**3. Materials used for the production of bio-binder**

#### **3.1. Bio-oil**

**1. Introduction**

4 Modified Asphalt

**2.1. Definition**

[14, 15].

**1.1. General introduction**

use of non-recoverable natural resources.

moisture resistance and good aging characteristics [6].

**2. Bio binder's definition and resources**

of highly oxygenated compounds [7–10].

**2.2. Bio-binder material sources**

Bio-materials that are used as binders in asphalt mixtures are termed "bio binders" [1]. The interest on using bio-binders in pavement engineering has significantly grown over the last decades due to the increasing scarcity of raw materials and environmental concerns about the

Common alternative binders include engine oil residue, bio-binder, soybean oil, palm oil, fossil fuel, swine waste, and materials from pyrolysis [2]. Chemical compositions of the majority of these alternative binders are similar to those of unmodified asphalt binders (e.g. Resin, saturates, aromatics, and asphaltene) [3]. On the other hand, tests indicate the wide variability in the properties of alternative binders. Also, the chemical modification mechanism for asphalt with alternative binders depends clearly on the unmodified asphalt and is consequently not well understood [4, 5]. For energy sustainability, environment-friendly materials and an urgent need for infrastructure rehabilitation that more research is needed to evaluate the alternative binders for use in asphalt modification. The alternative binders should have

Bio-binder is an eco-friendly asphalt binder alternative obtained from non-petroleum-based renewable resources, which should not rival any food material. From the definition, biobinder can be described as dark brown, high flow, organic liquids that are comprised mainly

A range of different vegetable oils has been investigated in recent times, through the application of scientific research and development, to determine their physical and chemical properties to study their applicability to be used as bio-binders in the pavement industry [11–13]. Bio-oils are produced from plant matter and residues, such as municipal wastes, agricultural crops, and byproducts from agricultural and forestry [8]. Other biomass sources include molasses and rice, sugar, potato starches and corn, gum resins and natural tree, vegetable oils and natural latex rubber, cellulose, lignin, waste oil of palm, peanut oil waste, coconut waste,

Utilize this bio-binder can be a great potential as a modifier for asphalt binder because of simi-

Currently, bio-binder is the second leading renewable energy in the nation after hydropower

lar chemical properties when compared with crude petroleum as shown in **Table 1**.

potato starch, canola oil waste, dried sewerage effluent, and others.

Bio-Oil is the liquid produced from the rapid heating of biomass in a vacuum condition [17]. There are many advantages for bio-oils over asphalt from crude oil as they are environmentfriendly, renewable, present a great economic opportunity, and provide energy security.

#### *3.1.1. Bio-oil sources and production*

#### *3.1.1.1. Thermochemical liquefaction*

To obtain more gasoline and other liquid fuels, the quality of the bio-oil is improved by using processes such as thermal cracking and hydrogenation [16, 17]. Upon fractionation, the light hydrocarbon fraction can be used as fuel. The remaining heavy residue called bio-binder can be used as an asphalt binder modifier.

#### *3.1.1.2. Pyrolysis process*

Fast pyrolysis is a thermal decomposition process that requires a high heat transfer rate to the biomass particles and a short vapor residence time in the reaction zone [8], which is a hightemperature process for the production of vapors, aerosols and some coal-like char where biomass is quickly heated in the vacuum and then decomposes. The dark brown mobile fluid (bio-oil) is formed after cooling and condensation of these vapors and aerosols. When organic matter is biomass, consisting of biopolymers (such as cellulose, hemicelluloses, and lignin), the oils produced are called bio-oils. Generally, fast pyrolysis is used to obtain high-grade biooil. Fast pyrolysis processes produce 60–75 wt% of liquid bio-oil, 15–25 wt% of solid char, and 10–20 wt% of non-condensable gases. Fast pyrolysis initially starts with slow heating rates, and then involves a rapid heating rate of the biomass, that can reach up to 300°C/min, but not as fast as flash pyrolysis.

Fast pyrolysis design variables include, but are not limited to the following ones reported by [8]: feed moisture content, particle size, pretreatment, reactor configuration, heat supply, heat transfer, heating rates, reaction temperature, vapor residence time, secondary cracking, char separation, ash separation, and liquid collection.

renewable raw materials, composite materials and manufactured products known as "biological materials." When deliberating biomaterials, it is noteworthy that there are no direct negative effects caused by plants on the ecosystem, they can recycle carbon dioxide for the Earth's crust, grow in different climatic zones, and much work on soil fertility improvement [22].

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Elastomers materials, or rubber materials, have a cross-linked structure. Natural and synthetic rubbers are both common examples of Elastomers [23]. Elastomer is a polymer with viscoelasticity property in general, especially at low Yung's modulus, and high yield strain compared to other materials. The plastics are very flexible and flexible, which means they can undergo large elastic deformities without rupture and greatly restore the shape and size after removal has been removed. Plastics are usually resistant to oil and fuel, not permeable to liquids and gases, but tend to deteriorate by oxidation [23]. Furthermore, plastics are either thermoplastic (can be thawed) or thermoplastic (which cannot be melted). The use of plant-derived triglycerides is a substance used in the production of plastics because it provides two interactive

sites, the double bond in the series of unsaturated fatty acids, and the ester group [24].

The introduction of crumb rubber in the production of asphalt-rubber mixtures for road pavement should be considered a sustainable technology that turns unwanted residues into a new mixture with high resistance to fatigue and breakage. According to ASTM D 6814–02, rubber is a synthetic or natural synthetic rubber that can be chemically cross-linked/vulcanized to enhance its useful properties. Rubber or elastic joints across the link are three-dimensional molecular networks, with long molecules held together by chemical bonds. It absorbs solvents and swells but does not melt. Moreover, it cannot be reprocessed simply by heating

The amount of waste cooking oil collected every year from food shops and restaurants is found to be 3 billion gallons; this is according to the U.S. Environmental Protection Agency (2011) [28]. This can be treated by polymerization and used as an alternative to bitumen [29]. The researchers investigated the potential use of cooking oil waste as an approved bitumen rejuvenation agent [30, 31]. The result was very promising because of the successful application of waste cooking oil with bitumen as an activated agent for used bitumen or older leads to an economical and environmentally friendly solution. More modification and research is

In general, the dumping of untreated waste into a land fill or river leads to a negative environmental impact. One of the main environmental issues arises the enrichment process that occurs when there is an obstacle to sunlight to penetrate the surface of the river caused by

*3.2.3. Using of bio-elastomers in asphalt modification*

needed to obtain more efficient and effective results.

*3.3.1. Problems caused by waste cooking oil and its treatment methods*

*3.2.2. Bio-elastomers*

[25–27].

**3.3. Waste cooking oil**

#### *3.1.2. Importance of using bio-oil in the modification of asphalt*

The bio-oil obtained from waste biomass at low cost is an environmentally friendly material containing the natural antioxidant lignin, bio-renewable asphalt modifier and asphalt substitutes potential to be successfully applied as an antioxidant additive in asphalt pavements. The other various chemicals that using as antioxidant additives are not environmentally and economically preferable [18].

#### **3.2. Biopolymers**

Bio-plastics or organic plastics are a form of plastics derived from renewable biomass sources, such as vegetable oil, corn starch, pea starch, or microbiota. Some of its advantages are often biodegradable, not toxic to produce and alternative to traditional plastics this is included in the definition of biodegradable polymers mentioned in [19]. Biopolymers are an alternative to petroleum based polymers produced by living organisms. The field of biopolymers is still in its early stage but is growing in popularity every day. Biodegradable polymers are produced by using micro-organisms, plants and animals (biological systems), or biological starting materials, which have been synthesized chemically from (e.g. starch, sugars, oils or natural fats, etc.). The biopolymers are biodegradable most of them and water-soluble some of them. Most of the biopolymer are compostable or will decompose in landfills, but the time can vary from a few days to even years, and will eventually decompose [20]. The natural rubber is the best example classified as a biopolymer. The natural rubber is the most common elastomer in almost all human activities due to its unique characteristics, raw or combined with synthetic elastomers. This elastomer has the ability to improve pavements performance and durability for being applied in road pavements as a recycled material from tires [21].

#### *3.2.1. Importance of using the biopolymers*

The bitumen degree controls the performance of the pavement mixture during the service temperature. In many cases, bitumen properties need to change to enhance their flexible characteristics at low temperatures to withstand adequate cracking and increase shear resistance through high-temperatures and continuous loads to resist corrosion. With the addition of SBS polymers, the physical properties of polymers are usually modified to produce an improved asphalt grade that improves the performance of hot mix asphalt. In 2008, there was a shortage of type spherical polymers for the asphalt industry forcing asphalt mixing producers and owner/agencies to search for different products that could be used as bitumen [21]. With expectations of increased demand from soft asphalt in the next time, the need for viable asphalt is cost-effective that can be used instead of typical spike-type rates will still strong. Of asphalt-modified polymer mixture, nearly 80% of the polymer modified asphalt uses the SB type polymers. Thus there is a great market opportunity to create new polymers that can complement and/or replace the type SBS polymers used in asphalt paving. The researchers of chemistry and engineering are currently working to obtain chemicals and polymers from renewable raw materials, composite materials and manufactured products known as "biological materials." When deliberating biomaterials, it is noteworthy that there are no direct negative effects caused by plants on the ecosystem, they can recycle carbon dioxide for the Earth's crust, grow in different climatic zones, and much work on soil fertility improvement [22].

#### *3.2.2. Bio-elastomers*

transfer, heating rates, reaction temperature, vapor residence time, secondary cracking, char

The bio-oil obtained from waste biomass at low cost is an environmentally friendly material containing the natural antioxidant lignin, bio-renewable asphalt modifier and asphalt substitutes potential to be successfully applied as an antioxidant additive in asphalt pavements. The other various chemicals that using as antioxidant additives are not environmentally and

Bio-plastics or organic plastics are a form of plastics derived from renewable biomass sources, such as vegetable oil, corn starch, pea starch, or microbiota. Some of its advantages are often biodegradable, not toxic to produce and alternative to traditional plastics this is included in the definition of biodegradable polymers mentioned in [19]. Biopolymers are an alternative to petroleum based polymers produced by living organisms. The field of biopolymers is still in its early stage but is growing in popularity every day. Biodegradable polymers are produced by using micro-organisms, plants and animals (biological systems), or biological starting materials, which have been synthesized chemically from (e.g. starch, sugars, oils or natural fats, etc.). The biopolymers are biodegradable most of them and water-soluble some of them. Most of the biopolymer are compostable or will decompose in landfills, but the time can vary from a few days to even years, and will eventually decompose [20]. The natural rubber is the best example classified as a biopolymer. The natural rubber is the most common elastomer in almost all human activities due to its unique characteristics, raw or combined with synthetic elastomers. This elastomer has the ability to improve pavements performance and durability

The bitumen degree controls the performance of the pavement mixture during the service temperature. In many cases, bitumen properties need to change to enhance their flexible characteristics at low temperatures to withstand adequate cracking and increase shear resistance through high-temperatures and continuous loads to resist corrosion. With the addition of SBS polymers, the physical properties of polymers are usually modified to produce an improved asphalt grade that improves the performance of hot mix asphalt. In 2008, there was a shortage of type spherical polymers for the asphalt industry forcing asphalt mixing producers and owner/agencies to search for different products that could be used as bitumen [21]. With expectations of increased demand from soft asphalt in the next time, the need for viable asphalt is cost-effective that can be used instead of typical spike-type rates will still strong. Of asphalt-modified polymer mixture, nearly 80% of the polymer modified asphalt uses the SB type polymers. Thus there is a great market opportunity to create new polymers that can complement and/or replace the type SBS polymers used in asphalt paving. The researchers of chemistry and engineering are currently working to obtain chemicals and polymers from

for being applied in road pavements as a recycled material from tires [21].

separation, ash separation, and liquid collection.

economically preferable [18].

*3.2.1. Importance of using the biopolymers*

**3.2. Biopolymers**

6 Modified Asphalt

*3.1.2. Importance of using bio-oil in the modification of asphalt*

Elastomers materials, or rubber materials, have a cross-linked structure. Natural and synthetic rubbers are both common examples of Elastomers [23]. Elastomer is a polymer with viscoelasticity property in general, especially at low Yung's modulus, and high yield strain compared to other materials. The plastics are very flexible and flexible, which means they can undergo large elastic deformities without rupture and greatly restore the shape and size after removal has been removed. Plastics are usually resistant to oil and fuel, not permeable to liquids and gases, but tend to deteriorate by oxidation [23]. Furthermore, plastics are either thermoplastic (can be thawed) or thermoplastic (which cannot be melted). The use of plant-derived triglycerides is a substance used in the production of plastics because it provides two interactive sites, the double bond in the series of unsaturated fatty acids, and the ester group [24].

#### *3.2.3. Using of bio-elastomers in asphalt modification*

The introduction of crumb rubber in the production of asphalt-rubber mixtures for road pavement should be considered a sustainable technology that turns unwanted residues into a new mixture with high resistance to fatigue and breakage. According to ASTM D 6814–02, rubber is a synthetic or natural synthetic rubber that can be chemically cross-linked/vulcanized to enhance its useful properties. Rubber or elastic joints across the link are three-dimensional molecular networks, with long molecules held together by chemical bonds. It absorbs solvents and swells but does not melt. Moreover, it cannot be reprocessed simply by heating [25–27].

#### **3.3. Waste cooking oil**

The amount of waste cooking oil collected every year from food shops and restaurants is found to be 3 billion gallons; this is according to the U.S. Environmental Protection Agency (2011) [28]. This can be treated by polymerization and used as an alternative to bitumen [29].

The researchers investigated the potential use of cooking oil waste as an approved bitumen rejuvenation agent [30, 31]. The result was very promising because of the successful application of waste cooking oil with bitumen as an activated agent for used bitumen or older leads to an economical and environmentally friendly solution. More modification and research is needed to obtain more efficient and effective results.

#### *3.3.1. Problems caused by waste cooking oil and its treatment methods*

In general, the dumping of untreated waste into a land fill or river leads to a negative environmental impact. One of the main environmental issues arises the enrichment process that occurs when there is an obstacle to sunlight to penetrate the surface of the river caused by the blocking of a thin layer of oil. Ultimately, oxygen supply to aquatic life is disturbed when nutrient enrichment occurs in the river [32, 33]. The balance of the water ecosystem balance in the lake or river has also affected water quality. Engine oil from vehicles or cooking oil waste from residential areas contributes to the main source of river pollution. The responsibility to overcome high construction costs and reduce waste disposal issues has begun to practice the recycling of waste as an alternative and an alternative way to prevent these problems [32]. According to Hamad et al. [33] and Singhbando and Tezuka [34], only the designated licensed companies responsible for collecting cooking waste World Customs Organization (WCO) from the food industry and especially the fast food restaurant before being sent to the recycling centers.

every passing year [42]. According to the food and drug administration (FDA) report [42, 43],

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Chemical properties gas chromatography–mass spectrometry test (GCMS) is one of the chemical tests that are used for the purpose of the identification of chemical compound in unknown waste cooking oil. Based on the observation, the major chemical compound identified in the WCO is oleic acid, which represents 43.67% of the entire compound. Meanwhile, palmitic acid represents for 38.35% whereas 11.39% is recorded linoleic acid as shown in **Table 2**.

Due to long chain of palmitic acid and oleic acid [44], the potential of being cracked is high by thermal cracking or catalytic cracking process. Based on the research conducted by Zahoor et al. [45], the properties of unused oil is differ from used cooking oil especially in term of

The main field of application of bio-binders is in the paving industry. However, market opportunities exist in housing products via roofing shingles and sealants [46]. There are three ways that a bio-binder reduces the use of bitumen from fossil fuels (as shown in the percentage) [8].

density, kinematic viscosity, and moisture content which presented in **Table 3**.

40% of the sewage system is blocked with frying oil which is cast in the kitchen sink.

*3.3.3. Chemical properties and characterization of waste cooking oil*

*3.3.4. Experimental application of bio-binders*

**1.** Directly alternative (75–100% bitumen substitute.

Heneicosanoic acid 0.08 Cis-11-Eicosenoic acid 0.16 Linolenic acid 0.29 Palmitic acid 38.35 Linoleic acid 11.39 Stearic acid 4.33 Myristic acid 1.03 ɣ-Linolenic acid 0.37 Lauric acid 0.34 Oleic acid 43.67 Total 100

**Free fatty acid's type Waste cooking oil %**

**2.** Bitumen extender (10–75% bitumen substitute)

**3.** Bitumen modifier (<10% bitumen substitute)

**Table 2.** Chemical properties of waste cooking oil [44].

#### *3.3.2. Production of waste cooking oil*

Waste cooking oil originates from frying activity at high-temperatures during food preparation, usually in the food industry, restaurants, hotels, and residences. The application of global customs organizations is diverse, for example, the use of yellow grease [35, 36], potential as a fuel source in biodiesel production [37], animal food [38], and making soap production [37]. Despite efforts to collect up to 15 million tons of WCO annually, only a small amount of cooking waste is properly managed through the recycling process [38]. Regular monitoring and management of the WCO creates a challenge to be addressed and becomes the primary consideration for overcoming serious dumping problems that eventually lead to serious water pollution [39]. **Figure 1** shows the total production of the WCO by States. The production of 10 million tons of WCO per year, accounting for 55%, makes the United States the highest producer of the WCO.

A large amount of vegetable oil consumption about 17 million tons causes a huge amount of waste that has reduced the production of oil resources, and this amount increases about 2%

**Figure 1.** Production of cooking oil based on the country [36, 40, 41].

every passing year [42]. According to the food and drug administration (FDA) report [42, 43], 40% of the sewage system is blocked with frying oil which is cast in the kitchen sink.

#### *3.3.3. Chemical properties and characterization of waste cooking oil*

Chemical properties gas chromatography–mass spectrometry test (GCMS) is one of the chemical tests that are used for the purpose of the identification of chemical compound in unknown waste cooking oil. Based on the observation, the major chemical compound identified in the WCO is oleic acid, which represents 43.67% of the entire compound. Meanwhile, palmitic acid represents for 38.35% whereas 11.39% is recorded linoleic acid as shown in **Table 2**.

Due to long chain of palmitic acid and oleic acid [44], the potential of being cracked is high by thermal cracking or catalytic cracking process. Based on the research conducted by Zahoor et al. [45], the properties of unused oil is differ from used cooking oil especially in term of density, kinematic viscosity, and moisture content which presented in **Table 3**.

#### *3.3.4. Experimental application of bio-binders*

the blocking of a thin layer of oil. Ultimately, oxygen supply to aquatic life is disturbed when nutrient enrichment occurs in the river [32, 33]. The balance of the water ecosystem balance in the lake or river has also affected water quality. Engine oil from vehicles or cooking oil waste from residential areas contributes to the main source of river pollution. The responsibility to overcome high construction costs and reduce waste disposal issues has begun to practice the recycling of waste as an alternative and an alternative way to prevent these problems [32]. According to Hamad et al. [33] and Singhbando and Tezuka [34], only the designated licensed companies responsible for collecting cooking waste World Customs Organization (WCO) from the food industry and especially the fast food restaurant before being sent to the recy-

Waste cooking oil originates from frying activity at high-temperatures during food preparation, usually in the food industry, restaurants, hotels, and residences. The application of global customs organizations is diverse, for example, the use of yellow grease [35, 36], potential as a fuel source in biodiesel production [37], animal food [38], and making soap production [37]. Despite efforts to collect up to 15 million tons of WCO annually, only a small amount of cooking waste is properly managed through the recycling process [38]. Regular monitoring and management of the WCO creates a challenge to be addressed and becomes the primary consideration for overcoming serious dumping problems that eventually lead to serious water pollution [39]. **Figure 1** shows the total production of the WCO by States. The production of 10 million tons of WCO per year, accounting for 55%, makes the United States

A large amount of vegetable oil consumption about 17 million tons causes a huge amount of waste that has reduced the production of oil resources, and this amount increases about 2%

cling centers.

8 Modified Asphalt

*3.3.2. Production of waste cooking oil*

the highest producer of the WCO.

**Figure 1.** Production of cooking oil based on the country [36, 40, 41].

The main field of application of bio-binders is in the paving industry. However, market opportunities exist in housing products via roofing shingles and sealants [46]. There are three ways that a bio-binder reduces the use of bitumen from fossil fuels (as shown in the percentage) [8].



**Table 2.** Chemical properties of waste cooking oil [44].


There are many other less obvious predictions:

• Expected interactions with fuels, oils, and so on.

• Will be available in large quantities upon request.

**4.3. Rheological properties of bio-modified asphalt**

• It will have a predictable interaction with contiguous mixtures.

• It will have a predictable mixing with a virgin binder as a reclaimed asphalt pavement

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Rolling thin film oven test (RTFO) and pressure aging vessel (PAV) may not sufficiently represent plant and field aging because an alternative binder may have significantly different aging characteristics. Start by identifying an aging index to compare with unmodified asphalt is suggested in experimental respects. RTFO It should be operated over a variety of times and temperatures to see if normal temperature correspondence is still present. The same is true for PAV. Use PAV at 60°C for excessive times and compare output performance with results

Bio-binder may it may completely break down or give suggestively different time-temperature relationships. A clear example is an alternative bond with a fine melting point. A binder with a melting point at 73°C may be well suited for use in heavy road traffic in the PG 64 environment, but the dynamic shear rheometer (DSR) test at a specific grade of 76°C will give

While strength characteristics and cracking are precarious to pavement performance, they are controlled by the total and the gradient and the effect of the alternative binder properties is not easily expected. Unlike low-temperature characteristics, it may be necessary to reduce the mixture test to explain the effect of a new material on cracking and strength properties.

As illustrious above, bio-binder may have a different shape to the master curve. They may also have varied stress tolerance. For more than a few reasons, the creep compliance is

• Predictable environmental characteristics.

• Predictable outflow characteristics.

• Expectable water solubility.

• It will have a predictable smell.

**4.2. Aging**

in standard conditions.

inappropriate results.

**4.4. Strength properties and cracking**

**4.5. Rutting performance at high-temperature**

**Table 3.** Comparison between properties of unused oil and used cooking oil.

In almost, all the road construction has been used modifiers in conventional bitumen binder. To decrease the demand for petroleum-based bitumen research is being done on bitumen extender as 100% replacement of bitumen. Additives are the resin, emulsions, crumb rubber, polymer and so on. Waste materials like waste cooking oil, waste engine oil and so on, may be the promising alternatives [47, 48].
