Comparative Study on Improvement in Mechanical and Flame Retarding Properties of Epoxy-CaCO3 Nano and Commercial Composites

ABSTRACT

Commercial and nano calcium carbonate (CaCO₃) filled epoxy composites were processed at 2 to 10 wt% compositions. Nano size CaCO₃ was synthesized using in-situ deposition technique. Its nanosize and mixing with epoxy were confirmed by X-ray diffraction (XRD) method. X-ray diffractograms show that complete exfoliation occurs in the case of nanosize particles while micron size particles do not exfoliate. The effect of nanosize and commercial CaCO₃ was studied on mechanical and flame retarding properties. The impact strength of composite increased up to 6 wt% loading of nano filler and further decreased. Young's modulus was observed at 1400 Mpa and 1100 Mpa for nano and commercial CaCO₃, respectively at their 10 wt% loading, while pure epoxy showed 1000 Mpa; likewise, flame retarding properties improved six to four times on loading of nano and commercial CaCO₃, respectively in comparison to pure epoxy resin. The improvement is due to exfoliation of nano in epoxy matrix, which is observed by X-ray diffractograms.     

Mechanical and flame‐retarding properties of styrene–butadiene rubber filled with nano‐CaCO3 as a filler and linseed oil as an extender

A nanosize CaCO₃ filler was synthesized by an in situ deposition technique, and its size was confirmed by X‐ray diffraction. CaCO₃ was prepared in three different sizes (21, 15, and 9 nm). Styrene–butadiene rubber (SBR) was filled with 2–10 wt % nano‐CaCO₃ with 2% linseed oil as an extender. Nano‐CaCO₃–SBR rubber composites were compounded on a two‐roll mill and molded on a compression‐molding machine. Properties such as the specific gravity, swelling index, hardness, tensile strength, abrasion resistance, modulus at 300% elongation, flame retardancy, and elongation at break were measured. Because of the reduction in the nanosize of CaCO₃, drastic improvements in the mechanical properties were found. The size of 9 nm showed the highest increase in the tensile strength (3.89 MPa) in comparison with commercial CaCO₃ and the two other sizes of nano‐CaCO₃ up to an 8 wt % loading in SBR. The elongation at break also increased up to 824% for the 9‐nm size in comparison with commercial CaCO₃ and the two other sizes of nano‐CaCO₃. Also, these results were compared with nano‐CaCO₃‐filled SBR without linseed oil as an extender. The modulus at 300% elongation, hardness, specific gravity, and flame‐retarding properties increased with a reduction in the nanosize with linseed oil as an extender, which helped with the uniform dispersion of nano‐CaCO₃ in the rubber matrix. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2563–2571, 2005     

Effect of Sizes of Nano Ca3(PO4)2 on Mechanical and Thermal Properties of Polyurethane Foam Composites

Particular sizes of nano inorganic filler, Ca₃(PO₄)₂ were prepared by following the matrix mediated growth technique. Composite foams were prepared on addition of different concentration (0.5–2.5 wt.%) of nano size filler in a single–phase polyurethane matrix. The differential Scanning Calorimetry (DSC) for composite as well as pure polyurethane was done to ascertain the degree of interaction of filler with the structure of the matrix as active sites. The degree of cell formation increases on increase in amount of reduced size nano filler in the composites where as decrease in case of larger size filler in composites. The increment in specific gravity from 0.17–0.25 for reduced nano size filler and 0.17–0.18 in case of larger size filler makes a strong support for the increment of cell numbers. The significant enhancement 250% in compressive strength, and the reduction of cell sizes shown in optical photographs satisfies the reasons of increment in heat of fusion (ΔH) in DSC. The decrement in (ΔH) cal/g in case of larger size filler for curing shows the conduction of heat is more due formation of cells less in numbers results in reduction of rate of heating more. Thermal gravimetric analysis (TGA) was done to know the degradation behavior. The TGA results, shows increment in onset temperature and mid temperature of the first step degradation in case of larger size nano filler. Decrement of flammability from 0.47–13.14 sec/mm for reduced nano size filler and 0.47–8.23 sec/mm in case of larger size filler, show that the incorporation of nano particles not only improves the mechanical properties but also retards the flammability.     

THE COMPARISON PROPERTIES OF RECYCLE RUBBER POWDER,CARBON BLACK,AND CALCIUM CARBONATE FILLED NATURAL RUBBER COMPOUNDS

The effects of filler loading on the curing characteristics, swelling behavior, and mechanical properties of natural rubber compounds were studied using a conventional vulcanization system. Recycle rubber powder (RRP), carbon black (CB) (N550), and calcium carbonate (CaCO₃) were used as fillers and the loading range was from 0 to 50 phr. Results show that the scorch time, t ₂, and cure time, t ₉₀, decrease with increase in filler loading. At a similar filler loading, RRP shows shortest t ₂ and t ₉₀ followed by CB and calcium carbonate. The tensile strength, tensile modulus, and hardness increase with increase in CB loading, whereas elongation at break, resilience, and swelling properties show opposite trend. For RRP and calcium carbonate filled natural rubber compounds, the tensile strength increases up to 10 phr and starts to deteriorate at higher filler loading. The other properties such as tensile modulus, hardness, elongation at break, resilience, and swelling percentage show a small change (increase or decrease) with increase in RRP and calcium carbonate loading in natural rubber compounds. Overall results indicate that RRP can be used as a cheapener to replace calcium carbonate in natural rubber compounds where improved mechanical properties are not critical.     

Effect of Nano-CaCO3 on Mechanical and Thermal Properties of Polyamide Nanocomposites

Polyamide-CaCO₃ nanocomposites were prepared by melt intercalation on twin-screw extruder. Various particle sizes (23, 17 and 11 nm) of CaCO₃ were synthesized by in-situ deposition technique. The shape and sizes of nano-CaCO₃ particles were confirmed by transmission electron microscopy (TEM). Nano-CaCO₃ was added from 1 to 4 wt% in the polyamide. Properties such as Tensile strength, Elongation at break, Hardness, and Flame retardency were studied. These results were compared with commercial CaCO₃ filled composites. Nano-CaCO₃ filled in polyamide shows, 3 fold improvement in Young's modulus in comparison to commercial CaCO₃ and 4–7 folds to virgin polyamide. Besides that, a polyamide nanocomposite shows 2 times improvements in flame retarding and vicat softening properties compared to commercial CaCO₃. Moreover, thermal degradation was studied on TGA and found to be improved compared to commercial CaCO₃. This was due to uniform dispersion of nano-CaCO₃ with greater surface area in comparison to commercial CaCO₃ in the polyamide matrix. Extent of dispersion of nano-CaCO₃ was studied along with microcracks generated during tensile testing using scanning electron microscope (SEM).     

Properties of biomineralized (CaCO3) PVP-CMC hydrogel with reference to its cytotoxicity

The authors focus on properties of biomineralized (CaCO₃) PVP-CMC hydrogel (designated as I–X) including cytotoxicity assay using primary mouse embryonic fibroblasts. The biomineralized samples (VII–X) showed >80% cell viability, was selected for further characterizations. FTIR and XRD indicate deposition of CaCO₃ within the PVP-CMC hydrogel matrix, SEM shows changes in morphology and pore diameter (VII and VIII: 1–12 µm; IX: 10–70 µm; X: 70–170 µm), TGA determines the decomposition scenario of CaCO₃, and tensile strength of samples (VII–X) ranged between 0.04 and 1.0 GPa, which practically corresponds to the modulus of cancellous bone.     

Novel Comb-Like Copolymer Dispersant for Polypropylene/CaCO3 Composites and Its Influence on Dispersion,Crystallization, Mechanical,and Thermal Properties

A novel comb-like copolymer with carboxyl group as an anchoring group and polycaprolactone as a solvent chain was first used as the dispersant of CaCO₃ particles in polypropylene (PP). The dispersion of CaCO₃ particles in PP matrix was significantly improved in the presence of comb-like copolymer dispersant because of the strong repulsive force caused by steric hindrance effect. The influences of the coating amount of comb-like copolymer dispersant on crystallization behaviors, mechanical properties, and thermal stabilities were systematically investigated. The crystallization temperature, crystallinity, and crystallization rate of PP/CaCO₃ composites prepared with monolayer-coated CaCO₃ were all improved, where the monolayer comb-like copolymer coating remained as a rigid layer and provided a noticeable nucleating effect. The PP/CaCO₃ composites coated with monolayer SP comb-like copolymer also had the best mechanical properties, including tensile strength, Young’s modulus, flexural modulus, and impact strength because of the good dispersion of CaCO₃ particles in PP matrix. The thermal stability of PP/CaCO₃ composites were measured by thermogravimetric analysis. The results showed that SP comb-like copolymer dispersant treated CaCO₃ filled composites had excellent thermal stability than untreated and neat PP, especially for the composite prepared with monolayer-coated CaCO₃.     

Comparison of the mechanical properties and interfacial interactions between talc,kaolin, and calcium carbonate filled polypropylene composites

Three types of mineral fillers—talc, calcium carbonate (CaCO₃), and kaolin (10–40 wt % filler loadings)—were compounded with polypropylene (PP) with a twin‐screw extruder. The composites were injection‐molded, and the effects of the filler loading on the mechanical, flow, and thermal properties for the three different types of filled composites were investigated. The aim was to compare their properties and to deduce prospective filler combinations that would yield hybrid PP composites in following studies. The results showed that in most cases, the strength and stiffness of the talc‐filled PP composites was significantly higher than those of the CaCO₃‐ and kaolin‐filled PP composites. However, CaCO₃, being a nonreactive filler, increased the toughness of PP. The kaolin‐filled PP composites also showed some improvement in terms of strength and stiffness, although the increases in these properties were not as significant as those of the talc‐filled PP composites. The effects of interfacial interactions between the fillers and PP on the mechanical properties were also evaluated with semiempirical equations. The nucleating ability of all three fillers was studied with differential scanning calorimetry, and the strongest nucleating agent of the three was talc, followed by CaCO₃ and kaolin. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3315–3326, 2004     

Physicochemical characterization of the filler–matrix interface in elastomer‐encapsulated fly ash/polyester particulate composites

An attempt was made to improve the toughness of fly ash (FA)/general‐purpose unsaturated polyester resin (GPR) composites. Elastomer [styrene–butadiene rubber (SBR) or acrylic copolymer (AC)]‐encapsulated fillers (FA or CaCO₃) were made through the coagulation of the emulsified elastomer containing the filler with constant stirring. The elastomer‐encapsulated fillers were added to GPR at concentrations as high as 15 wt % to make FA/SBR or AC/GPR composites. The mechanical properties (i.e., the tensile strength, tensile modulus, tensile elongation, flexural strength, flexural modulus, impact strength, and hardness) of FA/GPR, FA/SBR/GPR, and FA/AC/GPR composites were studied. The tensile‐fractured surfaces of all the composites were studied with scanning electron microscopy. The thermal stability was studied with thermogravimetric analysis. An analysis of the results indicate that this modification technique is rather easy and more economical than the chemical modification of filler surfaces with functional silane coupling agents. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 171–184, 2005     

Mechanical properties of i-PP/CaCO3 composites

Tensile and impact behavior of CaCO₃-filled polypropylene was studied in the composition range 0–60 wt % filler. Tensile modulus increased while tensile strength and breaking elongation decreased with increase in CaCO₃ content. The modulus increase and elongation decrease were attributed to increased filler–polymer interaction resulting in reduction in molecular mobility, while increased amorphization and obstruction to stress transfer accounted for the tensile strength decrease. Analysis of tensile strength data showed introduction of stress concentration in the composites. Izod impact strength at first increased up to a critical CaCO₃ content, beyond which the value decreased. Surface treatment of CaCO₃ with a titanate coupling agent LICA 12 enhances the adhesion of the filler and polymer, which further modifies the strength properties. Scanning electron microscopic studies indicated better dispersion of CaCO₃ particles upon surface treatment, which effected the changes in the strength properties of the composites.     

Renewable thermoplastic multiphase systems from dimer fatty acids,with mineral microfillers

Renewable thermoplastic blends based on polyurethane (TPU) and polyamide (DAPA) obtained from dimers of fatty acids were reinforced with mineral microfillers, surface coated calcium carbonate (CaCO₃) or high aspect ratio talc (HAR), to prepare different micro‐biocomposites systems. The influence of the nature of the filler, the aspect ratio and the filler content (5, 10, and 15 wt %), for different TPU/DAPA ratios (20/80, 50/50, and 80/20 wt %/wt %), were specifically investigated. Differential scanning calorimetry (DSC) and thermogravimetric analyses were conducted to investigate the thermal properties. DSC analyses showed that the addition of CaCO₃ had no influence on the glass transition and the melting temperature of the corresponding composites. Moreover, the morphology and the mechanical properties in the solid state of the different multiphase systems were investigated. SEM observations after tensile tests showed that the best matrix/filler interactions were obtained in the case of the 20/80‐based systems. Uniaxial tensile tests have shown that the addition of HAR or CaCO₃ fillers led to a clear increase of the Young modulus. Micromechanical models based on a two‐phase composite approach, including Mori–Tanaka and Davies models were used to describe the dependence of the elastic modulus on the volume fraction of HAR or CaCO₃ fillers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43055.     

An investigation on the mechanical and dynamic rheological properties of single and hybrid filler/polypropylene composites based on talc and calcium carbonate

Some results of experiments on the mechanical and rheological properties of mineral filled polypropylene were presented. Single filler and hybrid filler composites of talc and calcium carbonate (CaCO₃) were prepared in a co‐rotating twin‐screw extruder. The effect of filler type, filler content, and coupling agent on the mechanical and rheological properties of the polypropylene were studied. The coupling agent was maleic anhydride‐grafted polypropylene (PP‐g‐MA). It was found that the mechanical properties are affected by filler type, filler concentration, and the interaction between filler and matrix. The tensile strength of the composite is more affected by the talc while the impact strength is influenced mostly by CaCO₃ content. The elongation at break of PP/CaCO₃ composites was higher than that of PP/talc composites. The incorporation of coupling agent into PP/mineral filler composites increased the mechanical properties. Rheological properties indicated that the complex viscosity and storage modulus of talc filled samples were higher than those of calcium carbonate filled samples while the tan δ was lower. The rheological properties of hybrid‐filler filled sample were more affected by the talc than calcium carbonate. The PP‐g‐MA increased the complex viscosity and storage modulus of both single and hybrid composites. POLYM. COMPOS., 2009. © 2009 Society of Plastics Engineers     

Effect of single‐mineral filler and hybrid‐mineral filler additives on the properties of polypropylene composites

The present study was carried out to determine the filler characteristics and to investigate the effects of three types of mineral fillers (CaCO₃, silica, and mica) and filler loadings (10–40 wt%) on the properties of polypropylene (PP) composites. The characteristics of the particulate fillers, such as mean particle size, particle size distribution, aspect ratio, shape, and degree of crystallinity were identified. In terms of mechanical properties, for all of the filled PP composites, Young's modulus increased, whereas tensile strength and strain at break decreased as the filler loading increased. However, 10 wt% of mica in a PP composite showed a tensile strength comparable with that of unfilled PP. Greater tensile strength of mica/PP composites compared to that of the other composites was observed because of lower percentages of voids and a higher aspect ratio of the filler. Mica/PP also exhibited a lower coefficient of thermal expansion (CTE) compared to that of the other composites. This difference was due to a lower degree of crystallinity of the filler and the CTE value of the mica filler. Scanning electron microscopy was used to examine the structure of fracture surfaces, and there was a gradual change in tensile fracture behavior from ductile to brittle as the filler loading increased. The nucleating ability of the fillers was studied with differential scanning calorimetry, and a drop in crystallinity of the composites was observed with the addition of mineral filler. Studies on the hybridization effect of different (silica and mica) filler ratios on the properties of PP hybrid composites showed that the addition of mica to silica‐PP composites enhanced their tensile strength and modulus. J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers     

Phase structure and mechanical properties of PP/EPR/CaCO3 nanocomposites: Effect of particle's size and treatment

Calcium carbonate (CaCO₃) reinforced polypropylene/ethylene propylene rubber (PP/EPR) copolymer composites for automotive use were developed by means of extrusion and injection molding process. Three kinds of CaCO₃ (stearic acid treated and untreated) nanoparticles and microparticles were used as fillers. The influence of stearic acid, particle size, and filler content on the state distribution and morphology were investigated by SEM and rheological measurements. Two different morphologies were observed: EPR and CaCO₃ dispersed in the PP matrix and a core shell structure, depending on the interactions between EPR and CaCO₃. Toughening mechanisms and mechanical properties of the different systems were investigated. Significant improvement in tensile modulus is observed in all composites, depending on filler content. Elongation and notched impact strength were drastically decreased, especially for composites with nano CaCO₃. Better impact properties were obtained with low content of treated particles, showing the importance of filler treatment. POLYM. ENG. SCI., 55:2859–2868, 2015. © 2015 Society of Plastics Engineers     

Studies of Thermal Conductivity of Nano CaCO3/HIPS Composites by Unsteady State Technique and Simulation with Nielsen's Model

Differential scanning calorimeter (DSC) and thermal conductivity meter were used for measurement of thermal conductivity by unsteady state technique of the high impact polystyrene (HIPS) composites filled with 0.5, 1.5, and 2.5 wt.% of CaCO₃ nano particles. A comparison of experimental and theoretical values of (K _c /K _m) was done using MATLAB software fitting in Nielsen's model of thermal conductivity for polymers containing low limit of volume fraction. The packing fraction (Φ _max) and geometry and orientation dependent parameter (A) of the nanofiller were assumed as 0.10 and 100, respectively, which are most fitted for this model. The effect of nanosize on thermal conductivity was well predicted by plotting different values of thermal conductivity at various source temperatures. The violation of the theoretical values because of local molecular vibration at higher temperature is highlighted promisingly in the plots.     

Composites of high density polyethylene and different grades of calcium carbonate: Mechanical,rheological, thermal,and morphological properties

Calcium carbonate (CaCO₃)/high density polyethylene (HDPE) composites were prepared in a HAAKE twin screw extruder, using the experimental conditions defined by the factorial experimental design presented in a prior study. In this study, the effect of different grades (Ca₁ and Ca₂) and CaCO₃ content (varying from 0 to 15 wt %) on the mechanical, rheological, thermal, and morphological properties was evaluated. The results showed that the addition of the filler provoked a decrease on the impact strength, stress at break, and yield stress properties in relation to the pure HDPE. A consequent increase on the modulus of elasticity, indicating an increase on the rigidity of the composite, was observed. It was also verified a tendency to increase the toughness and the viscosity of the composites as CaCO₃ was added. Scanning electron micrographs showed that as the filler was incorporated to HDPE matrix, CaCO₃ particles tended to agglomerate, especially that grade constituted of particles of smaller size. The thermal analysis showed that the addition of mineral filler caused a decrease on the crystallinity degree. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2559–2564, 2006     

Effect of Nano–Magnesium Hydroxide on Mechanical and Flame-Retarding Properties of SBR and PBR: A Comparative Study

Magnesium hydroxide [Mg(OH)₂] is one of the potential inorganic fillers. In this work, nanoparticles (37±5 nm) of the magnesium hydroxide were prepared using matrix-mediated growth and control technique, and their size was confirmed by X-ray diffraction technique. Nano-Mg(OH)₂-SBR and nano-Mg(OH)₂-PBR composites with 2–10% (w/w) filler loading were prepared by compounding on laboratory-scale two-roll mill and a compression molding machine. These composites were tested for tensile and physical properties, and the properties were compared with the composites of commercial Mg(OH)₂. The incorporation of nanofiller improved the properties of nanocomposites.     

Properties of Ferrite-Filled Natural Rubber Composites

Nickel zinc ferrite (Ni-ZnFe₂O₄)-filled natural rubber (NR) composite was prepared at various loading of ferrite. The tensile properties included in this study were tensile strength, tensile modulus and elongation at break. The tensile strength and elongation at break of the composites increased up to 40 parts per hundred rubber (phr) of ferrite and then decreased at higher loading whereas the tensile modulus was increased gradually with increasing of ferrite loading. Scanning electron microscopy (SEM) was used to determine the wettability of filler in rubber matrix. From the observation, the increase of filler loading reduced the wettability of the filler. Thermal stability of the composites was conducted by using a thermogravimetry analyser (TGA). The incorporation of ferrite in NR composites enhanced the thermal stability of NR composites. The swelling test results indicate that the swelling percentage of the composites decreased by increasing of ferrite loading. The initial permeability, μ_i and quality factor, Q of magnetic properties of NR composites achieved maximum value at 60 phr of ferrite loading for frequency range between 5000–40,000 kHz. The maximum impedance, Z _max of the NR composites was at the highest value at 80 phr ferrite loading for frequency range between 200–800 MHz.     

MWCNT/Hectorite hybrid filled acrylonitrile butadiene rubber/ ethylene-co-vinyl acetate blend nanocomposites: preparation and properties

Multiwalled carbon nanotube/hectorite hybrid filler (HMH) was prepared by simple dry grinding method. It was subsequently used for the reinforcement of technologically compatible acrylonitrile butadiene rubber (NBR)/ ethylene-co-vinyl acetate (EVA) blend through solution intercalation method. Analysis of the prepared blend nanocomposites confirms homogeneous dispersion of the constituent fillers in the polymer matrix and significant interaction between two types of constituent fillers. Mechanical properties of NBR/EVA blend are significantly improved with HMH content up to 4 wt.% followed by reversion. Maximum improvement observed in tensile strength, elongation at break and toughness are 106%, 37% and 171% respectively without significant rise in Young’s modulus. Results also show best dynamic mechanical and dielectric response at 4 wt.% and 3 wt.% HMH content respectively. Enhanced mechanical, dynamic mechanical and dielectric properties of the blend nanocomposites attained may be attributed to fair degree of compatibility between the two polymer matrices, homogeneous dispersion of fillers and improved polymer-filler interaction.     

Mechanical properties and morphologies of PP/mPE/filler composites

Because of the poor impact behavior of polypropylene (PP) at low temperatures, the blending of PP with metallocene‐polymerized polyethylene (mPE) elastomers was investigated in this study. However, a reduced modulus of the overall blend was inevitable because of the addition to elastomers. To obtain a balance of the properties, we introduced rigid inorganic fillers to PP/mPE blends. The performance of the composites was characterized with tensile and Charpy notched impact tests, and the fracture morphology was examined with scanning electron microscopy. The results showed that the effects of fillers in a brittle matrix and in a ductile matrix were quantitatively different. For PP/mPE/filler ternary composites, the dependence of Young's modulus and yield strength on CaCO₃ content was not significant compared with that of PP/filler binary composites, whereas the elongation at break and tensile toughness at room temperature for PP/mPE/filler systems were more improved. The impact strength of the PP/mPE blends filled with untreated glass beads and CaCO₃ at a low temperature was lowered because of the weak interfacial bond. However, the values of the impact strength of the PP/mPE/filler composites at a low temperature remained at a high level compared with that of pure PP. In particular, a PP/mPE blend filled with surface‐treated kaolin had a higher low‐temperature impact toughness than the unfilled blend. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 3029–3035, 2002; DOI 10.1002/app.2333