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NATURAL and APPLIED SCIENCES Published BYAENSI Publication http://www.aensiweb.com/ANAS
ISSN: 1995-0772 EISSN: 1998-1090 2016 December10(17):pages 143-154
Open Access Journal
Characterization and compare between two groups of hybrid nanocomposite materials prepared from ternary polymer blend 1Sihama
Issa Salih, 2Wleed Bdaiwi Salih, 2Mustafa Satam Mohammed
1Department 2Department
of Materials Engineering, University of Technology, Baghdad, Iraq. of Physics, College of Education for pure sciences, University of Anbar, Iraq.
Received 2 September 2016; Accepted 2 December 2016; Published 31 December 2016 Address For Correspondence: Sihama Issa Salih, Department of Materials Engineering, University of Technology, Baghdad, Iraq. E-mail:
[email protected] Copyright © 2016 by authors and American-Eurasian Network for ScientificInformation (AENSI Publication). This work is licensed under the Creative Commons Attribution International License (CC BY).http://creativecommons.org/licenses/by/4.0/
ABSTRACT
The polymer blend nanocomposites have emerged as new materials due to their new properties when compared to the neat polymers or their traditional composites. In the present work, prepare a set of ternary polymer blend as a first part, consisting of unsaturated polyester resin (UP) and poly methyl methacrylate (PMMA) and natural rubber material (NR), by hand lay-out technique. The binary polymer blend as basic material was prepared from (polyester (UP) 98% with 2% natural rubber (NR)), and the ternary polymer blend was prepared by adding (poly methyl methacrylate resin (PMMA) with chosen weights % (0, 5, 10 and, 15%) to the binary polymer blend. then is studied the effect of the selected weight ratios of (PMMA) in ternary polymer blend on tensile properties in addition to the study of infrared spectroscopy (FTIR). In second part: prepare two sets of nanocomposites materials which have basis of ternary polymer blend which is prepared from (93% UP+ 2% NR + 5% PMMA), by adding two type of nanoparticles (silica (SiO2) and zirconia (ZrO2)) in the individually form, with different ratio of the selection volume fractures (0, 0.5, 1,1.5%) according to the following formula: [(100-X) (93%UP+2%NR+5%PMMA): (X%SiO2 or X%ZrO2)]. The one group is composed of basis material reinforced by zirconia oxide nanoparticles (ZrO2) with average particle size (56.88nm), while the second group is composed of basis material reinforced by silica dioxide nano particles (SiO2) with average particle size (56.88nm). Then study the mechanical properties, as well as study infrared spectroscopy (FTIR) for the prepared nanocomposite materials. The results showed that the addition of nanoparticle of (silica or zirconia) to ternary polymer blend (93%UP: 2%NR: 5%PMMA) led to the improvement the tensile properties, compressive strength and hardness values of the prepared nanocomposites samples. It was conclusion that the addition of nano silica to ternary polymer blend gave the higher mechanical properties, so, these prepared samples promising in the field of structural applications
KEYWORDS: Unsaturated Polyester, PMMA ,Natural Rubber, zirconia and Silica nanoparticles,
Mechanical and thermos-physical
properties.
INTRODUCTION The polymeric blend materials is one of modern science, polymer blends is play an important role in extend the plastics application because of their capacity to produce new products with a wide range of properties benefit with minimal investment and became one of the fastest growing segments and development in polymers technology in commercial and structural applications [1].Major researches interests are focused on new polymeric materials obtained by blending two or more polymers [2]. The main feature of such a process is that the intermediate properties are in some statuses better than those presented by either of the single components. In addition, some modification in terms of processing characteristics, durability, corrosion resistance and plasticity and cost can be achieved via polymer blending [3]. it was processing at different ToCite ThisArticle: Sihama Issa Salih, Wleed Bdaiwi Salih, Mustafa Satam Mohammed., Characterization and compare between two groups of hybrid nanocomposite materials prepared from ternary polymer blend. Advances in Natural and Applied Sciences. 10(17);Pages: 143-154
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condition and at different weights fracture materials to get homogeneity and compatibility of the mixture in high specifications. Blending is an attractive method of creating new materials with improvement and flexibility in performance, and better properties than existing polymers [4]. A composite material is made by combining two or more materials to give a unique combination and superior properties that cannot be met by conventional monolithic materials. The reinforcement materials consist from many materials such as ceramic or metallic or polymeric which have generally characterized a high strength and more stiffness of the matrix material, while it's rubbery between high and low depending on the type of reinforcement material and end user purpose [5]. Nassier, prepared nanocomposites materials from unsaturated polyester reinforced with different weight percentages of carbon black (0, 3, 6, 9 and 12 %) nanoparticles using hand lay out. The results show that the tensile strength, modulus of elasticity, impact strength, fracture toughness, flexural strength and maximum shear stress was achieved at (3wt. %) of carbon black [6]. Effect of palm fiber deformation, by compression loads (2-6 MPa) on the mechanical properties as well as on the thermal and acoustic insulation properties of unsaturated polyester composites. It was concluded that the deformation the fibers improves the thermal and acoustic insulation properties of prepared composite, as well as an increase in the tensile strength and hardness values with increasing Compressive load on the palm fibers [7]. Sand reinforced polyester composites containing 10% to 60% sand with respect to the weight of unsaturated polyester resin have been prepared by compression molding. The results indicated that amount of reinforcing agent plays a vital role in the properties of Sand reinforced polyester composites [8]. Incorporation of multi-walled carbon nanotubes (MWCNTs) with unsaturated polyesters through oxidation reactions and chemical deposition, it was observed that the carbon nanotubes added in a polymer matrix leads to a significant increase in surface and volume electrical conductivity [9]. Nanocomposite materials based on two different types of polyester matrix (a commercial type and a laboratory produced one) with embedded barium titanate (BaTiO3) nano-particles were characterized. Mechanical strength appears to reduce with the increase of filler content. Commercial polyester’s composites exhibit brittle behavior, while laboratory polyester’s composites exhibit an elastomeric performance [10].Strengthen unsaturated polyesters with two sets of metallic powders (copper and aluminum), using hand lay out technique, the results showed increase in the tensile strength, modules of elasticity and the hardness values with increase the volume fraction of metal powder, and reach to maximum value at 15 % ratio for both types, whereas the flexural strength and flexural modulus showed high values at 10 % ratio for both type of composites [11].Polymer Matrix Composites were prepared, by blending vinyl ester resin with silane surface treated ZnO nanoparticles of various weight percentages. The results of the studies reveal that surface treated composites found to have more significant improvement in overall properties than the untreated one[12]. Nassier et al., prepare and characterize the mechanical properties of unsaturated polyester reinforced with nanoparticles Chinese clay, the results indicated that the bending and tensile strength of the unsaturated polyester decreased with increased Chinese clay content, while the compressive strength and hardness increased with increasing clay content in composite materials [13]. The goal of research is to characterization and comparison between two groups of nano hybrid composite materials prepared from matrix of ternary blend of the polymeric material (unsaturated polyester, poly methyl methacrylate and natural rubber) used for structural applications. 2-(Experimental part): The used materials in this research, consists of the unsaturated polyester (UP) is one of thermally hardened polymeric materials manufactured in (Bonyan Kala Chemie) Iranian origin, the polyester resin is liquids, clear, adhesive pinky color in room temperature mix with hardener; a transparent component (peroxide methyl ethyl keton (MEKP) through adding (2 gm) from hardness for each (100gm) from resin. Natural rubber (NR); is one of the flexible polymer that have the ability for expansion and contraction used as one of the polymer mixtures. Poly methyl methacrylate (PMMA) resin type )Castavaria) manufactured by ((Vertex -Dental Company)) consists of a fine powder, is one of the thermally plasticity polymeric materials. And reinforcement nanomaterials is ceramic powdery, composed of nano silica oxide (SiO2) Chinese origin (Nanjing Nano technology) company, with purity (% 99.5) average particles diameter ((24.59 nm) (figure (a 1)) and zirconia oxide nanoparticles (ZrO2) Chinese origin manufactured in (Hongwu Nanometer) company; purity (99%) Average diameter (56.88nm) form ((figure (b 1)). Atomic force microscope (AFM) is used to determine the average diameter of nanoparticle as mentioned above and distribution of nanoparticles.
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Fig. 1: Atomic force microscope (AFM) to determine the average diameter of nanoparticle and nanoparticles distribution. Where (a): is SiO2 nanoparticles and (b): is ZrO2 nanoparticles. 2-1 preparations of samples: polymer blend samples prepared from the unsaturated polyester and natural rubber in fixed weight ratio as a basis sample (98% UP + 2% NR) then was added (poly methyl methacrylate (PMMA)) in chosen weights ratio (0, 5, 10 and 15% wt.) to the binary polymer blend according to the following formula: ((100-X)% UP: X% PMMA + 2% NR), and nano-composite material were prepared from ternary polymer blend as a matrix material (93% UP + 2% NR + 5% PMMA), reinforced with two different reinforcement materials which is silica (SiO2) nanoparticles and zirconia (ZrO2) nanoparticles, incorporated in the individually form, according to the following formula:[(100-X) (93%UP+2%NR+5%PMMA): (X%SiO2 or X%ZrO2)]. All the prepared mixtures were done at room temperature. Then the liquid mixture was poured into the mold continuously and regularly to fill the mold to the desired level. Leave the sample within the mold to cure for 24h at room temperature (27°C). to complete processing the samples are placed in drying oven for two hours at temperature (50 °C) according to the manufacturer instructions, this process is important to complete the polymerization and to remove the stresses generated by the manufacturing process. 2-2 Mechanical and physical tests: Test of (Fourier transformation Infrared spectrum FTIR) is used to obtain specific information about the chemical bonds and molecular structure. Chemical bonds vibrated in special frequencies, and when exposed to infrared radiation, it will absorb radiation at frequencies that are compatible with their vibrations line. The (FTIR) test completed according to the international measurements (ASTM E-1252) [14], by using a spectrometer of the (Fourier infrared)) manufactured by (Bruker optier company) type (TENSOR-27). Infrared spectrum was used within range of (400- 4000) cm-1. For the purpose of tensile test prepared specimens cut in standard dimensions according to international standards (ASTMD638-03) to test the tensile [15], using the tensile testing device type (LARYEE Yaur Tasting Solutions). With using tracer diagram of the device, it was obtained directly results in the form of a curved (stress - strain) which was calculated tensile properties (tensile strength and tensile modulus elasticity and ductility). The test was conducted at a constant speed load (5 mm / min), and at a laboratory temperature. The tensile stress was applied on the test sample until obtain the fails. The compressive strength is calculated by applied the compression load on standard dimensions samples according to the American specification (ASTMD-695) [16]. The test was conducted at a constant speed load (5 mm / min), and at a laboratory temperature. Three samples were tested for each mixing ratio, of the tests mentioned above and the final results recorded represent the average rate for the three tested samples. The hardness measurement by (Shore D) at a laboratory temperature ,this method suitable for the thermoplastic polymeric material, as well as thermosets polymeric materials according to international standards (ASTMD2240) [17], it has been taking a hardness in five different locations for each sample and the recorded results represents the average rate of five
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readings. Morphology test, analytical Scanning Electron Microscope (SEM), model (Tescan VEGA-SB) made in Belgium is used to examine the morphology of polymer blends composites. RESUITS AND DISCUSSION 3-1 Fourier transforms infrared spectroscopy (FTIR): In order to fully characteristic band of tri-polymer blend (93%UP+2%NR+5%PMMA) composite specimens. Fourier transforms infrared spectroscopy (FTIR) was used. Figure (2) illustrated the infrared spectrum of unsaturated polyester. The presence of symmetric (C=O) stretching was confirmed by the presence of strong bend at (1721.04) cm-1, this band confirms the presence of (C=O) ester group and also confirms the formation of unsaturated polyester [18]. Two aromatic, ring breathing bands a doublet at (1600. 7) cm-1 and an addition medium absorption bend peak at (1449.26) cm-1 can be attributed to (C―H) bending .Spectrum absorption bend at 1156.83cm-1 confirms the presence of (C―O―C) of ester linkage [19]. Unsaturated in plane deformation at (1071.45) cm-1, a strong absorption band at (741.93)cm-1 and (700.22)cm-1 attributed to (C―H) out of plane bending deformation in benzene ring [19].
Fig. 2: FTIR spectrum for neat unsaturated polyester material The infrared spectrum of binary polymer blend (98%UP+2%NR) and the infrared spectrum of tri-polymer blend ((100-X)%UP: X% PMMA)+2%NR) are shown in Figure (3). From this figure it was observed that, all the characteristics vibration bands of unsaturated polyester (figure 2) are presented in (FTIR) spectrum of binary and ternary polymer blend. Moreover, from this figure it was found that the main characteristic vibration bands of PMMA appear at (1720.14) cm-1 (C = O) and (1450.85 and 1476.30) cm-1 (C– O). The bands at (2923.33) cm-1 correspond to the (C–H) stretching of the methyl group (CH3) and the bands at (1376.30 and 1450.84) cm-1 are associated with (C–H) symmetric and asymmetric stretching modes, respectively. The (1256.77) cm-1 band is assigned to torsion of the methylene group (CH2), while (C–C) stretching band are at (977.18 and 843.81) cm-1 [20], as well as no other new peak or peak shifts were observed for the binary and ternary polymer blend.
Fig. 3: FTIR spectrum for binary polymer blend (UP+NR) and ternary polymer blend ((100-x) % UP+2%NR+x%PMMA) as a function of PMMA in the polymeric blend The FTIR spectra of first group polymer blend nano composites specimens, reinforced with different ratio of SiO2 nanoparticles (0, 0.5, 1 and 1.5%) are shown in Figure (4). From this figure it was observed that, all the
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characteristics vibration bands of unsaturated polyester (figure 2) and of ternary polymer blend (93%UP+2%NR+5%PMMA) (figure 3) are presented in (FTIR) spectra of ternary polymer blend nano composite samples. The presence of SiO2 particle in tri-polymer blend nano composites caused the weakening and finally the disappearance of the bands attributed to (O–Si–O) bands in (SiO2). Except the peak appear at (449.9) cm-1 attributed to (Si–O) bands in (SiO2) [21]. On the other hand, it can be seen from the infrared spectrum of the first group composite specimens (figure (4)), no other new peak or peak shifts were observed for the tri-polymer blend (93%UP+2%NR+5%PMMA) composite specimens with the addition (SiO 2) nanoparticles, this is due to find physical bond and absence any cross linking in these specimens. There is a clear increase in peaks intensity for all of characteristic peak with increasing (SiO 2) ratio and it reaches a maximum at (1% SiO2) and then peaks intensity decrease when (SiO2) ratio reaches to 1.5% in content of polymer blend nano composite.
Fig. 4: FTIR spectrum for ternary polymer blend nano composites as a function of SiO2 content in composite samples The infrared spectrum of tri-polymer blend (93%UP+2%NR+5%PMMA) was reinforced with different ratio of (ZrO2) nanoparticles (0, 0.5, 1 and 1.5%) as the second group composite materials are shown in Figure (5). All the characteristics vibration bands of unsaturated polyester (figure 2) and of ternary polymer blend (93%UP+2%NR+5%PMMA) (figure 3) are presented in infrared spectrum of second group nano composites specimens, The presence of ZrO2 particle in tri-polymer blend nano composites caused the weakening and finally the disappearance of the bands attributed to (O–Zr–O) bands in (ZrO2). Except the weak peak appear at (494.44) cm-1 region is due to the Zr–O vibration, which confirm the formation of ZrO2 structure [22]. No new peaks or peak shifts were observed for the second group composites specimens, this is due to find physical bond and absence any cross linking in these specimens, except the sample reinforced with 1.5% ratio of (ZrO2) nanoparticle, which shows the disappearance or decay peaks own to unsaturated polyester material, and that may be related with (ZrO2) nanoparticles agglomerated, which are accumulation of isolated particles which are connected to each other and with constituents of composite material by attractive physical interactions forces, and this, may be done in a adversely effect on radiation absorption, and that may be caused in reflected the infrared radiation rather than absorbed by the components of material. There is a clear increasing in peak intensity for all the characteristic peaks with increasing (ZrO 2) ratio and it reaches a maximum at (1% ZrO2) and then highly decreases with increase in (ZrO2) content in tri-polymer blend composites specimens.
Fig. 5: FTIR spectrum for ternary polymer blend nanocomposites as a function of ZrO 2 nanoparticles content in composite samples
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Mechanical Test Result: Tensile Test Results: Figure (6) and (7 a and b) illustrates the behavior of the (stress- emotion) curves for (binary polymer blend samples ((98% UP + 2% NR) and ternary polymer blend samples [(100-X)% UP: X% PMMA +2% NR)] as a function of PMMA content in the blend), and for the first and second groups of ternary polymer blend nano composites as function of nanoparticle (ZrO2 or SiO2) in composites respectively. It’s notes from these figures that the (stress – strain) curves, It consists of elastic deformation zone represented by linear relationship between stress and strain in elastic region, from this region, it can be calculated the elasticity modulus. Polymeric material it is suffer within the boundaries of this region, from flexible deformation caused by tension and elongation of polymeric chains without get any broken in these bonds. Then this curve deviates from linear behavior is a result of generate a micro-cracks within the polymeric material, these cracks grow and accumulate with increasing stress, and then formation a larger cracks, which continues to growth with applied stress, until to get the fracture in the sample [4]. The strong linkage between the polymer blend components and between the polymeric chains, it will not be allowed to formation of internal defects (cracks) rapidly, and these in turn reduces the molecules motion, and thus lead to reduce the elongation and sliding polymeric chains during tensile load. In other cases, the crack starts at the outer surfaces of the distortions zone or defects locations, such as for scratches or internal cracks that act as zones of stresses concentration and that lead to the high values of the stresses, which exceed the internal bond limits and that lead to fracture occur [2 and 4]. 45 40
Stress (MPa)
35 30 25 20 UP+NR UP+NR+ 5%PMMA UP+NR+10%PMMA UP+NR+15%PMMA
15 10 5 0 0
2
4 Strain(%)
6
8
Fig. 6: (stress – strain) curves for binary polymer blend (UP+NR) and ternary polymer blend ((100-x) % UP+2%NR+x%PMMA) as a function of PMMA in the blend 50 45 35 30
Stress (MPa)
Stress(MPa)
40
25 20
Blend Blend +ZrO2 0.5% Blend +ZrO2 1% Blend +ZrO2 1.5%
15 10 5 0
a
0
2
4 Strain(%)
6
50 45 40 35 30 25 20 15 10 5 0
8
b
Blend Blend+SiO2 0.5% Blend+SiO2 1% Blend+SiO2 1.5% 0
2
4
6
8
Strain(%) Fig. 7: (stress - strain) curves for ternary polymer blend nano-composites as a function of (ZrO2 or SiO2) nanoparticles content in the composite, where (a):ZrO2 nano- composites and (b): SiO2 nano-composites Figures )8a) and (8b) shows the effect of added (PMMA) on the properties of tensile strength and elasticity modulus of ternary polymer blend, from these figures, it is clearly shows that the tensile strength and elasticity modulus which is increases with the increasing the weight ratio of PMMA material in the blend, this is due to
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50
Modulus Of Elasticty (GPa)
Tensile Strength (MPa)
the homogenized distribution of PMMA inside the ternary polymer blend which will work to increase the entanglement of the chains for the polymer blend materials, as well as the good interaction reaction and good compatibility between all components of the ternary polymer blend, all of this led to an increase of tensile properties of prepared ternary polymer blend materials [11]. Figure (9) shows the relationship between the weighted ratio (PMMA) resin and ductility of the ternary polymer blend samples, where its notes that the ductility values increase with increasing (PMMA) material in the blend. The tensile test results show that the addition of (PMMA) material to unsaturated polyester blend change the (stress- emotion) curves behavior of prepared polymer blend material from (hard) behavior to the (strong and tough) behavior. 45 40 35 30 25 20
a
0
5 10 15 Weight Fraction(%)
20
10 8 6 4 2 0
b
0
5
10 15 Weight Fraction(%)
20
(b): modulus of elasticity
Elongation at break(%)
(a): Tensile strength
12
c
9 8 7 6 5 4 3 2 1 0 0
5
10 15 Weight Fraction(%)
20
(c): percentage of elongation at break Fig. 8: (a): Tensile stress and (b): Modulus of elasticity and (c): Percentage of elongation at break, for ternary polymer blend ((98 - x) % UP+2%NR+x%PMMA) as a function of PMMA in the blend Based on the tensile properties of ternary polymer blend of prepared samples, it has been selected the sample which have 5% ratio of PMMA as optimal sample from among these blend samples. Accordingly, this sample was considered as a basis for the preparation of nano-composite samples. Figure (10 a) represents the relationship between the volume fraction for the reinforcement material and tensile strength of the composite specimens, the tensile strength little decreased with increasing volume fraction of nanoparticles in composite. and that may be related to the nanoparticles agglomerated, which are accumulation of isolated particles which are connected to each other by attractive physical interactions forces, and that may be lead to bad connected with constituents of composite material and this may be cause in a adversely effect on tensile properties of composite materials[11]. It was also observed that the tensile strength of the composite samples reinforced by silica nanoparticles is little higher than the tensile strength values of the composite sample reinforced by zirconia nanoparticles, due to the nature of characteristics silica nanoparticles compared with the zirconia nanoparticles, beside to strong correlation between silica nanoparticles and basis material [6] Figure (9b) represents the relationship between the volume fraction of the reinforcement materials with tensile elasticity of the nano-composite samples, the values of the elastic modulus of the composite samples which reinforced by silica nanoparticles it is little increase with increases of silica nanoparticles content in composite samples, While the opposite happens when composite reinforced with zirconia nanoparticle, the elastic modulus decrease with increases of silica nanoparticles content in composite samples. the addition of (silica or zirconia) nanoparticles in composite material, it was found that, each of these nanoparticles have a based role in their effect on the elasticity modulus, depends on the nature of penetration these nanoparticles inside composite components, since the compatibility between nanoparticle and composite components, plays an important role by restrict the increase slipping inside the polymeric composite and between polymeric
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a
48
ZrO2
45
SiO2
14
33
Modulus Of Elasticty (GPa)
Tensile Strength (MPa)
chains, the heterogeneous distribution of reinforcement nanoparticles inside the matrix of polymer composite materials, will work to limit the movement of polymeric chains of the polymer blend nano-composite materials All of this leads to an increase or decrease in the tensile elastic of the prepared polymer blend nanocomposite material [6 and12] Figure (9c) represents the relationship between the volume fractions of (silica or zirconia) reinforcement nanoparticle material with percentage of elongation at break of the polymer blend nano composite samples. From this figure it was found that, the percentage of elongation at break values for polymer blend nanocomposite samples decreases with addition (silica or zirconia) nanoparticles to the ternary polymeric blend and ductility values of nanocomposite samples reinforced silica nanoparticles is higher compared with ductility values of their counterparts of the other group samples reinforced with zirconia nanoparticles, And this related to the nature of reinforcement particles, the surface nature and the shapes of the nanoparticle. which it makes it easy to wetting by the basis material (ternary polymer blend), thereby increasing the contact area between the components of prepared composite materials and then increase the bonding strength between them then increase the viability of external stresses, or reduce the vulnerability of wetting by the basis material and to increase the creation of defects and aerobic spaces and thus reduce bearing composite materials outer loads [11, 13]
30
0
12 10
42
8
39
6
36
0
1 Volume Fraction (%)
2
b
(a): tensile strength
4
ZrO2
2
SiO2 0
1 Volume Fraction (%)
2
(b): modulus of elasticity
Elongation at break %
10 9 8 7 6 5 4 3 2 1 0
ZrO2 SiO2
1 1.5 2 Volume Fraction % (c): Percentage of elongation at break Fig. 9: (a): Tensile stress and (b): Modulus of elasticity and (c): Percentage of elongation at break, for ternary polymer blend nano-composite samples as a function of (silica or zirconia) nanoparticles content in composites
c
0
0.5
Compression Test Results: Figure (10) represents the relationship between the volume fraction for reinforcement nanoparticle materials and compressive strength of the prepared samples, it was observed from this figure that, the compressive strength increased with addition of (silica or zirconia) nanoparticles to ternary polymer blend samples, and that may be related to the nature of the penetration of nanoparticles inside interfaces spaces in the polymer chains, which will further reduce the free spaces inside the composite materials, thus increasing the compressive strength [6- 7]. As well as it was noticed that the compressive strength reach to maximum values at 0.5% ratio of the volume fraction of (silica or zirconia) nanoparticles content in composites. Moreover the values of compressive strength for ternary polymer blend samples reinforced with zirconia nanoparticles have higher values of the compressive strength as compared with their counterparts of ternary polymer blend samples reinforced with silica nanoparticles, and this result may be relative to the increase in the viscosity of the
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polymer blend matrix, which caused difficulty of reinforcement material in penetration inside the viscous basis material and this it will be cause in reduced wettability before hardening of the basis material, and that causing weakness in the adhesion between the constituents of base material and reinforcement material [4 and 6].
Compression Strength (MPa)
100 95 90 85 80
ZrO2
75
SiO2
70 65 60 0
0.5
1 1.5 2 Volume Fraction (%) Fig. 10: compressive strength for ternary polymer blend nano-composite samples as a function of (silica or zirconia) nanoparticles content in composites Hardness Test Results: Figure (11) represents the relationship between the hardness values of ternary polymer blend nanocomposite samples and the volume fraction of nanoparticle reinforcement material content in composite samples, From this figure it was observed that, the hardness values increase with increasing of volume fracture of nanoparticle content in composite materials, and this related to the nature of the reinforcement nanoparticles, and good distribution of these nanoparticle between polymer chains, as well as within the constituents of nanocomposite materials, and this lead to make the composite samples possess the high hardness, if the nanoparticles was tend to form hard agglomerates inside polymer blend matrix [6]. On the other hand the ternary polymer blend samples reinforced with silica nanoparticles its hardness slightly higher values as compared with their counterparts of ternary polymer blend samples reinforced with zirconia nanoparticles, and this goes back to the low viscosity which gained by the polymer blend material when increased volume fraction of silica dioxide nanoparticles inside polymer blend matrix materials in the liquid state, causing ease of penetration of reinforced material into the interfaces spaces and pores interfaces within the composite substances, resulting in a reduction of gaps inside the prepared material, in addition to owning nanoparticles silica was tended to form hard agglomerates inside polymer blend matrix as compared with the nanoparticles zirconia [6 and 11].
Hardness (Shore-D)
90 85 80 75 70 ZrO2
65
SiO2
60 0
0.5
1 1.5 2 Volume Fraction (%) Fig. 11: Shore hardness of ternary polymer blend nano-composite samples as a function of (silica or zirconia) nanoparticles content in composites 3.3 Morphology of Fracture Surface: The fracture surfaces of the tensile specimens were examined using a scanning electron microscope (SEM). The morphology of polymer blends depends on the nature of components, constituents’ ratios, component melt viscosities, and processing conditions.
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The fracture surface of the modified polymer blend (polyester resin+2%NR +%5PMMA) at magnification (3000x) it was shown in Figure (12). This figure showed the smooth surface of the polymer blend matrix with good dispersed rubber particle in the polymer blend matrix, clearly showed two distinct phases, a continuous polymer blend matrix and dispersed rubber phase. Rubber particles present will act as energy dissipating center in the polyester resin matrix. From the micrographs, deformation lines were observed to propagate through rubber particles and it proved the ductile fracture did occurred. Similar observations were found by LEE YIP SENG et al. [23]. Heterogeneous morphology surfaces resulted on the fracture surfaces. The holes observed in the micrograph indicate that the rubber particles dispersed in the polyester resin of polymer blend. The cavitation show that the addition of liquid rubber acts as the toughening agent to the polyester resin of polymer blend [24].
Fig. 12: SEM micrographs of polymer blend (polyester resin+2%NR +%5PMMA), at the magnification of 3000x The SEM micrograph of the fractured surface at the magnification of 3000x for (polyester resin+2%NR +%5PMMA) polymer blend reinforced in individually form with 1 and 1.5% volume fraction of (silica and zirconia) nanoparticles was shown in Figure (13a, b, c and d) respectively. The SEM micrographs of the fracture surface for these nano-composites showed different morphology depends on the type and volume fracture of nanoparticles in composite materials, moreover these image showed some characteristics of discontinuous phase structure or so called phase inversion which contributes to the composite toughening [25]. As well as, morphology of connected globules was clearly observed when add 1% of volume fraction of zirconia nanoparticle to polymer blend as its shows in Figure (13 C). Whereas add 1.5% volume fraction of zirconia nanoparticle lead to segregations and agglomeration of these nanoparticle in the some regions of polymer blend composite as shown in Figure (13 d). And this is Causing the deterioration of the mechanical properties of the prepared composite samples.
Fig. 13: SEM micrographs of hybrid nano-composite as a function of nanoparticles content in composite, where (a): polymer blend reinforced with 1%V.F.of nano- silica, (b): polymer blend reinforced with 1.5%V.F.of nano- silica, (c): polymer blend reinforced with 1%V.F.of nano- zirconia, (d): ): polymer blend reinforced with 1.5%V.F.of nano- zirconia, at the magnification of 3000x
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Conclusions: In the present work, has been study. the effect of addition poly methyl methacrylate on the tensile properties of the unsaturated polyester modified resin (UP: 2%NR) It was found that, the sample which have 5% PMMA ratio, has the optimum tensile properties from among of ternary blend samples. Accordingly, this sample was considered as a basis for the preparation of nano-composite samples. So, two different types of nanoparticles which are silica (SiO2) and zirconia (ZrO2), add individually, to the ternary polymer blend, to prepare nano composites materials, and it was concluded the following item: - The addition of (silica and zirconia) nanoparticle to ternary polymer blend (93%UP: 2%NR: 5%PMMA), led to the improvement in tensile properties, compressive strength and hardness values. As well as, it is concluded from the (FTIR) spectra, that all the characteristics of vibration bonds of unsaturated polyester resin, were appeared in infrared spectrum of ternary polymer blend and for polymer blend nano-composites samples, except the sample reinforced with 1.5% ratio of zirconia nanoparticle, which shows the disappearance or decay peaks own to unsaturated polyester material, The SEM provide physical evidence of improved energy absorption during the fracture process for all the prepared samples, except the nano composite sample reinforced with 1.5% ratio of zirconia nanoparticle, which the appeared of segregations and agglomeration of zirconia nanoparticle in polymer blend matrix, and this cause the deterioration of the mechanical properties of the prepared composite. So, this requires treatment the nanoparticles powders and special for nano zirconia in order to be the prepared samples promising in the field of structural applications Future works: Study the effect of surface chemical treatment of nanoparticle on mechanical properties of the prepared nano composites, as well as study the effect of addition the Kevlar fibers and glass fibers on the mechanical properties of the prepared hybrid nano composites. Moreover study the influence of coupling agents for the nanoparticles powders and fibers on the mechanical characteristics of polymer blend hybrid nano composite to use in structural applications ACKNOWLEDGMENT We would like to express our thanks to All employees of the University of Technology And private Head and professors the Department of Materials Engineering for helping us in carrying out this research, As well as, we would like to say thanks for all the laboratories staff of the Materials Engineering Department for their continuous efforts, help and in carrying out us experimental tests, And also extend my thanks to the Presidency and professors of the Department of Physics Faculty of Education Sciences Pure Anbar University, all of what they gave me many facilities. REFERNCES 1. 2. 3. 4.
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