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Production and characterization of thermoplastic elastomer foams based on the styrene–ethylene–butylene–styrene (SEBS) rubber and thermoplastic material

  • Ceren Kıroğlu EMAIL logo and Nilgün Kızılcan
Published/Copyright: September 13, 2021
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Open Chemistry
From the journal Open Chemistry Volume 19 Issue 1

Abstract

Thermoplastic elastomer foams based on styrene–ethylene–butylene–styrene (SEBS)/polypropylene (PP) were produced by using different processing techniques such as extrusion and injection molding to achieve optimized mechanical and thermal properties in terms of strength, elongation, and damping capability. Foaming is a method of introducing gas-filled cells into the material and it is considered an effective way to meet the requirements for higher impact resistance with low density and relatively low hardness. In this study, microspheres were used as a foaming agent and were introduced to the system by using an injection molding machine. They were used in different percentages and ranged from 1 and 3%. They decrease the density of the product thereby lowering the weight and cost. Besides improving damping abilities and decreasing the density, inorganic fillers such as talc, silica, and calcium carbonate were used to increase the mechanical strength, and their effectivity was also investigated. It was observed that a higher amount of foaming agent lowered the density by creating voids in the blend, as expected. The introduction of fillers increases the mechanical properties; however, the density had a negative effect even in the presence of foaming agents. About 3% density reduction can be achieved in the presence of talc and a foaming agent whereas the other fillers had an opposite effect on the density. Accordingly, the impact resistance was affected negatively because of the stiffness of the filler materials, and the highest Izod impact value was 50.2 kJ/m2. The elastic modulus values for foamed samples and filled with CaCO3, talc, and silica were 808, 681, and 552 MPa respectively. Combining foaming and thermoplastic elastomers (TPEs) offers a wide variety of possibilities to new and existing applications. In addition to low hardness and density, foaming provides better damping ability thanks to its morphological structure.

Keywords: TPEs; PP; SEBS; foaming technology; damping

1 Introduction

Thermoplastic elastomer (TPE) is a generic term used to describe a family of polymeric materials that can be processed as a thermoplastic but shows many characteristics normally associated with the traditional thermoset rubbers. They combine the properties of elastomers with the easy processability of thermoplastics [1,2]. As a member of the TPE family, styrene–ethylene–butylene–styrene (SEBS)/polypropylene (PP)/oil blends have been commercialized since the early 1990s for soft-touch applications, such as grips on tools, sports goods, and in automotive and medical domains owing to the fact that the properties of the rubber and the PP phase can be easily combined into a single product [3,4,5,6,7].

SEBS, which is a member of copolymers combining elastomeric properties, thanks to a double carbon bond C–C, has an excellent thermal resistance [8]. SEBS is generally blended with oils, fillers, or other types of polymers to obtain optimum mechanical and physical properties and better processability [9]. SEBS is generally used in combination with PP to obtain compounds of more strength and as a thermoplastic, PP also increases the processability [10].

It is known that there are valuable studies about the foaming of TPEs but reported studies are scarce. Foaming and the blend of SEBS/PP have been mostly investigated as two distinct research areas [11,12,13,14,15,16]. Considering the increasing importance and global usage of the thermoplastic elastomer family, density optimization as well as mechanical properties and processability have become more important recently and need more detailed investigations. Foaming is a highly efficient and preferred method for several purposes in the polymer world and foaming of TPEs is still a virgin area to be deep-dived in. Besides foaming and TPE engagement, microspheres are promising materials as foaming agents in terms of their easy usability, relatively reasonable costs, and efficiency as well. The present work aims to study TPE foams based on SEBS/PP with different fillers and different microsphere ratios as foaming agents to achieve optimized mechanical and physical properties in terms of density, strength, elongation, and also impact properties.

2 Experimental

2.1 Materials and instruments

Globalprene 7551 from LCY Company was used as a SEBS block copolymer in powder form. Borealis HE 125MO PP was used as polypropylene in a pellet form. As a foaming agent, Palmarole EXP 141/168-B from Adeka, which is a microsphere type was used. They can be used for foaming resins like PE, PP, PS, and TPE by injection molding and extrusion process. In order to achieve optimum efficiency, a working temperature in the range of 160–170°C is recommended. An additional level of 1.0–4.0% (depending on the desired degree of foaming) is recommended. Additionally, in order to obtain optimum mechanical and damping results, different types of fillers have been added to the extruder with different loading amounts.

In this study, an intermeshing co-rotating twin-screw extruder was used, which is PRISM TSE 24 HC with two K-Tron feeders, with a screw diameter of 24 mm and an L/D ratio of 28:1 (shaft length/screw diameter). An Arburg 370S 800–150 injection machine was used to produce specimens according to ISO standards. Tensile strength measurements were conducted according to the ISO 37 standard test method by using a Zwick Universal Tensile Test Machine Z020 with a load cell of 2.5 kN. Density measurements were conducted according to ISO 2781-2018. For each mechanical test, up to six replications were made and reported as average results. For the determination of morphological properties, a JSM 6400 JEOL scanning electron microscope was used in this study. All test specimens were covered with carbon and then analyzed. Different resolution and zoom values were chosen.

2.2 Production of SEBS/PP TPE specimens and addition of fillers

The powder form SEBS and 125MO PP pellets were used and blended in a twin-screw extruder. Sample plates were produced for primary tests and characterization was performed in an injection molding machine. Different PP/SEBS ratios in percentages of 70/30, 80/20, and 90/10 as well as neat PP (90/0) were prepared in a twin-screw extruder. Processing temperatures were around 200°C through the extrusion zones and 225°C at the die. As already known from the literature, the addition of fillers into plastomeric blends increases the processability, thermal stability, and mechanical strength [17]. For this purpose, talc, silica, and CaCO3 (calcium carbonate or calcite) were used in different amounts in a base elastomer formulation. The filler addition was settled as 10% of the total amount for all filler types. Fillers are introduced into the extrusion by using a side feeder and they were used in a powder form. The PP and SEBS were fed from main feeders simultaneously and blended with different fillers through the screw.

As a first step, before starting the extrusion process, both PP and SEBS were weighed in the required weight percentages. Also, all powder form filler materials were kept in the oven for 6 h at 60°C to dry them and then they were sent through the twin-screw extruder for mixing.

2.3 Preparation of foamed SEBS/PP samples

For this study, foaming is considered to be an effective way to meet the requirements of a high impact resistant material with low density and relatively low hardness. Foaming is a method of introducing gas-filled cells into the material. It decreases the density of the product by lowering the weight and the material cost. Combining foaming and thermoplastic elastomers offers a wide variety of possibilities to new and existing applications. In addition to low hardness and density, foaming provides better damping ability thanks to its morphological structure [1]. Several voids are formed during the foaming process, which will create damping areas in the polymeric matrix. The foaming agent from Adeka Palmorole EXP 141/168-B was used in different amounts ranging from 1 to 3%. It was introduced to the system by injection molding and dry mixed with the pelletized SEBS/PP/filler blend coming out from the extrusion step. The zone temperatures were around 220°C with an injection speed of 90 ccm/s and an injection pressure of 900 bar (Figure 1). The system temperatures for foaming are crucial as known from the previous research work about microsphere foaming. Riou et al. stated that the temperature dependency of foaming is clear. As expected, foaming efficiency is lower at lower temperatures and higher at an elevated temperature scale of 200–210°C according to Riou and coworker’s experiments. In fact, Riou stated that there is a lack of information for the true experimental temperature profile and also an approximation for the microsphere foaming dynamics [18].

Figure 1 Samples of test plates after foaming (randomly selected samples).
Figure 1

Samples of test plates after foaming (randomly selected samples).

3 Results and discussion

3.1 Density results

After the extrusion and injection molding process and foaming, samples were investigated in terms of their densities. As already known from the previous studies about density reduction in polymers via foaming technology, our results are highly compatible in terms of lower density with higher foaming amounts [19] (Table 1).

Table 1

Density values of samples containing talc, CaCO3, silica, and foaming agent of 1 and 3%

Density (g/cm3) 90-10 PP SEBS 80-20 PP SEBS 70-30 PP SEBS
Neat SEBS/PP blend 0.962 0.981 0.990
CaCO3 10% 1.058 1.079 1.089
CaCO3 + FA 1% 1.025 1.035 1.055
CaCO3 + FA 3% 0.953 0.952 0.980
Talc 10% 1.029 1.028 1.058
Talc + FA 1% 1.007 1.017 1.036
Talc + FA 3% 0.936 0.935 0.963
Silica 10% 1.049 1.069 1.079
Silica + FA 1% 1.016 1.026 1.045
Silica + FA 3% 0.945 0.944 0.971

The lowest density results were achieved by talc addition into the TPE matrix and foaming with a higher amount of foaming agent (3%). It was observed that increasing the elastomer amount yields higher density results in all specimens.

Comparing the neat SEBS/PP blend with only filler-added blends without foaming agents such as SEBS/PP/CaCO3 10%, SEBS/PP/talc 10%, and SEBS/PP/silica 10%, it was clearly seen that filler addition increases the overall density as expected. CaCO3 gave the highest density value whereas talc had the lowest density value.

3.2 Elastic modulus test results

The effects of the foaming and filler content on the elastic modulus (Young’s modulus), E, as a measure of blend and composite stiffness are shown in Figures 2–6.

Figure 2 Elastic modulus of neat and 10% talc-containing samples.
Figure 2

Elastic modulus of neat and 10% talc-containing samples.

Figure 3 The elastic modulus of neat and 10% CaCO3 containing samples.
Figure 3

The elastic modulus of neat and 10% CaCO3 containing samples.

Figure 4 Elastic modulus of neat and 10% silica-containing samples.
Figure 4

Elastic modulus of neat and 10% silica-containing samples.

Figure 5 Elastic modulus of neat and 10% filler containing samples.
Figure 5

Elastic modulus of neat and 10% filler containing samples.

Figure 6 Elastic modulus of neat, 10% filler containing samples, and foamed samples with 1 and 3% foaming agents.
Figure 6

Elastic modulus of neat, 10% filler containing samples, and foamed samples with 1 and 3% foaming agents.

It can be seen from Figure 2 that the talc introduction increases the elastic modulus, which shows a higher strength over less elongation. This type of tensile behavior of all blends is reasonable because incorporation of talc into the PP-SEBS matrix causes a ductile/brittle transition and causes a stiff construction thermoplastic. There is an introduction of filler having significantly much higher stiffness as mentioned in previous studies among thermoplastics [20].

Among TPE samples with PP and SEBS, the E value decreases with the increasing SEBS content. In ternary SEBS/PP/talc composites, the E value decreases with the addition of SEBS. It is known from the literature that the addition of even small amounts of SEBS decreases the E values considerably [20].

It can be seen from Figure 3 that the introduction of CaCO3 by 10% caused an increase in the elastic modulus, which shows higher strength over less elongation.

As shown in Figure 4, the introduction of silica gives a lower elastic modulus, which shows lower strength over an increased elongation. The expectation is a higher modulus of silica when introduced into SEBS/PP matrix but in practice, it is lower. Akbari and coworker’s study supports that this behavior is directly related to the morphology of the SEBS phase in each component and it can be assumed that the introduction of silica into the polymeric matrix and interaction with SEBS particles is low [21].

Considering the filler effect without the addition of any foaming agents (Figure 5), the highest E value was obtained with talc addition where the lowest value was obtained with the silica usage. Hence, silica and matrix introduction has not been achieved effectively.

From Figure 6. it can be observed that the introduction of the foaming agent into the matrix yields a lower modulus for all types of filler additions. More foaming agent gives lower elastic modulus, which is not a drastic decrease.

3.3 Yield strength results

According to the data of Ling and coworkers, incorporation of an elastomer into the PP matrix causes a decrease in the yield stress and flexural strength [22]. Similarly, the yield stress is also reduced by CaCO3, which is a result of poor interfacial adhesion between the matrix and filler. The results, as shown in Figures 7–9, supports this statement and an increased elastomer ratio gives lower yield strength compared to the neat SEBS/PP blend and the lower yield strength with the introduction of CaCO3 into the matrix as well. Comparing filler-added SEBS/PP blends, the yield strength was observed the highest with the addition of talc.

Figure 7 Yield strength of neat and 10% talc-containing samples.
Figure 7

Yield strength of neat and 10% talc-containing samples.

Figure 8 Yield strength of neat and 10% CaCO3 containing samples.
Figure 8

Yield strength of neat and 10% CaCO3 containing samples.

Figure 9 Yield strength of neat and 10% silica-containing samples.
Figure 9

Yield strength of neat and 10% silica-containing samples.

As mentioned in Akbari and coworkers’ study [23], incorporation of nanoclay into the plastic matrix resulted in a reduction in the yield stress of the samples since the introduction of nanoclay facilitates crazing in plastics (Figure 10).

Figure 10 Yield strength of neat, 10% filler containing samples, and foamed samples with 1 and 3% foaming agents.
Figure 10

Yield strength of neat, 10% filler containing samples, and foamed samples with 1 and 3% foaming agents.

3.4 Izod (notched) impact results

It is obvious from the results shown in Table 2 that an increase in the elastomer content causes improved impact resistance value as shown in the previous studies [21,24].

Table 2

Izod impact resistance of neat and 10% talc, CaCO3, and silica-containing samples

Izod impact resistance (kJ/m2) 90-10 PP SEBS 80-20 PP SEBS 70-30 PP SEBS
Neat 5.10 10.91 51.25
Talc 10% 4.89 9.90 48.51
CaCO3 10% 4.54 9.42 50.25
Silica 10% 4.33 8.14 23.64

When it is evaluated within each SEBS/PP composition, CaCO3 incorporation yields a slightly lower Izod impact value for each blend because these clays create a higher stiffness area in the TPE matrix.

The introduction of the foaming agent gives a higher Izod impact resistance value, thanks to the damping ability of the foamed cells. Hence, the foaming agent creates voids and these voids increase the impact damping. Optimum results in terms of mechanical strength and impact resistance were observed with the addition of talc and a 3% foaming agent ratio (Figure 11).

Figure 11 Izod impact resistance of neat, 10% filler-containing samples, and foamed samples with 1 and 3% foaming agents.
Figure 11

Izod impact resistance of neat, 10% filler-containing samples, and foamed samples with 1 and 3% foaming agents.

3.5 SEM morphology analysis

The SEM morphology analysis was conducted to investigate structural changes inside the sample body before and after the introduction of the foaming agent. The SEM images of samples are shown in Figure 12.

Figure 12 SEM images of foamed PP/SEBS samples containing inorganic filler: (a) 90% PP–10% SEBS–3% FA, (b) 70% PP–30% SEBS–3% FA, (c) 90% PP–10% SEBS–10% CaCO3–3% FA, (d) 80% PP–20% SEBS–10% CaCO3–3% FA, (e) 70% PP–30% SEBS–10% CaCO3–3% FA, (f) 90% PP–10% SEBS–10% talc–3% FA, (g) 80% PP–20% SEBS–10% talc–3% FA, and (h) 70% PP–30% SEBS–10% talc–3% FA.
Figure 12

SEM images of foamed PP/SEBS samples containing inorganic filler: (a) 90% PP–10% SEBS–3% FA, (b) 70% PP–30% SEBS–3% FA, (c) 90% PP–10% SEBS–10% CaCO3–3% FA, (d) 80% PP–20% SEBS–10% CaCO3–3% FA, (e) 70% PP–30% SEBS–10% CaCO3–3% FA, (f) 90% PP–10% SEBS–10% talc–3% FA, (g) 80% PP–20% SEBS–10% talc–3% FA, and (h) 70% PP–30% SEBS–10% talc–3% FA.

In terms of foamed cell distribution and size, the finest cells were obtained by using CaCO3 as a filler in the matrix that has a 70/30 SEBS/PP ratio. Smaller cell diameters and well distributed in the matrix were observed during morphological analysis. Without any foaming agent, foaming was also observed but cell diameters were very diverse. The talc addition had also promising foaming ability but closed bubbles were observed (Table 3).

Table 3

Cell diameters from SEM analysis for foamed samples

Sample Average cell diameter (μm)
90% PP–10% SEBS–3% FA 159.2
70% PP–30% SEBS–3% FA 150.8
90% PP–10% SEBS–10% CaCO3–% 3FA 109.9
80% PP–20% SEBS–10% CaCO3–3% FA 116.4
70% PP–30% SEBS–10% CaCO3–3% FA 88.1
90% PP–10% SEBS–10% talc–3% FA 135.7
80% PP–20% SEBS–10% talc–3% FA 119.4
70% PP–30% SEBS–10% talc–3% FA 212.8

4 Conclusion

Combining foaming and TPEs offers a wide variety of possibilities to new and existing applications. In addition to low hardness and density, foaming provides better damping ability thanks to its morphological structure. In this study, TPE foams based on SEBS/PP were produced by using different processing techniques such as extrusion and injection molding to achieve optimized mechanical and thermal properties in terms of strength, elongation, and damping capability. In order to increase the mechanical strength and optimize the cost, inorganic fillers were also added. Talc, CaCO3, and silica were used and their effectivity and synergistic effect with foaming agents were also examined. According to the mechanical test results and morphological studies, talc and CaCO3 were the best candidates for better foamed TPE samples in terms of low density, high mechanical strength, and impact resistance.

  1. Funding information: The authors received no external funding.

  2. Author contributions: All authors contributed to this work.

  3. Conflict of interest: The authors declare no conflict of interest, financial or otherwise.

  4. Ethical approval: The conducted research is not related to either human or animal use.

  5. Data availability statement: All data generated during this study are included in this published article.

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Received: 2021-01-25
Revised: 2021-06-23
Accepted: 2021-08-20
Published Online: 2021-09-13

© 2021 Ceren Kıroğlu and Nilgün Kızılcan, published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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  71. Overview of the major classes of new psychoactive substances, psychoactive effects, analytical determination and conformational analysis of selected illegal drugs
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  74. COVID-19 and SARS-CoV-2: Everything we know so far – A comprehensive review
  75. Challenge of diabetes mellitus and researchers’ contributions to its control
  76. Advances in the design and application of transition metal oxide-based supercapacitors
  77. Color and composition of beauty products formulated with lemongrass essential oil: Cosmetics formulation with lemongrass essential oil
  78. The structural chemistry of zinc(ii) and nickel(ii) dithiocarbamate complexes
  79. Bioprospecting for antituberculosis natural products – A review
  80. Recent progress in direct urea fuel cell
  81. Rapid Communications
  82. A comparative morphological study of titanium dioxide surface layer dental implants
  83. Changes in the antioxidative properties of honeys during their fermentation
  84. Erratum
  85. Erratum to “Corrosion study of copper in aqueous sulfuric acid solution in the presence of (2E,5E)-2,5-dibenzylidenecyclopentanone and (2E,5E)-bis[(4-dimethylamino)benzylidene]cyclopentanone: Experimental and theoretical study”
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  92. Selection of oil extraction process from Chlorella species of microalgae by using multi-criteria decision analysis technique for biodiesel production
  93. Special Issue on the 14th Joint Conference of Chemistry (14JCC)
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  95. CO2 gas separation using mixed matrix membranes based on polyethersulfone/MIL-100(Al)
  96. Effect of synthesis and activation methods on the character of CoMo/ultrastable Y-zeolite catalysts
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  99. Investigation of the spectroelectrochemical behavior of quercetin isolated from Zanthoxylum bungeanum
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  102. Special Issue on Applied Biochemistry and Biotechnology 2020
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  105. Quality evaluation of Cabernet Sauvignon wines in different vintages by 1H nuclear magnetic resonance-based metabolomics
  106. Special Issue on the Joint Science Congress of Materials and Polymers (ISCMP 2019)
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  109. Special Issue on the Conference of Energy, Fuels, Environment 2020
  110. Assessment of the mercury contamination of landfilled and recovered foundry waste – a case study
  111. Primary energy consumption in selected EU Countries compared to global trends
  112. Modified TDAE petroleum plasticiser
  113. Use of glycerol waste in lactic acid bacteria metabolism for the production of lactic acid: State of the art in Poland
  114. Topical Issue on Applications of Mathematics in Chemistry
  115. Theoretical study of energy, inertia and nullity of phenylene and anthracene
  116. Banhatti, revan and hyper-indices of silicon carbide Si2C3-III[n,m]
  117. Topical Issue on Agriculture
  118. Occurrence of mycotoxins in selected agricultural and commercial products available in eastern Poland
  119. Special Issue on Ethnobotanical, Phytochemical and Biological Investigation of Medicinal Plants
  120. Acute and repeated dose 60-day oral toxicity assessment of chemically characterized Berberis hispanica Boiss. and Reut in Wistar rats
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  122. Antiplasmodial potential of Eucalyptus obliqua leaf methanolic extract against Plasmodium vivax: An in vitro study
  123. Prunus padus L. bark as a functional promoting component in functional herbal infusions – cyclooxygenase-2 inhibitory, antioxidant, and antimicrobial effects
  124. Molecular and docking studies of tetramethoxy hydroxyflavone compound from Artemisia absinthium against carcinogens found in cigarette smoke
  125. Special Issue on the Joint Science Congress of Materials and Polymers (ISCMP 2020)
  126. Preparation of cypress (Cupressus sempervirens L.) essential oil loaded poly(lactic acid) nanofibers
  127. Influence of mica mineral on flame retardancy and mechanical properties of intumescent flame retardant polypropylene composites
  128. Production and characterization of thermoplastic elastomer foams based on the styrene–ethylene–butylene–styrene (SEBS) rubber and thermoplastic material
  129. Special Issue on Applied Chemistry in Agriculture and Food Science
  130. Impact of essential oils on the development of pathogens of the Fusarium genus and germination parameters of selected crops
  131. Yield, volume, quality, and reduction of biotic stress influenced by titanium application in oilseed rape, winter wheat, and maize cultivations
  132. Influence of potato variety on polyphenol profile composition and glycoalcaloid contents of potato juice
  133. Carryover effect of direct-fed microbial supplementation and early weaning on the growth performance and carcass characteristics of growing Najdi lambs
  134. Special Issue on Applied Biochemistry and Biotechnology (ABB 2021)
  135. The electrochemical redox mechanism and antioxidant activity of polyphenolic compounds based on inlaid multi-walled carbon nanotubes-modified graphite electrode
  136. Study of an adsorption method for trace mercury based on Bacillus subtilis
  137. Special Issue on The 1st Malaysia International Conference on Nanotechnology & Catalysis (MICNC2021)
  138. Mitigating membrane biofouling in biofuel cell system – A review
  139. Mechanical properties of polymeric biomaterials: Modified ePTFE using gamma irradiation
https://doi.org/10.1515/chem-2021-0084
Keywords for this article
TPEs; PP; SEBS; foaming technology; damping
Creative Commons
BY 4.0

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  117. Topical Issue on Agriculture
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