**Author details**

Aurelio Ramírez Hernández

Address all correspondence to: chino\_raha@hotmail.com

Departamento de Química, Universidad del Papaloapan, Tuxtepec, Oaxaca, México

## **References**


[4] Sabetzadeh M, Bagheri R, Masoomi M. Study on ternary low density polyethylene/linear low density polyethylene/thermoplastic starch blend films. Carbohydrate Polymers. 2015; **119**:126-133

[21] Krevelen DW, Nijenhuis K. Properties of Polymers. Amsterdam: Elservier; 2009

tions of polymers. European Polymer Journal. 1996;**32**(11):1337-1344

Communications. 1998;**19**(6):283-286

Materials Science. 2012;**35**(3):415-418

Science Edition. 2014;**29**(6):1187-1190

2016;**69**(5). DOI: 10.1002/star.201600197

2005;**60**(1):103-109

[22] Rogošić M, Mencer H, Gomzi Z. Polydispersity index and molecular weight distribu-

Chemical Modification of Starch with Synthetic http://dx.doi.org/10.5772/intechopen.72384 19

[23] Mua JP, Jackson DS. Fine structure of corn amylase and amylopectin fractions with various molecular weights. Journal of Agricultural and Food Chemistry. 1997;**45**:3840-3847 [24] Yoo SH, Jane JL. Molecular weights and gyration radii of amylopectins determined by high-performance size-exclusion chromatography equipped with multiangle laser-light scattering and refractive index detectors. Carbohydrate Polymers. 2002;**49**:307-314 [25] Mani R, Tang J, Bhattacharya M. Synthesis and characterization of starch-graft-polycaprolactone as compatibilizer for starch/polycarprolactone blends. Macromolecular Rapid

[26] Wootthikanokkhan J, Kasemwananimit P, Sombatsompop N, Kositchaiyong A, Isarankurana S, Kaabbuathong N. Preparation of modified starch-grafted poly(lactic acid) and a study on compatibilizing efficacy of the copolymers in poly(lactic acid)/ther-

[27] Qingling W, Yingmo H, Jianhua Z, Yang L, Xue Y, Jing B. Convenient synthetic method of starch/lactic acid graft copolymer catalyzed with sodium hydroxide. Bulletin of

[28] Yingmo H, Mingru T. Synthesis of starch-g-lactic acid copolymer with high grafting degree catalyzed by ammonia water. Carbohydrate Polymers. 2015;**118**:79-82

[29] Hu Z. The optimized synthesis of starch-g-lactic acid copolymer with high grafting degree catalyzed by sulfuric acid. Journal of Wuhan University of Technology—Materials

[30] Chen L, Nia Y, Biana X, Xueyu Q, Zhuanga X, Chena X, Jinga X. A novel approach to grafting polymerization of ε-caprolactone onto starch granules. Carbohydrate Polymers.

[31] Dubois P, Krishnan M, Ramani N. Aliphatic polyester-grafted starch-like polysaccha-

[32] Ramírez-Hernández A, Aparicio-Saguilán A, Mata-Mata JL, González-García G, Hernández-Mendoza H, Gutiérrez-Fuentes A, Báez-García E. Chemical modification of banana starch by the in situ polymerization of e-caprolactone in one step. Starch-Starke.

[33] De Bruyn H, Sprong E, Gaborieau M, David G, Roper JA, Gilbert RG. Starch-graftcopolymer latexes initiated and stabilized by ozonolyzed amylopectin. Journal of

[35] Wang S, Wang Q, Xuerong F, Jin X, Ying Z, Jiugang Y, Heling J, Cavaco-Paulo A. Synthesis and characterization of starch-poly(methyl acrylate) graft copolymers using horseradish

rides by ring-opening polymerization. Polymer. 1999;**40**:3091-3100

Polymer Science Part A: Polymer Chemistry. 2006;**44**(20):5832-5845 [34] Bemiller J, Whistler R. Starch: Chemistry and Technology. Vol. 729. 2009

peroxidase. Carbohydrate Polymers. 2016;**136**:1010-1016

moplastic starch blends. Journal of Applied Polymer Science. 2012;**126**:389-396


[21] Krevelen DW, Nijenhuis K. Properties of Polymers. Amsterdam: Elservier; 2009

[4] Sabetzadeh M, Bagheri R, Masoomi M. Study on ternary low density polyethylene/linear low density polyethylene/thermoplastic starch blend films. Carbohydrate Polymers. 2015;

[5] Bikiaris D, Prinos J, Koutsopoulos K, Vouroutzis N, Pavlidou E, Frangis N, Panayiotou C. LDPE/plasticized starch blends containing PE-g-MA copolymer as compatibilizer.

[6] Kittisak J, Noppol L, Phisit S, Somchai W, Charin T, Toshiaki O. Reactive blending of thermoplastic starch and polyethylene-graft-maleic anhydride with chitosan as com-

[8] Pereira CS, Cuncha AM, Reise RL, Vázquez B, Sanroman J. New starch-based thermoplastic hydrogels for use as bone cements or drug-delivery carriers. Journal of Materials

[9] Miller-Chou BA, Koenig JL. A review of polymer dissolution. Progress in Polymer

[11] Ueberreiter K. The solution process. In: Crank J, Park GS, editors. Diffusion in Polymers.

[12] Krasicky PD, Groele RJ, Rodriguez F. Measuring and modeling the transition layer during the dissolution of glassy polymer films. Journal of Applied Polymer Science.

[13] Hamaide T, Deterre R, Feller JF. Environmental Impact of Polymers. 10. United kingdom:

[15] Barton A. Handbook of Solubility, Parameters and Other Cohesion Parameters. 2nd ed.

[16] Small PA. Some factors affecting the solubility of polymers. Journal of Applied

[17] Cecopieri-Gómez ML, Palacios J. Cálculo teórico y experimental del parámetro termodinámico de interacción de Flory del Poli(adipato de etileno). Revista de la Sociedad

[18] Sun SF. Physicalchemistry of Macromolecules: Basicprinciples and Issues. USA: Wiley; 2004 [19] Laura F, Villamizar LF, Martínez F. Physicochemical study of the solubility of eudragit s100® in some aqueous and organic systems. Revista Colombiana de Quimica. 2008;**37**

[20] Ramírez-Hernández A, Mata-Mata JL, Aparicio-Saguilán A, González-García G, Hernández-Mendoza H, Gutiérrez-Fuentes A, Báez-García JE. The effect of ethylene gly-

col on starch-g-PCL graft copolymer synthesis. Starch-Starke. 2016;**68**:1148-1157

Polymer Degradation and Stability. 1998;**59**(1):287-291

patibilizer. Carbohydrate Polymers. 2016;**153**:89-95

Science Materials in Medicine. 1998;**9**(12):825-833

New York, NY: Academic Press; 1968. pp. 219-257

New York: CRC Press; 1991. pp. 157-193

Química de México. 2001;**45**(2):82-88

Science. 2003;**28**(8):1223-1270

1988;**35**(3):641-651

Editorial Wiley; 2014

Chemistry. 1953;**3**:71-80

(2):173-187

[7] Ritter W, Gardenier KJ, Kempf W. German Offen. DE 4 038 700; 1992.

[10] Billmeyer FW. Ciencia de los polímeros. Editorial Reverte, 23. España; 2004

[14] Walter RH. Polysaccharide Association Structures in Food. 100. USA; 1998

**119**:126-133

18 Applications of Modified Starches


[36] Yongjun M, Xiyan D, Jianan S, Leli W, Zhengping L. Preparation of corn starch-g-polystyrene copolymer in ionic liquid: 1-Ethyl-3-methylimidazolium acetate. Carbohydrate Polymers. 2015;**121**:348-354

[51] Graaf RA, Lammers G, Janssen LPBM, Beenackers AACM. Quantitative analysis of chemically modified starches by1H-NMR spectroscopy. Starch/Stärke. 1995;**47**:469-475

Chemical Modification of Starch with Synthetic http://dx.doi.org/10.5772/intechopen.72384 21

[52] Cheng HN, Neiss T. Solution NMR spectroscopy of food polysaccharides. Polymer

[53] Ming L, Torsten W, Fengwei X, Frederick J, Halley P, Gilbert G. Biodegradation of starch films: The roles of molecular and crystalline structure. Carbohydrate Polymers. 2015;

[54] Ming L, Torsten W, Fengwei X, Frederick J, Halley P, Gilbert G. Shear degradation of molecular, crystalline, and granular structures of starch during extrusion. Starch-Starke.

[55] Vega GA, Lara AE, Lemus MR. Isotermas de adsorción en harina de maíz (*Zea mays* L.).

[56] Czepirski L, Komorowska-Czepirska E, Szymonska J. Fitting of different models for water vapour sorption on potato starch granules. Applied Surface Science. 2002;**196**:150-153

[57] Staudt PB, Kechinski CP, Tessaro IC, Marczak LDF, Soares R, Cardozo NSM. A new method for predicting sorption isotherms at different temperatures using the BET

[58] Deepak P, Reena S. Synthesis and characterization of graft copolymers of methacrylic acid onto gelatinized potato starch using chromic acid initiator in presence of air. Advanced

[59] Apopei DF, Dinu MV, Drăgan ES. Graft copolymerization of acrylonitrile onto potatoes starch by ceric ion. Digest Journal of Nanomaterials and Biostructures. 2012;**7**(2):707-716

[60] Martinez-Arellano AC, Rivera-Armenta JL, Mendoza-Martínez AM, Díaz-Zavala NP, Sandoval-Robles J, Banda-Cruz E. Study of graft copolymerization of butyl acrylate on

[61] Lu DR, Xiao CM, Xu SJ. Starch-based completely biodegradable polymer materials.

[62] Kugler S, Spychaj T, Wilpiszewska K, Gorący K, LendzionBieluń Z. Starchgraft copolymers of N-vinylformamide and acrylamide modified with montmorillonite manufactured by reactive extrusion. Journal of Applied Polymer Science. 2013;**127**(4):2847-2854

[63] Worzakowska M. Starch-g-poly(benzyl methacrylate) copolymers. Journal of Thermal

starch using redox initiator system. Química Nova. 2014;**37**(3):426-430

Food Science and Tecnhology (Campinas). 2006;**26**(4):821-827

model. Journal of Food Engineering. 2013;**114**(1):139-145

Materials Letters. 2012;**3**(2):136-142

Express Polymer Letters. 2009;**3**(6):366-375

Analysis and Calorimetry. 2016;**124**:1309-1318

Reviews. 2012;**52**:81-114

**122**:115-122

2014;**66**:595-605


[51] Graaf RA, Lammers G, Janssen LPBM, Beenackers AACM. Quantitative analysis of chemically modified starches by1H-NMR spectroscopy. Starch/Stärke. 1995;**47**:469-475

[36] Yongjun M, Xiyan D, Jianan S, Leli W, Zhengping L. Preparation of corn starch-g-polystyrene copolymer in ionic liquid: 1-Ethyl-3-methylimidazolium acetate. Carbohydrate

[37] Chang GC, Kiho L. Preparation of starch-g-polystyrene copolymer by emulsion polym-

[38] Vladimir N, Sava V, Dušan A, Aleksandar P. Biodegradation of starch–graft–polystyrene and starch–graft––Poly(methacrylic acid) copolymers in model river water. Journal of

[39] Hashem A, Afifi MA, EI-Alfy EA, Hebeish A. Synthesis, characterizations and saponification of poly(AN)-starch composites and properties of their hydrogels. American

[40] Hashem A, Afifi MA, EI-Alfy EA, Hebeish A. Synthesis, characterizations and saponification of poly(AN)-starch composites and properties of their hydrogels. American

[42] Jingyuan X, Krietemeyer E, Finkenstadt V, Solaiman D, Ashby R, Garcia R. Preparation of starch–poly–glutamic acid graft copolymers by microwave irradiation and the charac-

[43] Kouroush S, Mehmet Y, Zakir MOR, Erhan P. Controlled graft copolymerization of lactic acid onto starch in a supercritical carbon dioxide medium. Carbohydrate Polymers.

[44] Wang S, Xu J, Wang Q, Fan X, Yu Y, Wang P, Zhang Y, Yuan J, Cavaco-Paulo A. Preparation and rheological properties of starch-g-poly(butylacrylate) catalyzed by horseradish per-

[45] Vandana S, Sadhana M. Microwave synthesis, characterization, and zinc uptake studies of starch-graft-poly(ethylacrylate). International Journal of Biological Macromolecules.

[46] Haradhan K, Subhadip D, Tridib T. Synthesis of starch-g-poly-(N-methylacrylamide-coacrylic acid) and its application for the removal of mercury (II) from aqueous solution by

[47] Swanson LC, Fanta GF, Fecht RG, Burr R. Polymer applications of renewable-resource materials: Starch-g-poly(methyl acrylate) effects of graft level and molecular weight on

[49] Alcázar-Alay SC, Almeida Meireles MA. Physicochemical properties, modifications and applications of starches from different botanical sources. Food Science and Technology

[50] Najemi L, Jeanmaire T, Zerroukhi A, Raihane M. Organic catalyst for ring opening polymerization of ε-caprolactone in bulk. Route to starch-graft-polycaprolactone. Starch-

terization of their properties. Carbohydrate Polymers. 2016;**140**:233-237

Polymers. 2015;**121**:348-354

20 Applications of Modified Starches

2014;**114**:149-156

2010;**47**(3):348-355

(Campinas). 2015;**35**(2):215-236

Starke. 2010;**62**:147-154

erization. Carbohydrate Polymers. 2002;**48**(2):125-130

the Serbian Chemical Society. 2013;**78**(9):1425-1441

Journal of Applied Sciences. 2005;**2**(3):614-621

Journal of Applied Sciences. 2005;**2**(3):614-621

oxidase. Process Biochemistry. 2017;**59**:104-110

adsorption. European Polymer Journal. 2014;**58**:1-10

tensile strength. Polymer Science and Technology. 1981;**17**:59-71 [48] Carballo SLM. Introducción a la catálisis heterogénea. Colombia; 2002

[41] Nguyen CC, Verne JM, Pauley EP. Patent US5130394A; 1992


**Chapter 3**

**Provisional chapter**

**Evaluation of Styrene Content over Physical and**

**Evaluation of Styrene Content over Physical and** 

**Feather Composites**

**Feather Composites**

José Luis Rivera-Armenta, Zahida Sandoval-Arellano,

**Abstract**

**1. Introduction**

José Luis Rivera-Armenta, Zahida Sandoval-Arellano,

María Leonor Méndez-Hernández,

María Leonor Méndez-Hernández,

Beatriz Adriana Salazar-Cruz and María Yolanda Chavez-Cinco

Beatriz Adriana Salazar-Cruz and María Yolanda Chavez-Cinco

http://dx.doi.org/10.5772/intechopen.72969

Additional information is available at the end of the chapter

presence of chicken feathers due its good thermal properties.

chicken feather (CF), thermal behavior

Additional information is available at the end of the chapter

**Chemical Properties of Elastomer/TPS-EVOH/Chicken**

**Chemical Properties of Elastomer/TPS-EVOH/Chicken** 

A series of styrene-butadiene (SB) elastomer/thermoplastic starch (TPS)/ethylene vinyl alcohol copolymer (EVOH) composites were modified including chicken feathers in its formulation, which have the main component keratin. The composites were prepared by means of melt blending, and their chemical interactions were evaluated by means of infrared spectroscopy (FTIR), and their thermal properties as Tg values were investigated using differential scanning calorimetry (DSC), thermal stability using thermogravimetric analysis (TGA), and viscoelastic properties with dynamic mechanical analysis (DMA). The styrene content in SB was changed in 3 levels, and chicken feather content also changed in 3 levels. It was identified that Tg value in composites decreases that is attributed to the styrene content in elastomer and that the chicken feather improved the storage modulus of composite. The thermal stability of composites also was affected by the

**Keywords:** styrene-butadiene copolymer (SBR), EVOH, thermoplastic starch (TPS),

© 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution,

© 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,

distribution, and reproduction in any medium, provided the original work is properly cited.

and reproduction in any medium, provided the original work is properly cited.

The poor disposition of solid wastes from natural resources that adversely affect the environment has developed interest related to the development of biodegradable polymers to obtain

DOI: 10.5772/intechopen.72969

#### **Evaluation of Styrene Content over Physical and Chemical Properties of Elastomer/TPS-EVOH/Chicken Feather Composites Evaluation of Styrene Content over Physical and Chemical Properties of Elastomer/TPS-EVOH/Chicken Feather Composites**

DOI: 10.5772/intechopen.72969

María Leonor Méndez-Hernández, José Luis Rivera-Armenta, Zahida Sandoval-Arellano, Beatriz Adriana Salazar-Cruz and María Yolanda Chavez-Cinco María Leonor Méndez-Hernández, José Luis Rivera-Armenta, Zahida Sandoval-Arellano, Beatriz Adriana Salazar-Cruz and María Yolanda Chavez-Cinco

Additional information is available at the end of the chapter Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/intechopen.72969

#### **Abstract**

A series of styrene-butadiene (SB) elastomer/thermoplastic starch (TPS)/ethylene vinyl alcohol copolymer (EVOH) composites were modified including chicken feathers in its formulation, which have the main component keratin. The composites were prepared by means of melt blending, and their chemical interactions were evaluated by means of infrared spectroscopy (FTIR), and their thermal properties as Tg values were investigated using differential scanning calorimetry (DSC), thermal stability using thermogravimetric analysis (TGA), and viscoelastic properties with dynamic mechanical analysis (DMA). The styrene content in SB was changed in 3 levels, and chicken feather content also changed in 3 levels. It was identified that Tg value in composites decreases that is attributed to the styrene content in elastomer and that the chicken feather improved the storage modulus of composite. The thermal stability of composites also was affected by the presence of chicken feathers due its good thermal properties.

**Keywords:** styrene-butadiene copolymer (SBR), EVOH, thermoplastic starch (TPS), chicken feather (CF), thermal behavior

#### **1. Introduction**

The poor disposition of solid wastes from natural resources that adversely affect the environment has developed interest related to the development of biodegradable polymers to obtain

© 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. © 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

improved composites, not only for environmental reasons but also for their properties and sustainability [1–3]. A valuable alternative with enormous potential is to manufacture composite materials using chicken feather (CF). Keratin is the main component of CF that has extraordinary properties of thermal and mechanical resistance, is also light and confers acoustic insulation, and is a light material with high mechanical and thermal resistance, and for some decades, it was the focus of attention to be used as a raw material in combination with different plastics products [4–12]. The CF that generates the poultry industry as solid waste represents more than five million tons per year. Recently, the literature points the keratin of CF as a material with low cost by its abundance in the nature and that can take advantage of the waste of the birds, which confers a status of material recycled environment friendly [10]. According to previous works, keratin can be used in conjunction with other biomaterials in medical applications suggesting affinity with cells and tissues, also in combination with other biopolymers as chitosan [13]. In addition, chicken feather keratin is a renewable and low-cost material [14–20] and is compatible with biodegradable polymers as chitosan-starch [21], cellulose, wool [4], including thermoplastic starch (TPS) [14–20] and ethylene vinyl alcohol copolymer (EVOH), which provides greater ductility and improves the elasticity of TPS. In nature, natural fibers are obtained with good physicochemical properties such as keratin, which is extracted from nature and can also be found in nails, wool, claws, horns, and feathers [8, 22]. Research has focused in conjunction with manufacturers in finding new directions for the application of keratin in polymer blends which have not been well known to the present. According to Cheng et al. [23], the feasibility of using the fiber of chicken feathers in compounds with polylactic acid (PLA) has been studied in terms of its mechanical and thermal properties. To test the mechanical and physical properties of the panels, Winandy et al. [8] have materialized a series of medium-density fiber panels containing several different blends of wood fiber and chicken feather fiber (CFF). **Figure 1** shows the constituents of a chicken feather.

It is a cheap material compared with synthetic polymers in packing applications. The TPS refers to granule starch, which has been destructurized, forming a mixture of its polymer constituents and various proteins, lipids, and smaller molecules that are also contained in the starch granule. With the aim to improve its processability and mechanical properties and moisture resistance, starch is blended by extrusion with other polymers, using plasticizers as glycerin and water. In this way, it is possible to obtain a material with desired physical properties [26]. The transformation of native starch to thermoplastic starch (TPS) by extrusion results in the loss of the natural chain structure. That is, processing in the presence of heat and water causes the starch granules to gel or break, progressively destroying crystallinity [26]. Starch has been used as a thermoplastic material because it is a renewable, biodegradable, and very low-cost resource [21]; the most effective plasticizer for starch-based materials is glycerol, water, sorbitol, and urea [26]. To improve the properties of thermoplastic starch (TPS) because it is not a good choice because of its poor mechanical properties and because of its susceptibility to moisture, the structure of the starch has been modified, mixed with other polymers (biodegradable and/or synthetic), and a better interfacial adhesion is obtained with compatibilizers. **Figure 2** shows the process of gelatinization and plasticization for starch [27]. One of the thermoplastic materials compatible with TPS is EVOH, which is widely used in the food packaging industry. It is a biodegradable polymer and considered a good compatibilizer that when added to a mixture of immiscible materials during the extrusion modifies the interfacial properties and stabilizes the mixture. It is known that EVOH provides it a better ductility and improves the elasticity of TPS [26]. Several researches have been carried out with TPS-EVOH composites reinforced with natural biopolymers, and among others are coir, cellulose fibers [15, 16], and hydroxyapatite [17–19], but there are no reports where CF is used as a reinforcer in TPS/EVOH composites. Several studies have been carried out on the composite materials using SB elastomers and keratin from the CF, which has allowed knowing about the influence of the different variables on the thermal and mechanical behavior, as well as the various valid tools for the observation of variations [2, 9, 20, 28–30]. With respect to

Evaluation of Styrene Content over Physical and Chemical Properties of Elastomer/TPS-EVOH/…

http://dx.doi.org/10.5772/intechopen.72969

25

**Figure 1.** Constituents of a chicken feather.

Barone and Schmidt [24] reported the use of feather keratin fiber as a short fiber reinforcement in low-density polyethylene composites. Research has been reported on high-density polyethylene-based compounds using keratin from chicken feathers. Taking into account the hydrophilic properties of keratin, its potential application in the manufacture of fibers with improved sorption characteristics is seen, being useful for the production of textile material that focuses on sanitary and medical applications.

In previous works [3], chicken feather keratin fibers were used as reinforcement in the poly(methylmethacrylate) (PMMA) matrix. The composites were evaluated by thermal and dynamic-mechanical analysis. The high-temperature stability and thermal transition of the keratin/PMMA base compound were found to be higher than that of virgin PMMA.

Villarreal-Lucio et al. [25] prepared composites from chicken feathers and polyvinyl chloride (PVC) finding that composites CF-PVC represent an opportunity to obtain materials with improved properties such as thermal stability and dynamic-mechanic properties, but with a low interfacial addition between PVC and CF. Starch is a biopolymer obtained from renewable plants such potato, maize, wheat, and others sources. The main components are amylose and amylopectin, the first one is a linear polysaccharide and second one has a branched structure. Evaluation of Styrene Content over Physical and Chemical Properties of Elastomer/TPS-EVOH/… http://dx.doi.org/10.5772/intechopen.72969 25

**Figure 1.** Constituents of a chicken feather.

improved composites, not only for environmental reasons but also for their properties and sustainability [1–3]. A valuable alternative with enormous potential is to manufacture composite materials using chicken feather (CF). Keratin is the main component of CF that has extraordinary properties of thermal and mechanical resistance, is also light and confers acoustic insulation, and is a light material with high mechanical and thermal resistance, and for some decades, it was the focus of attention to be used as a raw material in combination with different plastics products [4–12]. The CF that generates the poultry industry as solid waste represents more than five million tons per year. Recently, the literature points the keratin of CF as a material with low cost by its abundance in the nature and that can take advantage of the waste of the birds, which confers a status of material recycled environment friendly [10]. According to previous works, keratin can be used in conjunction with other biomaterials in medical applications suggesting affinity with cells and tissues, also in combination with other biopolymers as chitosan [13]. In addition, chicken feather keratin is a renewable and low-cost material [14–20] and is compatible with biodegradable polymers as chitosan-starch [21], cellulose, wool [4], including thermoplastic starch (TPS) [14–20] and ethylene vinyl alcohol copolymer (EVOH), which provides greater ductility and improves the elasticity of TPS. In nature, natural fibers are obtained with good physicochemical properties such as keratin, which is extracted from nature and can also be found in nails, wool, claws, horns, and feathers [8, 22]. Research has focused in conjunction with manufacturers in finding new directions for the application of keratin in polymer blends which have not been well known to the present. According to Cheng et al. [23], the feasibility of using the fiber of chicken feathers in compounds with polylactic acid (PLA) has been studied in terms of its mechanical and thermal properties. To test the mechanical and physical properties of the panels, Winandy et al. [8] have materialized a series of medium-density fiber panels containing several different blends of wood fiber and chicken

feather fiber (CFF). **Figure 1** shows the constituents of a chicken feather.

that focuses on sanitary and medical applications.

24 Applications of Modified Starches

Barone and Schmidt [24] reported the use of feather keratin fiber as a short fiber reinforcement in low-density polyethylene composites. Research has been reported on high-density polyethylene-based compounds using keratin from chicken feathers. Taking into account the hydrophilic properties of keratin, its potential application in the manufacture of fibers with improved sorption characteristics is seen, being useful for the production of textile material

In previous works [3], chicken feather keratin fibers were used as reinforcement in the poly(methylmethacrylate) (PMMA) matrix. The composites were evaluated by thermal and dynamic-mechanical analysis. The high-temperature stability and thermal transition of the

Villarreal-Lucio et al. [25] prepared composites from chicken feathers and polyvinyl chloride (PVC) finding that composites CF-PVC represent an opportunity to obtain materials with improved properties such as thermal stability and dynamic-mechanic properties, but with a low interfacial addition between PVC and CF. Starch is a biopolymer obtained from renewable plants such potato, maize, wheat, and others sources. The main components are amylose and amylopectin, the first one is a linear polysaccharide and second one has a branched structure.

keratin/PMMA base compound were found to be higher than that of virgin PMMA.

It is a cheap material compared with synthetic polymers in packing applications. The TPS refers to granule starch, which has been destructurized, forming a mixture of its polymer constituents and various proteins, lipids, and smaller molecules that are also contained in the starch granule. With the aim to improve its processability and mechanical properties and moisture resistance, starch is blended by extrusion with other polymers, using plasticizers as glycerin and water. In this way, it is possible to obtain a material with desired physical properties [26]. The transformation of native starch to thermoplastic starch (TPS) by extrusion results in the loss of the natural chain structure. That is, processing in the presence of heat and water causes the starch granules to gel or break, progressively destroying crystallinity [26]. Starch has been used as a thermoplastic material because it is a renewable, biodegradable, and very low-cost resource [21]; the most effective plasticizer for starch-based materials is glycerol, water, sorbitol, and urea [26]. To improve the properties of thermoplastic starch (TPS) because it is not a good choice because of its poor mechanical properties and because of its susceptibility to moisture, the structure of the starch has been modified, mixed with other polymers (biodegradable and/or synthetic), and a better interfacial adhesion is obtained with compatibilizers. **Figure 2** shows the process of gelatinization and plasticization for starch [27].

One of the thermoplastic materials compatible with TPS is EVOH, which is widely used in the food packaging industry. It is a biodegradable polymer and considered a good compatibilizer that when added to a mixture of immiscible materials during the extrusion modifies the interfacial properties and stabilizes the mixture. It is known that EVOH provides it a better ductility and improves the elasticity of TPS [26]. Several researches have been carried out with TPS-EVOH composites reinforced with natural biopolymers, and among others are coir, cellulose fibers [15, 16], and hydroxyapatite [17–19], but there are no reports where CF is used as a reinforcer in TPS/EVOH composites. Several studies have been carried out on the composite materials using SB elastomers and keratin from the CF, which has allowed knowing about the influence of the different variables on the thermal and mechanical behavior, as well as the various valid tools for the observation of variations [2, 9, 20, 28–30]. With respect to

to take advantage of its properties to obtain materials with a higher performance than conventional ones. In this work, three SB elastomers with different styrene contents were combined with a TPS-EVOH blend, and additional to that, CF was added to obtain a composite that presents enhanced properties. The effect of styrene content in SB elastomer was studied. **Table 1** shows the identification codes for prepared composites. By means of infrared spectroscopy (FTIR), the possible chemical reactions between components in composite were evaluated, and thermal properties were evaluated by means differential scanning calorimetry (DSC), dynamic

SB1-elastomer with 45% styrene content, SB2-elastomer with 32% styrene content, SB3-elastomer with 25% styrene

**Material Elastomer (g) TPS-EVOH (g) Chicken feathers (g)**

Evaluation of Styrene Content over Physical and Chemical Properties of Elastomer/TPS-EVOH/…

http://dx.doi.org/10.5772/intechopen.72969

27

SB1-45/TPS-EVOH/CF 45 12 3 SB1-50/TPS-EVOH/CF 50 8 2 SB1-55/TPS-EVOH/CF 55 4 1 SB2-45/TPS-EVOH/CF 45 12 3 SB2-50/TPS-EVOH/CF 50 8 2 SB2-55/TPS-EVOH/CF 55 4 1 SB3-45/TPS-EVOH/CF 45 12 3 SB3-50/TPS-EVOH/CF 50 8 2 SB3-55/TPS-EVOH/CF 55 4 1

Chicken feather (CF) was obtained from a local slaughterhouse in Altamira city, México, and three types of styrene-butadiene (SB) used were SB1 45% styrene content, SB2 32% styrene content, and SB3 25% styrene content, provided by Dynasol Elastomers S.A. de C.V. Chicken feathers (CFs) were cleaned with several washes, first with distilled water and then with acetone and finally with ethanol; after that CFs were dried at room temperature to be clean, sanitized, and odor free, and then proceeded to remove the barbules from quill, that was cut it into small pieces [1, 25]. A twin screw extruder ZSK30 with nine heating zones was used to obtain the mixtures of TPS-EVOH. The EVOH melted at 200°C was fed in zone 5 using the single-screw extruder Killion KTS-100 at full speed. The mixing of EVOH with TPS started from zone 5 to zone 8. In the pumping zone 9, the pressure of the extrudate was increased. The screw speed for all blends was 150 rpm. Mixtures were prepared with 75% TPS proportion [36]. **Figure 3** shows the configuration of double screw extruder to obtain the blends with

mechanical analysis (DMA), and thermogravimetric analysis (TGA).

**2. Experimental**

content, TPS-EVOH with 75% TPS content.

**Table 1.** Identification codes for prepared composites.

**2.1. Materials**

EVOH.

**Figure 2.** Gelatinization and plasticization of starch.

the above, several important aspects are listed namely dynamic-mechanical behavior, hydrophilic, acoustic, and thermal stability properties of keratin, and its study per se represents a vast field of scientific exploration. In the other hand, the use of elastomers in combination with other materials as compound has been reported, trying to improve ductility and oxygen barrier of elastomers [31–33]. Among the elastomers, the styrene-butadiene (SB) copolymers are the most valuables due to the wide application areas as adhesives, asphalt modifiers, sealants, shoe soles, impact modifiers, and also can be compounded to produce materials that enhance grip, feel, and appearance in applications such as tires, automotive parts, and packing [34, 35]. SB copolymers are considered a thermoplastic material, whose elastic behavior1 and thermoplastic behavior2 are combined at same time. The combination of good mechanical properties and processability makes the SB copolymers an interesting kind of materials. It is essential that hard (styrene block) and soft (butadiene) segments are immiscible on a microscopic scale. One important variable is SB copolymer properties, the styrene content, which gives a plastic characteristic to copolymer with high styrene content, and elastomer behaves as a vulcanized elastomer at low styrene content. Because of its good processability behavior, thermal, and mechanical properties, SB copolymers have been widely used in composite materials, trying

<sup>1</sup> Property to change and recover the shape when a force has applied and then removed.

<sup>2</sup> The property to become viscous and free-flowing liquid when heated and resolidified when cooled to room temperature.

Evaluation of Styrene Content over Physical and Chemical Properties of Elastomer/TPS-EVOH/… http://dx.doi.org/10.5772/intechopen.72969 27


SB1-elastomer with 45% styrene content, SB2-elastomer with 32% styrene content, SB3-elastomer with 25% styrene content, TPS-EVOH with 75% TPS content.

**Table 1.** Identification codes for prepared composites.

to take advantage of its properties to obtain materials with a higher performance than conventional ones. In this work, three SB elastomers with different styrene contents were combined with a TPS-EVOH blend, and additional to that, CF was added to obtain a composite that presents enhanced properties. The effect of styrene content in SB elastomer was studied. **Table 1** shows the identification codes for prepared composites. By means of infrared spectroscopy (FTIR), the possible chemical reactions between components in composite were evaluated, and thermal properties were evaluated by means differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and thermogravimetric analysis (TGA).

### **2. Experimental**

#### **2.1. Materials**

and thermo-

the above, several important aspects are listed namely dynamic-mechanical behavior, hydrophilic, acoustic, and thermal stability properties of keratin, and its study per se represents a vast field of scientific exploration. In the other hand, the use of elastomers in combination with other materials as compound has been reported, trying to improve ductility and oxygen barrier of elastomers [31–33]. Among the elastomers, the styrene-butadiene (SB) copolymers are the most valuables due to the wide application areas as adhesives, asphalt modifiers, sealants, shoe soles, impact modifiers, and also can be compounded to produce materials that enhance grip, feel, and appearance in applications such as tires, automotive parts, and packing [34, 35].

and processability makes the SB copolymers an interesting kind of materials. It is essential that hard (styrene block) and soft (butadiene) segments are immiscible on a microscopic scale. One important variable is SB copolymer properties, the styrene content, which gives a plastic characteristic to copolymer with high styrene content, and elastomer behaves as a vulcanized elastomer at low styrene content. Because of its good processability behavior, thermal, and mechanical properties, SB copolymers have been widely used in composite materials, trying

The property to become viscous and free-flowing liquid when heated and resolidified when cooled to room temperature.

are combined at same time. The combination of good mechanical properties

SB copolymers are considered a thermoplastic material, whose elastic behavior1

Property to change and recover the shape when a force has applied and then removed.

plastic behavior2

**Figure 2.** Gelatinization and plasticization of starch.

26 Applications of Modified Starches

1

2

Chicken feather (CF) was obtained from a local slaughterhouse in Altamira city, México, and three types of styrene-butadiene (SB) used were SB1 45% styrene content, SB2 32% styrene content, and SB3 25% styrene content, provided by Dynasol Elastomers S.A. de C.V. Chicken feathers (CFs) were cleaned with several washes, first with distilled water and then with acetone and finally with ethanol; after that CFs were dried at room temperature to be clean, sanitized, and odor free, and then proceeded to remove the barbules from quill, that was cut it into small pieces [1, 25]. A twin screw extruder ZSK30 with nine heating zones was used to obtain the mixtures of TPS-EVOH. The EVOH melted at 200°C was fed in zone 5 using the single-screw extruder Killion KTS-100 at full speed. The mixing of EVOH with TPS started from zone 5 to zone 8. In the pumping zone 9, the pressure of the extrudate was increased. The screw speed for all blends was 150 rpm. Mixtures were prepared with 75% TPS proportion [36]. **Figure 3** shows the configuration of double screw extruder to obtain the blends with EVOH.

*2.3.3. Dynamic mechanical analysis (DMA)*

*2.3.4. Thermogravimetric analysis (TGA)*

600°C with 10°C/min rate, using 10 ± 2 mg sample.

**3.1. Infrared spectroscopy of elastomer/TPS-EVOH/keratin composite**

**Figure 4.** FTIR spectra of SB3, TPS-EVOH, CF, and SB3/TPS-EVOH/CF composite.

equipment under an N<sup>2</sup>

**3. Results**

The dynamic mechanical analysis was carried out in a DMA-Q800 TA-Instrument, with a double cantilever clamp, and sample dimensions were 30 × 12 × 3 mm in a rectangular shape (length, wide, thickness). Analysis were carried out in multifrequency mode with temperature range from −100 to 200°C, with a heating rate 5°C min−1, 1 Hz frequency, and amplitude 2 μm.

The thermogravimetric analysis was carried out in an SDT (DSC-TGA) Q600 TA Instrument

**Figure 4** shows the IR spectra for SB3, TPS-EVOH, CF, and SB3/TPS-EVOH/CF composites from 4000 to 600 cm−1. It is possible to identify some of the functional groups in the blends of the elastomers with TPS-EVOH and CF. The SB3 signals at 3000 and 3100 cm−1 are associated with unsaturated carbons; meanwhile, at 2900 and 2850 cm−1, the signals are related to the

atmosphere with 100 mL/min flow, in a temperature range from 40 to

Evaluation of Styrene Content over Physical and Chemical Properties of Elastomer/TPS-EVOH/…

http://dx.doi.org/10.5772/intechopen.72969

29

**Figure 3.** Configuration of double screw extruder with nine heating zones, to obtain TPS-EVOH mixtures using a single screw extruder to melt at 200°C the EVOH.

#### **2.2. Preparation elastomer/TPS-EVOH/keratin composite**

The elastomer/TPS-EVOH/keratin composites were prepared by melting the mix using a plasticorder/Brabender PL2000 torque rheometer, establishing the optimum conditions at 185°C with 20 min of mixing, using roller blades at 100 rpm speed. Then, the materials were compressed in a Dake press with 10 tons during 20 min, using appropriate molds. **Table 1** shows the codes used for identification of composites.

#### **2.3. Composites characterization**

#### *2.3.1. Infrared spectroscopy (FTIR)*

The infrared spectroscopy technique was used to identify functional groups of materials, and for that purpose, equipment Perkin Elmer Spectrum One model was used, with attenuated total reflectance (ATR) technique with ZnSe plates in a range of 4000–600 cm−1 with 12 scans.

#### *2.3.2. Differential scanning calorimetry (DSC)*

The differential scanning calorimetry (DSC) was used to determine the thermal transitions of the composites, using Perkin Elmer DSC8000 equipment. The employed method first consists of heating cycle from 30 to 200°C at 10°C/min, then a cooling cycle from 200°C up to −100°C, and the sample was kept for 5 min at this temperature and a second heating ramp from −100 to 200°C was carried out, with heating rate of 10°C/min, taking the second heating for analysis. The sample amount used was 10 ± 2 mg, in an inert atmosphere of nitrogen, with a flow rate of 20 mL/min.

#### *2.3.3. Dynamic mechanical analysis (DMA)*

The dynamic mechanical analysis was carried out in a DMA-Q800 TA-Instrument, with a double cantilever clamp, and sample dimensions were 30 × 12 × 3 mm in a rectangular shape (length, wide, thickness). Analysis were carried out in multifrequency mode with temperature range from −100 to 200°C, with a heating rate 5°C min−1, 1 Hz frequency, and amplitude 2 μm.

#### *2.3.4. Thermogravimetric analysis (TGA)*

The thermogravimetric analysis was carried out in an SDT (DSC-TGA) Q600 TA Instrument equipment under an N<sup>2</sup> atmosphere with 100 mL/min flow, in a temperature range from 40 to 600°C with 10°C/min rate, using 10 ± 2 mg sample.
