantly higher flexural strength and modulus was achieved in bacterial cellulose nanofibril-reinforced polyurethanes nanocomposites even at the loading of less than 0.5 wt%. In addition, the transparency of bacterial cellulose nanofibrilreinforced polyurethanes nanocomposites was not significantly affected as it stays in the same range with the neat polyurethane. On the other hand, in the development of lignin nanocomposites, emphasis should be put on the molecular uniformity of the lignin as it is an important factor that influences the final properties of the composites. The preparation procedure of lignin is, therefore, very vital. Recently, lignin-based nanocomposites have been synthesized by using different grafting strategies. Lignin-based carbon/CePO4 nanocomposites were produced by Li et al. [54] and showed great potential to be utilized in luminescent devices. Hilburg et al. [35] produced lignin-based nanocomposites using synthetic thermoplastic polymers grafted from kraft lignin. The polymers were synthesized with the application of atom transfer radical polymerization (ATRP) and possessed an average particle size of 5 nm. The results reported that, the poly(methyl methacrylate)-grafted samples exhibited ultimate elongation of approximately two times higher compared to that of the polystyrene grafts at high graft density. Both types of grafted nanocomposites possessed 10-times higher toughness values in comparison to that of the corresponding kraft-lignin/polymer blend system. In comparison to the other inorganic nanoparticles-based nanocomposites, lignin grafted with thermoplastic polymers is an inexpensive, renewable, and worthwhile material that bestows unique properties to the resultant nanocomposites. Nano-lignin could be used as partial replacement of carbon black in the production of natural rubber composites. Nano-lignin filled natural rubber composites were successfully produced by Jiang et al. [55] through coprecipitation of colloidal lignin-cationic polyelectrolyte complexes and rubber latex. PF resin is widely used as a binder in wood composite. Various studies have shown that phenol which is the main component in the resin can be substituted with lignin from plants. However, for the proper reaction to take place during resin synthesis, the lignin used will first have to be synthesized into lignosulfonate (LS). Phenol can be substituted with LS at a relatively high level which is about 50 wt%. PF adhesive with the addition of 50% LS displayed better strength performance when compared to conventional pure PF adhesive. With the substitution of phenol with LS, PF resin with cheaper cost can be produced because LS is relatively cheaper than pure phenol. Although PF resin with different level of LS substitution can be synthesized, PF resin with 20% LS replacement showed the highest shear strength in both wet and dry conditions [31]. In another study, Domı´nguez et al. [32] investigated the various properties of lignin-based phenol formaldehyde (LPF) resin containing a 30 wt% of ammonium
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LS (extracted from softwood) such as chemical structure, thermal stability, and rheological behavior. The results obtained in the study confirmed the similarity of the chemical structures of a typical PF resin and the modified lignin-based PF resin. Furthermore, the results also showed that PF resin has a higher reactivity than the LPF while LPF resin has a higher thermal stability. Thermogravimetric analysis (TGA) results showed that the thermal stability of LPF resin was improved in comparison with the commercial resin. This is because LS used during resin formation possesses high thermal stability. The study also suggested that a better mechanical performance could be obtained for the LPF resins than for PF resins based on the viscoelasticity properties found for the LPF resins as a consequence of the increase of their branching. The addition of LSs also modified the rheological behavior of LPF resin, changing its flow behavior from Newtonian to pseudoplastic. Sugarcane bagasse is also a good source of lignin. Lignin extracted can be used to partially replace the phenol in PF resin. In order to obtain an optimal LPF resin for the applications such as in coating and composite materials, thermal and rheological tests were performed with different wt% of lignin substitution into PF resins. Differential scanning calorimetry (DSC) scans exhibited a typical small exothermic peak and a large endothermic peak. The thermal transition (Tg) of the resins was seen between 125°C and 150°C. This transition was clearly evident when the lignin content was increased from 10 to 40 wt%. The increase of lignin content in the PF resin also increased the curing rate and reaction heat. Water absorption tests showed that the lignin-PF resin films were an effective water-barrier coating for cardboard substrates. Coated cardboard substrates (30 wt% lignin PF adhesive) demonstrated a better repellence against water despite having high contact angles. Results from water absorption showed that coated substrate had lower water absorption percentage (40%–72%) compared to the substrate without coating (148%). Therefore, it can be concluded that lignin PF coating offers desirable water resistance and thus better dimensional stability. However, to obtain the favorable LNP to be used in the lignin PF adhesive synthesis, lignin used should undergo purification process with cyclohexane/ethanol mixture. It is because the mixture when comparing to acid precipitation offers a more uniform modification of lignin and thus give a better control of sample structure for the LNP produced [33]. Polymethyl methacrylate (PMMA) sheets which are used as various element in construction and building material can be reinforced with LNP to produce a better nanocomposite material. The reinforced PMMA nanocomposite with added LNP displays a higher thermal resistance and molecular weight over conventional PMMA. This happened owing to the fact that during the polymerization process of the nanocomposite, LNP assists the cross-linking between the monomers present. Results from the study showed that, with the addition of 1 wt% of LNP, the light transmittance at 320 nm achieve only 15.3%, demonstrating a good UV resistance performance. Besides that, the PMMA composite reinforced with LNP showed better thermal stability. The addition of LNP also improved the hardness and scratch resistance of PMMA composite despite showing no obvious improvement on the tensile
4 Challenges and limitations
strength. PMMA-LNP biocomposite can be used in many building applications where the optical and aesthetic properties are important such as the windows used in skyscraper [34].
4 Challenges and limitations Despites having a lot of advantages and benefits, production of these nanomaterials is very costly and energy consuming. Particularly in the developing countries, due to the financial constraints, many developers are still clinging to the traditional building industry. Lack of exposure to the nanotechnology is also one of the main reasons that inhibited the growth of application of nanomaterials in construction and building sector [56]. In many countries, there is no specific standard for design and execution of the construction elements using nanomaterials. Taking LNP as example, LNP have wide range of benefits especially in wood composite adhesive synthesis. Nevertheless, lignin has complex structure and low reactivity and therefore is very difficult to blend with other polymers. As a result, lignin-based resins are generally having weaker adhesion properties and high degree of variability in adhesion performance. Low bond strength was also reported and could be attributed to the existence of the plasticizers or contaminants, some very low molecular weight lignin monomeric units. These impurities are responsible in causing a fluctuated transition temperature. Hence, purification of lignin must be carried out using specific process in order to attain desirable material properties. Besides that, the lack of confidence from users toward its biological impacts is one of the biggest barriers for the development and promotion of lignocellulosic nanomaterials. Similar to the other biodegradable materials, CNC has a life cycle starting from isolation, compounding, product formation, postmanufacturing processing and use, and disposal [57]. All stages pose potential human exposure with inhalation and skin exposure being the main two exposure routes to human. However, there is currently lack of understanding and information to the biological impacts of these lignocellulosic nanomaterials upon exposure. Such information is vital for the future determination of biocompatibility and hazard assessment of the lignocellulosic nanomaterials. Although some preliminary studies on the toxicity of unmodified nanocellulose revealed low-to-minimal adverse health effects from oral or dermal, the health risks associated with nanomaterials remain uncertain. Contradictory results have been reported particularly on the health effects on the respiratory system and cytotoxicity [12]. The absence of the information inevitably restricted the application of these lignocellulosic nanomaterials. In order to enhance the popularity of lignocellulosic nanomaterials and make it more socially acceptable, principles of green chemistry must be strictly adhered. The principles including prevent waste or leaving no waste, safer chemicals, lesser hazardous chemical syntheses, utilization of renewable feedstocks, biodegradable after use, pollution prevention, high energy efficiency must all be taken into consideration to comply with the stringent environmental rules, regulations, and standards. At last,
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in finding a path to facilitate the commercialization of lignocellulosic materials, communications and mindset between researchers and producers must be on the same page. Most of the studies conducted are only focused on solving particular problem and lacking of commercially components and procedures involved is inappropriate for industrial-scale processes. Therefore, exposure of the researchers to the needs of the marketplace and product value chain is a vital future topic.
5 Conclusions Lignocellulosic nanomaterials are the future materials and interesting tools to tailor desired function and performance into construction and building sector. They can be acted as reinforcement into various construction and building materials such as wood, concrete, and cement composite and polymer nanocomposites for properties enhancement. In cement and concrete, incorporation of lignocellulosic nanomaterials such as nanocellulose fiber could improve the bonding interface between nanofibers and the cement paste and subsequently resulted in products with better performance. In wood, nanocellulose could be dispersed into coatings system for wood protection and enhancement of mechanical strength and abrasion resistance. In polymer nanocomposite, mechanical strength could be improved with the lignocellulosic nanomaterials act as nanofiller. Nevertheless, despite owning a number of advantages, the applications of lignocellulosic nanomaterials are still not prevalent in the developing countries mainly due to lack of exposure and financial constraints. Lacking of understanding and information to the biological impacts of these lignocellulosic nanomaterials upon exposure is also another important factor that contributed to the indecisiveness of the consumers. In the future, a comprehensive understanding on the potential threats posed by nanomaterials toward human and environmental health is the matter of the utmost important. The current researches are ambiguous and scattered. Despite some studies revealed that nanomaterials have no detrimental effects to human health, some contrary opinions regarding the potential threats of nanomaterials did prevail among other researchers. Therefore, the biological impacts and its effects on the human health must be addressed in the future for boosting the user’s confidence in the adoption and utilization of these nanomaterials. Apart from that, exposure of the researchers to the needs of the marketplace and product value chain is also a vital future topic.
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