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A review: role of interfacial adhesion between carbon blacks and elastomeric materials
  • 비영리 CC BY-NC
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ABSTRACT

Carbon blacks (CBs) have been widely used as reinforcing materials in advanced rubber composites. The mechanical properties of CB-reinforced rubber composites are mostly controlled by the extent of interfacial adhesion between the CBs and the rubber. Surface treatments are generally performed on CBs to introduce chemical functional groups on its surface. In this study, we review the effects of various surface treatment methods for CBs. In addition, the preparation and properties of CB-reinforced rubber composites are discussed.


KEYWORD
rubber , carbon blacks , surface treatments , interfacial adhesion
  • 1. Introduction

    Rubber exhibits superior viscoelastic properties and improves the lifespan of products which continue to be transformed. At first, natural rubber (NR), which is composed of isoprene monomers, was obtained from nature. Later, as industries developed, synthetic rubbers were produced to supplement the production of NR. In particular, studies have been conducted on a new kind of rubber that is made of butadiene, namely, a copolymer of acrylonitrile butadiene rubber (NBR) and styrene butadiene rubber (SBR) as shown in Fig. 1 [1-6].

    However, rubber lacks sufficient physical strength, which makes it unsuitable for various applications. For this reason, fillers, such as carbon materials and silica, are added to rubber to form rubber composites with improved mechanical behaviors [7-27].

    In recent years, carbon materials have been widely used as reinforcing agents in high-performance composite materials [28-35], adsorbents [36], electrochemistry [37], and energy storage materials [38]. Among various carbon materials used as reinforcing agents, carbon blacks (CBs) are the oldest carbon derivatives produced by the incomplete combustion of petroleum products, such as fluid catalytic cracking tar and coal tar. Moreover, the particle size, structure, and surface conditions of CBs (Fig. 2) make them popular reinforcing agents [19-21].

    CBs contain more than 95% amorphous carbon, and their particle sizes vary from 5 to 500 nm. The physical properties of CBs vary with the production method and the raw materials used, which makes them suitable for applications in various fields. The mixing ratio of CBs in automobile tires is 50%, while that in other rubber products is approximately 30%. Relatively large amounts of reinforced CBs should be added to NR to attain acceptable mechanical properties. Cohesion occurs between CB particles due to chemical and physical bonds. The chemical composition of CB aggregates is 90%–99% carbon, 0.1%–1.0% hydrogen, 0.2%–2.0% oxygen, and a small amount of sulfur and ash. In addition, oxygen-containing functional groups, such as the carboxyl, hydroxyl, and quinine groups, exist on the surfaces of CBs. These are called surface functional groups. These surface functional groups increase the chemical and physical bonding between the CBs particles and the rubber matrix [39-43].

    Therefore, the addition of CBs to rubber results in the formation of composites with improved mechanical properties, such as tensile strength, tearing strength, hardness, and abrasion resistance [4,22-25].

    In addition, surface treatments of CBs render them suitable for practical applications in CB-reinforced rubber composites. The surface treatments mainly introduce chemical functional groups to the CBs surfaces. These functional groups increase the bonding between the CBs and rubber, which results in stronger interfacial adhesion compared to the case when untreated CBs are used. Various surface treatment methods may be applied to CBs, including chemical, plasma, ozone, electrochemical, and heat treatment [44-54].

    In this paper, methods for the surface treatment of CBs and for the preparation of rubber/CB composites are reviewed in detail. A classification of surface treatment methods is shown in Fig. 3. In addition, the effects of various surface treatment methods on the mechanical properties of CB-reinforced rubber composites are discussed.

    2. Methods and Effects of Surface Treatments on Carbon Blacks

       2.1. Surface free energy

    Surface free energy is commonly related to the mechanical properties of a material. Fowkes [55] proposed that the total surface free energy can be divided into two components:

    image

    where γL is the London dispersive component of surface free energy, and γSP is the specific (or polar) component of surface free energy.

    The term γSP is further divided into two parameters using the geometric mean:

    image

    The surface free energies between the liquid and solid are calculated according to the following equation using van der Waals acid-base parameters:

    image

    where the subscripts S and L represent solid and liquid phases, respectively. Here, γL is the experimentally determined surface tension of the liquid, θ is the contact angle, γ+ is the electron-acceptor parameter, and γ is the electron-donor parameter of the specific polar component of surface free energy (or tension) [55-57].

       2.2. Chemical treatments

    Virgin carbon blacks (VCBs) were produced at temperatures over 1400℃. Neutral-treated carbon blacks (NCBs), base-treated carbon blacks (BCBs), and acid-treated carbon blacks (ACBs) were prepared by treating VCB with C6H6, 0.1 N KOH, and 0.1 N H3PO4 for 24 h, respectively. Prior to each analysis, the CBs were washed several times with distilled water and dried in a vacuum oven at 90℃ [58-60].

    Ketone (C=O) and hydroxyl (O-H) groups exist on the surface of VCB. According to some reports, an increased number of oxygen-containing groups, such as pyrone and chromene, and other stable basic surface functional groups has been observed in CBs produced at temperatures higher than 800℃. Thus, basic functional groups are already present on the surface of CBs produced at high temperature. For this reason, the intensity of the oxygen-containing groups rapidly increases through an acid-base interaction when CBs are treated with an acid. Meanwhile, the interaction between oxygen radicals and the surface of CBs generates oxides, and the intensity of the functional groups increases slightly when CBs are treated with a basic solution. When CBs are treated with a non-polar solution, a decrease in the intensity of the functional groups that exists on the surface of VCB is observed [61-63].

    As observed from Fig. 4, for the case of ACBs, γSP of the polar component increases largely through the acid-base interaction between the surface of VCBs containing basic functional groups and the oxygen radicals from the solution. On the other hand, the BCBs show a large increase in γSP and γL of the non-polar component owing to the presence of stable basic functional groups. For NCBs, a decrease in the number of polar functional groups resulted in a decrease in the strength of the chemical bond between CBs or an increase in γL due to dispersion interactions resulting from the stabilization of the surface functional groups [55-57,59,60].

       2.3. Ozone treatment

    Ozone is composed of three oxygen atoms, and it resonates into four structures. Ozone, as a powerful oxidizing agent, is highly reactive with various organic and inorganic substances as well as with all metals except platinum and gold. Ozone is formed from OH radicals by various methods, such as silent electric discharge, electrolysis, the photochemical method, high frequency silent discharge, and irradiation. Among these, the silent electric discharge method is most widely used. In general, the CBs surface contains 3%–4% oxygen. However, ozone surface treatment of CBs breaks the unstable bonds present on the surface and produces highly reactive radicals and oxygen-containing functional groups. This causes a large increase in the number of oxygen-containing functional groups present on the CBs surface [64,65].

    Ozone treatment of CBs was performed at various ozone concentrations: 0, 10, 20, 30, and 50 mg L−1 at room temperature. The as-prepared samples were labeled as OCB-0, OCB-10, OCB-20, OCB-30, and OCB-50 corresponding to the ozone concentrations of 0, 10, 20, 30, and 50 mg L−1, respectively [66].

    The surface free energy of the CBs after ozone treatment is shown in Fig. 5. Fig 5a shows the polar and non-polar components of the surface free energy, and an increase in both components is observed. This can be explained as follows. Ozone with a strong oxidizing power attacked the unstable functional groups present on the CB surfaces resulting in the activation of a large number of stable functional groups, which in turn, led to an increase in the non-polar components of the surface free energy. In addition, Fig. 5b shows the γ+ (acid) and γ (base) components of the surface free energy. After ozone treatment, γ+ increased greatly, while γ decreased. This trend was observed because of the increase in the number of −OH and −COOH groups on the CB surfaces caused by ozone treatment. As a result, the polar component of the surface free energy also increased with an increase in γ+. In addition, the polar functional groups present on the CB surfaces react and form a chemical bond with the −CN group of NBR. Therefore, the interactions of interface between NBR and the CBs were activated by an increase in the number of the oxygen-containing polar functional groups present on the CB surfaces after ozone treatment. Finally, the cross-linking density increased due to the network structure [65].

       2.4. Plasma treatment

    Plasma is a gas in which negatively charged electrons are separated from the positively charged protons at high temperature. In plasma, interactions between particles produce light, and the active movement of the particles causes a high reactivity. Plasma gases used for the surface treatment of polymers can be classified into inactive gases, such as argon, helium, and nitrogen, and active gases, such as ammonia and carbon tetrafluoride. For each type of gas, the surface is modified by the introduction of specific functional groups on the surface [67-69].

    Plasma surface treatment is a dry process that produces less pollution and does not cause changes in the mechanical properties of composites, such as strength and modulus of elasticity. In contrast to other treatments, this process changes the surface characteristics [70].

    2.4.1. O2 plasma treatments

    The plasma power used for oxygen plasma treatment was 20 W at a frequency of 13.56 MHz under a pressure of about 0.1 kPa. The treatment was carried out for various durations of 0, 5, 10, 20, and 30 minutes for which the as-prepared samples were named CB-5, CB-10, CB-20, and CB-30, respectively [67].

    O2 plasma surface treatment oxidizes the surface of polymers and introduces oxygen-containing polar functional groups, such as hydroxyl, carboxyl, quinine, and lactone. These polar functional groups increase the hydrophilicity of the surface of hydrophobic polymers and improve their wettability and adhesion. It is generally known that the introduction of oxygen-containing polar functional groups on the CB surface by oxygen plasma treatment increases the interfacial adhesion between CBs and organic elastomers, such as butyl rubber (BR), NR, and NBR, which is polar rubber [67-69].

    Table 1 shows the oxygen content of the CB surface in terms of O1S/C1S ratio after plasma surface treatment. As seen in Table 1, as the plasma processing time was increased, increases in the O1S/C1S ratio were observed. The most significant increase of 5.31% was observed with the processing time of 20 min. The ratio decreased to 4.08% when the processing time was 30 min [67].

    [Table 1.] Results of the O1S/C1S ratio of the carbon black treated by oxygen plasma studied

    label

    Results of the O1S/C1S ratio of the carbon black treated by oxygen plasma studied

    2.4.2. Plasma treatments in N2 condition

    Plasma treatment of CB samples was carried out using a radio frequency for N2 gas. The radio frequency (13.56 MHz) generated by N2-plasma was operated at 30 W. The input treatment time for the N2-plasma treatment was varied to 0, 5, 10, and 20 min under a pressure of 0.1 kPa [71].

    As seen in Table 2, an increase in the duration of the plasma treatment of the CB samples resulted in an increase in the γs+ and γs of the CBs along with an increase in the non-polar components. The oxygen or hydrogen released from the surface of the CBs by the plasma surface treatment was plasmanized, which activated the polar functional groups present on the surface. In addition, the non-polar components increased greatly. In the case of plasma surface treatment using inactive gas N2, the parts of the CB surfaces having the most unstable chemical bonds were attacked and either hydrogen or oxygen was released. The stable functional groups that remained on the CB surface or the surface itself were stabilized. As a result, the non-polar components also increased significantly [70].

    [Table 2.] Surface tension components and parameters of the carbon blacks studied, measured at 20℃

    label

    Surface tension components and parameters of the carbon blacks studied, measured at 20℃

       2.5. Treatment of other carbon materials

    2.5.1. Graphene

    Three grams of graphene was dispersed in 300 mL of a concentrated H2SO4:HNO3 solution at 35℃. The mixture was stirred for 12 h followed by sonication for 1 h. The reaction mixture was then filtered and washed with double-distilled water and acetone until the pH reached 6-7. The resulting oxidized graphene was then dried under vacuum at 80℃ for 12 h [72].

    2.5.2. Multi-walled carbon nanotubes

    Multi-walled carbon nanotubes (MWCNTs) were produced by chemical vapor deposition and had a diameter of 10–30 nm and a length of 20–50 μm. The MWCNTs were chemically purified in 5 M nitric acid for 2 h at room temperature. They were filtered and thoroughly washed with distilled water several times and then dried in a vacuum oven for 24 h at 60℃. The purified MWCNTs were immersed in 2 M phosphoric acid and were treated for 2, 5, and 10 h [73,74].

    2.5.3. Activated carbons

    2.5.3.1. Preparation method I

    The nature of activated carbons (ACs) depends on their ash content because liquid-phase modification can cause the removal of some inorganic species followed by structural changes. The ACs were obtained by chemical surface treatment in an aqueous solution consisting of 35 wt% HCl and 35 wt% NaOH for 24 h, which thus modified the AC surfaces. Prior to use, the residue of chemical solutions in the modified ACs was removed by Soxhlet extraction by boiling with acetone at 80℃ for 2 h. The treated ACs were washed several times with distilled water and then dried in a vacuum oven at 85℃ for 24 h [75,76].

    2.5.3.2. Preparation method II

    ACs were treated by ozone produced from pure oxygen at the rate 6 g O3/h. The reaction time was varied from 1–4 h and the corresponding samples obtained after treatment were denoted as 1, 2, and 4 h, respectively. The surfaces of the samples were analyzed by X-ray photoelectron spectrometry [52].

    2.5.4. Carbon fiber

    2.5.4.1. Preparation method I

    This method was used for the oxidation of carbon fiber (CF) s. A 3:1 mixture of concentrated H2SO4/HNO3 was sonicated at 60℃. In a typical reaction, several small pieces of CF paper were added to 60 mL of the above mentioned mixture in a reaction flask. The flask was placed in an ultrasonic water bath operating at 152 W and 47 kHz and maintained at 60℃. The treatment duration was varied from 10 s to 240 min. The treated substrate was then washed twice with de-ionized water [77].

    2.5.4.2. Preparation method II

    CFs were used in various plasma treatments. Prior to the plasma treatments, CFs were washed with trichloroethylene and were then heated at 120℃ in a vacuum oven overnight. All the treated CFs were stored in vacuo prior to the treatments. Argon and oxygen were supplied from gas cylinders and were more than 99.9% pure [78].

    3. Sample Preparation Methods

       3.1. Natural rubber/carbon blacks composites

    NR was added to the mixing chamber having a rotor speed of 70 rpm. The CBs were then added and the contents were mixed for 2 min. The rotors were stopped and the filler caught in the chute was then swept down into the chamber and mixed for 5 min before dumping. Dump temperatures were around 150 ℃. The density values determined by pycnometer were used to maintain a volume fraction of 0.20 for each grade of filler. This is equivalent to 50 phr mass loading of the unmodified CBs. A second mixing step was performed in a laboratory two-roll mill [79].

       3.2. Butyl rubber/carbon blacks composites

    The 10–100 phr samples of BR were prepared using a high-abrasion furnace, a fast-extruding furnace, and a semi-reinforcing furnace. The preparation techniques have been described elsewhere. The composites were vulcanized at 150℃±2℃ under a pressure of 40 kg cm−2. The duration of vulcanization was 30 min. The samples were thermally aged at 90℃ for 35 days to attain reasonable stability and reproducibility. Disc-like samples with a thickness of 3 mm and a diameter of 10 mm were obtained [80-82].

       3.3. Acrylonitrile butadiene rubber/carbon blacks composites

    3.3.1. Preparation method I

    The NBR/CBs composites were prepared by mixing bio-based engineering polyester elastomer with 40 phr of carbon blacks and 2 phr of dicumyl peroxide at 50℃ and a speed of 40 rpm. All the composites were finally vulcanized under 15 MPa at 160℃ for 20 min to produce 2 mm thick sheets [83].

    3.3.2. Preparation method II

    The NBR/CBs composites were produced in a laboratory two-roll mill. The mixing ratio of CBs was fixed in the range 0–30 phr. The rubber composites were prepared by vulcanization of the rubber compound during compression molding in a hydraulic press. This was done under a pressure of 1500 psi and at temperature of 150℃ using a 1 mm thick mold [84].

       3.4. Styrene butadiene rubber/carbon blacks composites

    3.4.1 Preparation method I

    We used SBR as an elastomer for preparing SBR/CBs composites. SBR is composed of 24.1% styrene and 75.9% butadiene. The CB-filled rubber composites were prepared using a mixer at a speed of 70 rpm at 110℃–150℃ for 4 min. The weight ratio of SBR:CBs was fixed as 2:1 [85,86].

    3.4.2 Preparation method II

    SBR/CBs compounds with varying filler concentrations were prepared as follows. Approximately 5 g of SBR cut into small pieces was placed in a Petri dish and dissolved in 200 mL of benzene. CBs were added to the rubber solution, and the solvent was evaporated. The film composed of rubber and CBs obtained after the evaporation of benzene was processed on a cold two-roll mill. Care was taken to ensure thorough dispersion of the filler into the rubber. After mixing, the compounds were compression molded for 1 h at 145℃ to prepare about 1 mm-thick film samples [87].

    4. Mechanical Properties

       4.1. Rubber/chemical-treated carbon blacks

    Park et al. [56,57] performed chemical surface treatments of CBs and investigated changes in the hardness of rubber reinforced with surface-treated CBs. Fig. 6a shows the changes in the hardness of CB-reinforced rubber after chemical surface treatments. Also, Fig. 6b shows the dependence of tensile strength on the London dispersive component of the surface free energy of the resulting composites, and a model of these properties is shown in Fig. 7. The hardness or elastic modulus of rubber depends heavily on filler properties, such as particle type and size; surface properties; and the cross-linking density of the polymer. The basic functional groups present on the surface of VCB and the active acid-base interactions lead to an increase in aggregation and a decrease in the cross-linking density of the polymer, which in turn, leads to a decrease in the hardness of rubber. In the case of BCB or NCB, the hardness increases, and the increased dispersion force of the CBs strengthens the filler and improves the cross-linking density of the polymer. NCB has a greater London (non-polar) component than BCB. However, a decrease in the number of surface functional groups weakens the physical bonding between the polymer and filler. Hence, NCB shows a lower hardness value [88]. Dai et al. [89] performed surface treatments on CBs using an acid and a base and measured the tensile strength and elongation of CB-reinforced rubber. The mechanical properties of BCB were improved according to the mechanism described above. In addition, the difference between the acid and base surface treatments was larger in terms of tensile strength than elongation [90].

       4.2. Rubber/carbon blacks treated with ozone

    Park et al. [65] treated the surface of CBs with ozone and investigated changes in the hardness of CBs. The tearing energy (GIIIC) measurement results of CBs/NBR composites are shown in Fig. 8. The GIIIC was characterized by a trouser beam test for analyzing the mechanical behavior of the composites, as shown schematically in Fig. 7. As shown in Fig. 8, the GIIIC of the ozone-treated composites significantly increased compared to OCB-0/NBR. This result shows a tendency similar to those of the cross-linking density. The polar functional groups present on the surface of CBs improved the interfacial bonding with NBR, and the mechanical properties of the interface increased according to the mechanism described above [91]. According to the experiment performed by Léopoldès et al. [92], the elastic modulus of CBs increases after oxidative gas-treatments [50].

       4.3. Rubber/carbon blacks after plasma treatments

    Park et al. [67] performed O2 plasma surface treatments on CBs and investigated the corresponding changes in the GⅢC of rubber filled with O2 plasma-treated CBs. Fig. 9 shows variations in the mechanical properties of the interface with GⅢC. The increase in GⅢC for the rubber composites filled with O2 plasma-treated CBs was greater than that for the rubber composites filled with VCB. The GⅢC of CBs/rubber composites increased generally with the duration of the surface treatments. In general, polar functional groups present on the surface of CBs react and form chemical bonds with the CN group of NBR when NBR is filled with CBs. Therefore, carboxyl, hydroxyl, lactone, and carbonyl groups formed on the surface of CBs by O2 plasma treatments increase the interactions between NBR and the interface, and as a result, these composites lead to substantial improvement in the mechanical properties of the interface as compared to that shown by of the rubber composites filled with VCB [93-95]. Akovali et al. [96] introduced additives after surface treatment of CBs using plasma and examined the change in the hardness of CB-reinforced rubber. As a result, the cohesion between other additives and rubber was strengthened after the plasma surface treatment of CBs. This was determined by tensile strength measurements [97,98]. Mathew et al. [99] found that there was less interaction between plasma-treated CBs and other fillers in rubber compounds from Payne effect data. This increases the affinity of CBs for rubber; thus, the mechanical properties of rubber composites are improved [100,101].

    5. Conclusions

    In this paper, we have reviewed various surface treatment methods for CBs and the procedures used to introduce functional groups onto CB surfaces. Good interfacial adhesion between CBs and rubber has been observed after the treatment of CBs due to changes in the surface free energy. We have reviewed the preparation methods in detail and have also discussed the mechanical interfacial properties of CB-reinforced rubber composites, such as hardness, tensile energy, and tearing energy in this system.

참고문헌
  • 1. Hosler D, Burkett SL, Tarkanian MJ (1999) Prehistoric polymers: rubber processing in ancient mesoamerica [Science] Vol.284 P.1988 google cross ref
  • 2. Cordier P, Tournilhac F, Soulie-Ziakovic C, Leibler L (2008) Self-healing and thermoreversible rubber from supramolecular assembly [Nature] Vol.451 P.977 google cross ref
  • 3. Gogotsi Y (2010) High-temperature rubber made from carbon nanotubes [Science] Vol.330 P.1332 google cross ref
  • 4. Ulfah IM, Fidyaningsih R, Rahayu S, Fitriani DA, Saputra DA, Winarto DA, Wisojodharmo LA (2015) Influence of carbon black and silica filler on the rheological and mechanical properties of natural rubber compound [Procedia Chem] Vol.16 P.258 google cross ref
  • 5. Woo CS, Park HS (2007) Mechanical properties evaluation of natural and synthetic rubber [Elastomers Compos] Vol.42 P.32 google
  • 6. Thongsang S, Vorakhan W, Wimolmala E, Sombatsompop N (2012) Dynamic mechanical analysis and tribological properties of NR vulcanizates with fly ash/precipitated silica hybrid filler [Tribol Int] Vol.53 P.134 google cross ref
  • 7. Hassan HH, Ateia E, Darwish NA, Halim SF, El-Aziz AKA (2012) Effect of filler concentration on the physico-mechanical properties of super abrasion furnace black and silica loaded styrene butadiene rubber [Mater Des] Vol.34 P.533 google cross ref
  • 8. Domenech SC, Bendo L, Mattos DJS, Borges NG Jr, Zucolotto V, Mattoso LHC, Soldi V (2009) Elastomeric composites based on ethylene?propylene?diene monomer rubber and conducting polymer-modified carbon black [Polym Compos] Vol.30 P.897 google cross ref
  • 9. Mao Y, Wen S, Chen Y, Zhang F, Panine P, Chan TW, Zhang L, Liang Y, Liu L (2013) High performance graphene oxide based rubber composites [Sci Rep] Vol.3 P.2508 google cross ref
  • 10. Salaeh S, Nakason C (2012) Influence of modified natural rubber and structure of carbon black on properties of natural rubber compounds [Polym Compos] Vol.33 P.489 google cross ref
  • 11. Park SJ, Cho KS (2003) Filler?elastomer interactions: influence of silane coupling agent on crosslink density and thermal stability of silica/ rubber composites [J Colloid Interface Sci] Vol.267 P.86 google cross ref
  • 12. Park SJ, Seo MK (2005) Interfacial characteristics of polymeric composite materials [Polymer (Korea)] Vol.29 P.221 google
  • 13. Park SJ, Cho KS, Zaborski M, Slusarski L (2002) Filler-elastomer interaction. 5. Effect of silane surface treatment on interfacial adhesion of silica/rubber composites [Polymer (Korea)] Vol.26 P.445 google
  • 14. Sung JH, Ryu SR, Lee DJ (2011) Effects of strain-induced crystallization on mechanical properties of elastomeric composites containing carbon nanotubes and carbon black [Trans Korean Soc Mech Eng A] Vol.35 P.999 google cross ref
  • 15. Peddini SK, Bosnyak CP, Henderson NM, Ellison CJ, Paul DR (2015) Nanocomposites from styrene?butadiene rubber (SBR) and multiwall carbon nanotubes (MWCNT) part 2: mechanical properties [Polymer] Vol.56 P.443 google cross ref
  • 16. Ismail H, Omar NF, Othman N (2011) Effect of carbon black loading on curing characteristics and mechanical properties of waste tyre dust/carbon black hybrid filler filled natural rubber compounds [J Appl Polym Sci] Vol.121 P.1143 google cross ref
  • 17. Frohlich J, Niedermeier W, Luginsland HD (2005) The effect of filler?filler and filler?elastomer interaction on rubber reinforcement [Compos Part A: Appl Sci Manuf] Vol.36 P.449 google cross ref
  • 18. Park SJ, Kim JS (2001) Influence of plasma treatment on microstructures and acid?base surface energetics of nanostructured carbon blacks: N2 plasma environment [J Colloid Interface Sci] Vol.244 P.336 google cross ref
  • 19. Thomas PS, Abdullateef AA, Al-Harthi MA, Atieh MA, De SK, Rahaman M, Chaki TK, Khastgir D, Bandyopadhyay S (2012) Electrical properties of natural rubber nanocomposites: effect of 1-octadecanol functionalization of carbon nanotubes [J Mater Sci] Vol.47 P.3344 google cross ref
  • 20. Park SJ, Kim JS (2000) Role of chemically modified carbon black surfaces in enhancing interfacial adhesion between carbon black and rubber in a composite system [J Colloid Interface Sci] Vol.232 P.311 google cross ref
  • 21. Leblanc JL (2011) Simplified modeling calculations to enlighten the mechanical properties (modulus) of carbon black filled diene rubber compounds [J Appl Polym Sci] Vol.122 P.599 google cross ref
  • 22. Omnes B, Thuillier S, Pilvin P, Grohens Y, Gillet S (2008) Effective properties of carbon black filled natural rubber: experiments and modeling [Compos Part A: Appl Sci Manuf] Vol.39 P.1141 google cross ref
  • 23. Tzounis L, Debnath S, Rooj S, Fischer D, Mader E, Das A, Stamm M, Heinrich G (2014) High performance natural rubber composites with a hierarchical reinforcement structure of carbon nanotube modified natural fibers [Mater Des] Vol.58 P.1 google cross ref
  • 24. Wang J, Vincent J, Quarles CA (2005) Review of positron annihilation spectroscopy studies of rubber with carbon black filler [Nucl Instrum Methods Phys Res B] Vol.241 P.271 google cross ref
  • 25. Kim JK (1998) Conductive carbon black filled composite (I): the effect of carbon block on the conductivity [Elastomers Compos] Vol.33 P.355 google
  • 26. Carli LN, Roncato CR, Zanchet A, Mauler RS, Giovanela M, Brandalise RN, Crespo JS (2011) Characterization of natural rubber nanocomposites filled with organoclay as a substitute for silica obtained by the conventional two-roll mill method [Appl Clay Sci] Vol.52 P.56 google cross ref
  • 27. Junkong P, Kueseng P, Wirasate S, Huynh C, Rattanasom N (2015) Cut growth and abrasion behaviour, and morphology of natural rubber filled with MWCNT and MWCNT/carbon black [Polym Test] Vol.41 P.172 google cross ref
  • 28. Matos CF, Galembeck F, Zarbin AJG (2014) Multifunctional and environmentally friendly nanocomposites between natural rubber and graphene or graphene oxide [Carbon] Vol.78 P.469 google cross ref
  • 29. Tang Z, Zhang L, Feng W, Guo B, Liu F, Jia D (2014) Rational design of graphene surface chemistry for high-performance rubber/graphene composites [Macromolecules] Vol.47 P.8663 google cross ref
  • 30. Jo JO, Saha P, Kim NG, Ho CC, Kim JK (2015) Development of nanocomposite with epoxidized natural rubber and functionalized multiwalled carbon nanotubes for enhanced thermal conductivity and gas barrier property [Mater Des] Vol.83 P.777 google cross ref
  • 31. Nakaramontri Y, Kummerlowe C, Nakason C, Vennemann N (2015) The effect of surface functionalization of carbon nanotubes on properties of natural rubber/carbon nanotube composites [Polym Compos] Vol.36 P.2113 google cross ref
  • 32. Takeuchi K, Noguchi T, Ueki H, Niihara KI, Sugiura T, Inukai S, Fujishige M (2015) Improvement in characteristics of natural rubber nanocomposite by surface modification of multi-walled carbon nanotubes [J Phys Chem Solids] Vol.80 P.84 google cross ref
  • 33. Kim SY, Baek SJ, Youn JR (2011) New hybrid method for simultaneous improvement of tensile and impact properties of carbon fiber reinforced composites [Carbon] Vol.49 P.5329 google cross ref
  • 34. Laoui T (2013) Mechanical and thermal properties of styrene butadiene rubber-functionalized carbon nanotubes nanocomposites [Fullerenes Nanotubes Carbon Nanostruct] Vol.21 P.89 google cross ref
  • 35. Lee SO, Rhee KY, Park SJ (2015) Influence of chemical surface treatment of basalt fibers on interlaminar shear strength and fracture toughness of epoxy-based composites [J Ind Eng Chem] Vol.32 P.153 google cross ref
  • 36. Jeong JM, Rhee KY, Park SJ (2015) Effect of chemical treatments on lithium recovery process of activated carbons [J Ind Eng Chem] Vol.27 P.329 google cross ref
  • 37. Lee SY, Kim BJ, Park SJ (2014) Influence of H2O2 treatment on electrochemical activity of mesoporous carbon-supported Pt?Ru catalysts [Energy] Vol.66 P.70 google cross ref
  • 38. Im JS, Kwon O, Kim YH, Park SJ, Lee YS (2008) The effect of embedded vanadium catalyst on activated electrospun CFs for hydrogen storage [Microporous Mesoporous Mater] Vol.115 P.514 google cross ref
  • 39. Jovanovi? V, Samar?ija-Jovanovi? S, Budinski-Simendi? J, Markovi? G, Marinovi?-Cincovi? M (2013) Composites based on carbon black reinforced NBR/EPDM rubber blends [Compos Part B: Eng] Vol.45 P.333 google cross ref
  • 40. Araby S, Meng Q, Zhang L, Zaman I, Majewski P, Ma J (2015) Elastomeric composites based on carbon nanomaterials [Nanotechnology] Vol.26 P.112001 google cross ref
  • 41. Griffini G, Suriano R, Turri S (2012) Correlating mechanical and electrical properties of filler-loaded polyurethane fluoroelastomers: the influence of carbon black [Polym Eng Sci] Vol.52 P.2543 google cross ref
  • 42. Korai Y, Wang YG, Yoon SH, Ishida S, Mochida I, Nakagawa Y, Matsumura Y (1997) Effects of carbon black addition on preparation of meso-carbon microbeads [Carbon] Vol.35 P.875 google cross ref
  • 43. Kanno K, Fernandez JJ, Fortin F, Korai Y, Mochida I (1997) Modifications to carbonization of mesophase pitch by addition of carbon blacks [Carbon] Vol.35 P.1627 google cross ref
  • 44. Park SJ, Cho KS, Ryu SK (2003) Filler?elastomer interactions: influence of oxygen plasma treatment on surface and mechanical properties of carbon black/rubber composites [Carbon] Vol.41 P.1437 google cross ref
  • 45. Park SJ, Kim JS (2001) Modifications produced by electrochemical treatments on carbon blacks: microstructures and mechanical interfacial properties [Carbon] Vol.39 P.2011 google cross ref
  • 46. Leblanc JL (2002) Rubber?filler interactions and rheological properties in filled compounds [Prog Polym Sci] Vol.27 P.627 google cross ref
  • 47. Ghosh AK, Maiti S, Adhikari B, Ray GS, Mustafi SK (1997) Effect of modified carbon black on the properties of natural rubber vulcanizate [J Appl Polym Sci] Vol.66 P.683 google cross ref
  • 48. Bandyopadhyay S, De PP, Tripathy DK, De SK (1996) Influence of surface oxidation of carbon black on its interaction with nitrile rubbers [Polymer] Vol.37 P.353 google cross ref
  • 49. Jiang HX, Ni QQ, Natsuki T (2011) Design and evaluation of the interface between carbon nanotubes and natural rubber [Polym Compos] Vol.32 P.236 google cross ref
  • 50. Serizawa H, Nakamura T, Ito M, Tanaka K, Nomura A (1983) Effects of oxidation of carbon black surface on the properties of carbon black?natural rubber systems [Polym J] Vol.15 P.201 google cross ref
  • 51. Ko KR, Ryu SK, Park SJ (2004) Effect of ozone treatment on Cr (VI) and Cu (II) adsorption behaviors of activated carbon fibers [Carbon] Vol.42 P.1864 google cross ref
  • 52. Park SJ, Jin SY (2005) Effect of ozone treatment on ammonia removal of activated carbons [J Colloid Interface Sci] Vol.286 P.417 google cross ref
  • 53. Jin FL, Park SJ (2015) Preparation and characterization of carbon fiberreinforced thermosetting composites: a review [Carbon Lett] Vol.16 P.67 google cross ref
  • 54. Kim S, Park SJ (2007) Effect of acid/base treatment to carbon blacks on preparation of carbon-supported platinum nanoclusters [Electrochim Acta] Vol.52 P.3013 google cross ref
  • 55. Fowkes FM (1962) Determination of interfacial tensions, contact angles, and dispersion forces in surfaces by assuming additivity of intermolecular interactions in surfaces [J Phys Chem] Vol.66 P.382 google cross ref
  • 56. Park SJ, Brendle M (1997) London dispersive component of the surface free energy and surface enthalpy [J Colloid Interface Sci] Vol.188 P.336 google cross ref
  • 57. Park SJ, Donnet JB (1998) Anodic surface treatment on carbon fibers: determination of acid-base interaction parameter between two unidentical solid surfaces in a composite system [J Colloid Interface Sci] Vol.206 P.29 google cross ref
  • 58. Kim S, Park SJ (2006) Effects of chemical treatment of carbon supports on electrochemical behaviors for platinum catalysts of fuel cells [J Power Sources] Vol.159 P.42 google cross ref
  • 59. Park SJ, Kim JS, Nah CW (2000) Filler-elastomer interactions. 1. Roles of modified carbon black surfaces to enhance mechanical properties of carbon black/rubber vulcanizates [Elastomers Compos] Vol.35 P.98 google
  • 60. Park SJ, Kim JS (2000) Filler-elastomer interactions. 2. Cure behaviors and mechanical interfacial properties of carbon black/rubber composites [Elastomers Compos] Vol.35 P.122 google
  • 61. Park SJ, Seo MK, Nah C (2005) Influence of surface characteristics of carbon blacks on cure and mechanical behaviors of rubber matrix compoundings [J Colloid Interface Sci] Vol.291 P.229 google cross ref
  • 62. Park SJ, Kang JY, Hong SK (2005) Effect of acid-base characteristics of carbon black surfaces on mechanical behaviors of EPDM matrix composites [Polymer (Korea)] Vol.29 P.151 google
  • 63. Park SJ, Kim JS, Lee JR, Shin CH, Nah CW (1999) Chemical surface treatment of carbon black to enhance interfacial adhesion between elastomer and carbon black [Elastomers Compos] Vol.34 P.222 google
  • 64. Kim KY, Rhyoo HY, Cho SJ, Yoon KE, Yang SI (2005) Oxidation and surface functional group analyses under ozone treatment of carbon black [Elastomers Compos] Vol.40 P.188 google
  • 65. Park SJ, Cho KS, Zaborski M, Slusarski L (2003) Filler-elastomer interactions. 10. Ozone treatment on interfacial adhesion of carbon Blacks/NBR compounds [Elastomers Compos] Vol.38 P.139 google
  • 66. Park SJ, Kim BJ (2005) Roles of acidic functional groups of carbon fiber surfaces in enhancing interfacial adhesion behavior [Mater Sci Eng: A] Vol.408 P.269 google cross ref
  • 67. Park SJ, Cho KS, Zaborski M, Slusarski L (2002) Filler-elastomer interactions. 6. Influence of oxygen plasma treatment on surface properties of carbon black [Elastomers Compos] Vol.37 P.99 google
  • 68. Poikelispaa M, Das A, Dierkes W, Vuorinen J (2013) Synergistic effect of plasma-modified halloysite nanotubes and carbon black in natural rubber―butadiene rubber blend [J Appl Polym Sci] Vol.127 P.4688 google cross ref
  • 69. Takada T, Nakahara M, Kumagai H, Sanada Y (1996) Surface modification and characterization of carbon black with oxygen plasma [Carbon] Vol.34 P.1087 google cross ref
  • 70. Park SJ, Kim JS, Choi KE (2001) Filler-elastomer interactions: 4. Effect of plasma treatment on surface properties of carbon blacks [Elastomers Compos] Vol.36 P.94 google
  • 71. Kim S, Cho MH, Lee JR, Park SJ (2006) Influence of plasma treatment of carbon blacks on electrochemical activity of Pt/carbon blacks catalysts for DMFCs [J Power Sources] Vol.159 P.46 google cross ref
  • 72. Kim DS, Dhand V, Rhee KY, Park SJ (2015) Surface treatment and modification of graphene using organosilane and its thermal stability [Arch Metall Mater] Vol.60 P.1387 google cross ref
  • 73. Lee SY, Park SJ (2010) Hydrogen adsorption of acid-treated multi-walled carbon nanotubes at low temperature [Bull Korean Chem Soc] Vol.31 P.1596 google cross ref
  • 74. Jin FL, Ma CJ, Park SJ (2011) Thermal and mechanical interfacial properties of epoxy composites based on functionalized carbon nanotubes [Mater Sci Eng: A] Vol.528 P.8517 google cross ref
  • 75. Park SJ, Jang YS (2002) Pore structure and surface properties of chemically modified activated carbons for adsorption mechanism and rate of Cr (VI) [J Colloid Interface Sci] Vol.249 P.458 google cross ref
  • 76. Park SJ, Kim KD (1999) Adsorption behaviors of CO2 and NH3 on chemically surface-treated activated carbons [J Colloid Interface Sci] Vol.212 P.186 google cross ref
  • 77. Park SJ, Kim MH (2000) Effect of acidic anode treatment on carbon fibers for increasing fiber-matrix adhesion and its relationship to interlaminar shear strength of composites [J Mater Sci] Vol.35 P.1901 google cross ref
  • 78. Yuan LY, Chen CS, Shyu SS, Lai JY (1992) Plasma surface treatment on carbon fibers. Part 1: Morphology and surface analysis of plasma etched fibers [Compos Sci Technol] Vol.45 P.1 google cross ref
  • 79. Tunnicliffe LB, Kadlcak J, Morris MD, Shi Y, Thomas AG, Busfield JJC (2014) Bus-field JJC. Flocculation and viscoelastic behaviour in carbon black-filled natural rubber [Macromol Mater Eng] Vol.299 P.1474 google cross ref
  • 80. Eatah AI, El-Nour KNA, Ghani AA, Hashem AA (1988) Dielectric and conduction properties of aged and unaged butyl rubber-carbon black mixtures [Polym Degrad Stab] Vol.22 P.91 google cross ref
  • 81. Abdel-Nour KN, Hanna FF, Abdel-Messieh SL (1992) Dielectric properties of some synthetic rubber mixtures: Part II. Butyl rubber-carbon black mixtures [Polym Degrad Stab] Vol.35 P.121 google cross ref
  • 82. Eatah AI, Ghani AA, Hashem AA (1989) Effect of concentration and temperature on the electrical conductivity in butyl rubber loaded with different types of carbon black [Polym Degrad Stab] Vol.23 P.9 google cross ref
  • 83. Gao S, Wang R, Fang B, Kang H, Mao L, Zhang L (2016) Preparation and properties of a novel bio-based and non-crystalline engineering elastomer with high low-temperature and oil resistance [J Appl Polym Sci] Vol.133 google cross ref
  • 84. Prukkaewkanjana K, Thanawan S, Amornsakchai T (2015) High performance hybrid reinforcement of nitrile rubber using short pineapple leaf fiber and carbon black [Polym Test] Vol.45 P.76 google cross ref
  • 85. Hoshikawa Y, An B, Kashihara S, Ishii T, Ando M, Fujisawa S, Hayakawa K, Hamatani S, Yamada H, Kyotani T (2016) Analysis of the interaction between rubber polymer and carbon black surfaces by efficient removal of physisorbed polymer from carbon-rubber composites [Carbon] Vol.99 P.148 google cross ref
  • 86. Nah CW, Rhee JM, Kim WD, Kaang, S, Chang YW, Park SJ (2001) Effects of chemical surface modification of carbon black on vulcanization and mechanical properties of styrene-butadiene rubber compound [Elastomers Compos] Vol.36 P.44 google
  • 87. Karasek L, Meissner B, Asai S, Sumita M (1996) Percolation concept: polymer-filler gel formation, electrical conductivity and dynamic electrical properties of carbon-black-filled rubbers [Polym J] Vol.28 P.121 google cross ref
  • 88. Kim YH, Wool RP (1983) A theory of healing at a polymer-polymer interface [Macromolecules] Vol.16 P.1115 google cross ref
  • 89. Dai SY, Ao GY, Kim MS (2007) Properties of carbon black/SBR rubber composites filled by surface modified carbon blacks [Carbon Lett] Vol.8 P.115 google cross ref
  • 90. Jia W, Chen X (1997) Effect of polymer-filler interactions on PTC behaviors of LDPE/EPDM blends filled with carbon blacks [J Appl Polym Sci] Vol.66 P.1885 google cross ref
  • 91. Oakey J, Marr DWM, Schwartz KB, Wartenberg M (1999) Influence of polyethylene and carbon black morphology on void formation in conductive composite materials: a SANS study [Macromolecules] Vol.32 P.5399 google cross ref
  • 92. Leopoldes J, Barres C, Leblanc JL, Georget P (2004) Influence of filler?rubber interactions on the viscoelastic properties of carbon-blackfilled rubber compounds [J Appl Polym Sci] Vol.91 P.577 google cross ref
  • 93. de Torre LEC, Bottani EJ, Martinez-Alonso A, Cuesta A, Garcia AB, Tascon JMD (1998) Effects of oxygen plasma treatment on the surface of graphitized carbon black [Carbon] Vol.36 P.277 google cross ref
  • 94. Pena JM, Allen NS, Edge M, Liauw CM, Hoon SR, Valange B, Cherry RI (2000) Analysis of radical content on carbon black pigments by electron spin resonance: influence of functionality, thermal treatment and adsorption of acidic and basic probes [Polym Degrad Stab] Vol.71 P.153 google cross ref
  • 95. Semaan ME, Nikiel L, Quarles CA (2001) Doppler broadening spectroscopy of carbon black and carbon black-filled rubbers [Carbon] Vol.39 P.1379 google cross ref
  • 96. Akovali G, Ulkem I (1999) Some performance characteristics of plasma surface modified carbon black in the (SBR) matrix [Polymer] Vol.40 P.7417 google cross ref
  • 97. Ayala JA, Hess WM, Joyce GA, Kistler FD (1993) Carbon-black-elastomer interaction II: effects of carbon black surface activity and loading [Rubber Chem Technol] Vol.66 P.772 google cross ref
  • 98. Ayala JA, Hess WM, Dotson AO, Joyce GA (1990) New studies on the surface properties of carbon blacks [Rubber Chem Technol] Vol.63 P.747 google cross ref
  • 99. Mathew T, Datta RN, Dierkes WK, Talma AG, van Ooij WJ, Noordermeer JWM (2011) Plasma polymerization surface modification of carbon black and its effect in elastomers [Macromol Mater Eng] Vol.296 P.42 google cross ref
  • 100. Hasirci N, Akovali G (1986) Polymer coating for hemoperfusion over activated charcoal [J Biomed Mater Res] Vol.20 P.963 google cross ref
  • 101. Ulkem I, Akovali G (1994) Mechanical properties of surface modified bauxite filled SBR vulcanizates―I [Eur Polym J] Vol.30 P.567 google cross ref
이미지 / 테이블
  • [ Fig. 1. ]  Chemical structures of various rubbers.
    Chemical structures of various rubbers.
  • [ Fig. 2. ]  Significant parts of carbon blacks.
    Significant parts of carbon blacks.
  • [ Fig. 3. ]  Classification of surface treatments.
    Classification of surface treatments.
  • [ ] 
  • [ ] 
  • [ ] 
  • [ Fig. 4. ]  Surface free energies and their components of the carbon blacks studied. VCB, virgin carbon black; ACB, acid-treated carbon black; BCB, base-treated carbon black; NCB, neutral-treated carbon black.
    Surface free energies and their components of the carbon blacks studied. VCB, virgin carbon black; ACB, acid-treated carbon black; BCB, base-treated carbon black; NCB, neutral-treated carbon black.
  • [ Fig. 5. ]  Surface free energy of the carbon blacks studied. OCB, Ozone-treated carbon black.
    Surface free energy of the carbon blacks studied. OCB, Ozone-treated carbon black.
  • [ Table 1. ]  Results of the O1S/C1S ratio of the carbon black treated by oxygen plasma studied
    Results of the O1S/C1S ratio of the carbon black treated by oxygen plasma studied
  • [ Table 2. ]  Surface tension components and parameters of the carbon blacks studied, measured at 20℃
    Surface tension components and parameters of the carbon blacks studied, measured at 20℃
  • [ Fig. 6. ]  (a) Hardness of carbon black/rubber vulcanizates. (b) Dependence of tensile strength on the London dispersive component of surface free energy of carbon black/rubber vulcanizates. VCB, virgin carbon black; ACB, acid-treated carbon black; BCB, base-treated carbon black; NCB, neutral-treated carbon black.
    (a) Hardness of carbon black/rubber vulcanizates. (b) Dependence of tensile strength on the London dispersive component of surface free energy of carbon black/rubber vulcanizates. VCB, virgin carbon black; ACB, acid-treated carbon black; BCB, base-treated carbon black; NCB, neutral-treated carbon black.
  • [ Fig. 7. ]  A model of tensile strength and tearing energy tests.
    A model of tensile strength and tearing energy tests.
  • [ Fig. 8. ]  GIIIC of the carbon black/NBR composites. GIIIC, tearing energy; OCB, Ozone-treated carbon black; NBR, acrylonitrile butadiene rubber
    GIIIC of the carbon black/NBR composites. GIIIC, tearing energy; OCB, Ozone-treated carbon black; NBR, acrylonitrile butadiene rubber
  • [ Fig. 9. ]  (a) GIIIC of the carbon black/rubber composites studied. (b) Dependence of GIIIC on the O1S/C1S ratio of the carbon blacks. GIIIC, tearing energy; CB, carbon black.
    (a) GIIIC of the carbon black/rubber composites studied. (b) Dependence of GIIIC on the O1S/C1S ratio of the carbon blacks. GIIIC, tearing energy; CB, carbon black.
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