Factors affecting the abrasiveness of filled rigid PVC dry blends

Abrasion due to the high speed mixing of rigid PVC dry blends filled with CaCO₃ was found to be a function of both the mixing conditions and type and level of CaCO₃ used. Laboratory scale tests showed that abrasion is a function of mix time, mix speed, and mixer blade geometry. These variables were standardized to develop a laboratory abrasion test using a Hockmeyer mixer equipped with a soft 3-in diameter aluminum mixing blade. This procedure was used to investigate the effect of CaCO₃ property variables on abrasion during rigid PVC dry blending. Multiple linear regression analysis at 30 phr CaCO₃ showed that abrasion increased with filler top cut, mean, acid insolubles, and MgCO₃ content, but diminished with an increase in percent less than 1 micron fraction. A more generalized abrasion predictor model was developed by considering surface area to be a linear function of top cut, mean, and percent less than 1 micron properties. Abrasion was greatly minimized by using finer particle size, higher surface area CaCO₃ with low acid insoluble and magnesium carbonate levels. These criteria also aid in reducing the abrasive effects of TiO₂ during dry blending through a CaCO₃/TiO₂ interaction.     

The experimental results and simulation of temperature dependence of brittle‐ductile transition in PVC/CPE blends and PVC/CPE/nano‐CaCO3 composites

The effect of chlorinated polyethylene (CPE) content and test temperature on the notched Izod impact strength and brittle‐ductile transition behaviors for polyvinylchloride (PVC)/CPE blends and PVC/CPE/nano‐CaCO₃ ternary composites is studied. The CPE content and the test temperature regions are from 0–50 phr and 243–363 K, respectively. It is found that the optimum nano‐CaCO₃ content is 15 phr for PVC/CPE/nano‐CaCO₃ ternary composites. For both PVC/CPE blends and PVC/CPE/nano‐CaCO₃ ternary composites, the impact strength is improved remarkably when the CPE content or test temperature is higher than the critical value, that is, brittle‐ductile transition content (C_BD) or brittle‐ductile transition temperature (T_BD). The T_BD is closely related to the CPE content, the higher the CPE content, the lower the T_BD. The temperature dependence of impact strength for PVC/CPE blends and PVC/CPE/nano‐CaCO₃ ternary composites can be well simulated with a logistic fitting model, and the simulation results can be illustrated with the percolation model proposed by Wu and Jiang. DMA results reveal that both PVC and CPE can affect the T_BD of PVC/CPE blends and PVC/CPE/nano‐CaCO₃ composites. When the CPE content is enough (20 phr), the CPE is more important than PVC for determining the T_BD of PVC/CPE blends and PVC/CPE/nano‐CaCO₃ composites. Scanning electron microscopy (SEM) observations reveal that the impact fractured mechanism can change from brittle to ductile with increasing test temperature for these PVC systems. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Processability,morphology, thermal,and mechanical properties of rigid PVC composites with liquid macromolecular modifier‐coated CaCO3

Rigid poly(vinyl chloride) (PVC)/CaCO₃ and PVC/liquid macromolecular modifier (LMM) coated CaCO₃ (PVC/LCC) composites were both fabricated by melt mixing. The processability, micro‐structure, dynamic mechanical behavior and mechanical properties of PVC/CaCO₃ and PVC/LCC composites were studied by using torque rheometer, scanning electron microscope (SEM), dynamic mechanical analysis (DMA), and universal mechanical testing machine. The results showed that the synergistic effect of LMM and CaCO₃ particles accelerated the plasticization of PVC resins. The processability of PVC/LCC composites was improved. The dispersion of LCC in PVC matrix was improved by the modification of CaCO₃ particles with LMM. The T_gs of PVC/LCC composites were enhanced by filling with LCC. Because of the synergistic toughening of LMM and CaCO₃ particles, the PVC/LCC composites exhibited excellent notched impact properties at the optimum value of LCC particles content. POLYM. COMPOS., 36:1286–1292, 2015. © 2014 Society of Plastics Engineers     

Surface modification of calcium carbonate by thiol-ene click reaction and its effect on the performance of PVC composite

Disposable PVC gloves are cost effective, but their mechanical properties can be compromised at extremely high concentrations of plasticizers. The tensile properties of PVC gloves can be improved by incorporating modified fillers into the PVC matrix. In this research, calcium carbonate (CaCO₃) was functionalized with γ-methacryloxy propyl trimethoxyl silane (KH-570) and then further modified through a click reaction with n-Octadecyl mercaptan. Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy have confirmed that n-Octadecyl mercaptan-modified KH-570 was successfully grafted onto the surface of CaCO₃. Composite films were manufactured by blending either pristine CaCO₃ or modified CaCO₃ with PVC resin paste and their tensile properties, light transmission, moisture permeability, and solvent resistance were evaluated. Compared with CaCO₃/PVC and KH-570-modified CaCO₃/PVC composite films, n-Octadecyl mercaptan-modified CaCO₃/PVC composite films showed higher light transmittance, lower moisture permeability, and higher tensile properties. Dynamic mechanical analysis revealed that these films had low glass transition temperatures, thus broadening their applicability to low-temperature conditions.     

Interfacial structures and mechanical properties of PVC composites reinforced by CaCO3 with different particle sizes and surface treatments

The effects of particle size and surface treatment of CaCO₃ particles on the microstructure and mechanical properties of poly(vinyl chloride) (PVC) composites filled with CaCO₃ particles via a melt blending method were studied by SEM, an AG‐2000 universal material testing machine and an XJU‐2.75 Izod impact strength machine. The tensile and impact strengths of CaCO₃/PVC greatly increased with decreasing CaCO₃ particle size, which was attributed to increased interfacial contact area and enhanced interfacial adhesion between CaCO₃ particles and PVC matrix. Titanate‐treated nano‐CaCO₃/PVC composites had superior tensile and impact strengths to untreated or sodium‐stearate‐treated CaCO₃/PVC composites. The impact strength of titanate‐treated nano‐CaCO₃/PVC composites was 26.3 ± 1.1 kJ m⁻², more than three times that of pure PVC materials. The interfacial adhesion between CaCO₃ particles and PVC matrix was characterized by the interfacial interaction parameter B and the debonding angle θ, both of which were calculated from the tensile strength of CaCO₃/PVC composites. Copyright © 2005 Society of Chemical Industry     

Toughening and reinforcement of rigid PVC with silicone rubber/nano‐CACO3 shell‐core structured fillers

To improve the mechanical properties and structure of poly(vinyl chloride) (PVC)/nano‐CaCO₃ nano composite, a core (nano‐CaCO₃)/shell (SR) structured filler (40–60 nm) was successfully prepared by refluxing methyl vinyl silicone rubber (SR) and nano‐CaCO₃ particles (coupling agent KH550, KH560, or NDZ‐101 as interfacial modifier) in toluene with vigorous stirring, according to an encapsulation model. It is effective in rigid PVC composite's toughness and reinforcement. The interfacial modifier's structure and interaction of nanocomposites of PVC/SR/nano‐CaCO₃ were studied. The results indicate that KH560 has the optimal interfacial modificatory effect. The environmental scanning electron microscope (ESEM) study testified that PVC/SR/nano‐CaCO₃ nanocomposites had a typical rubber–plastics‐toughening mechanism. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2560–2567, 2006     

Ultraviolet light aging properties of PVC/CaCO3 composites

The ultraviolet radiation aging behaviors of PVC/CaCO₃ and PVC/CaCO₃/macromolecular modifier composites were studied through whiteness measurement, Fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, scanning electron microscopy, and mechanical properties test. It was found that nano‐CaCO₃ particles used as ultraviolet light screening agents could significantly enhance the antiaging properties of PVC materials. Due to the macromolecular modifier coated on nano‐CaCO₃ particles, the compatibility of nano‐CaCO₃ and PVC matrix was improved, resulting in uniform dispersion of nano‐CaCO₃ in PVC matrix. Therefore, the PVC/CaCO₃/MP composite exhibited better antiaging properties than PVC/CaCO₃ composite. After 12 h of ultraviolet irradiation, the tensile strength retention, elongation at break retention, and impact strength retention of PVC/CaCO₃/MP composite were 79.5%, 74.5%, and 75.3%, which were much higher than that of neat PVC and PVC/CaCO₃ composite. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Nanocomposites of poly(vinyl chloride) and nanometric calcium carbonate particles: Effects of chlorinated polyethylene on mechanical properties,morphology, and rheology

Nanocomposites of poly(vinyl chloride) (PVC) and nano‐calcium carbonate (CaCO₃) particles were prepared via melt blending, and chlorinated polyethylene (CPE) as an interfacial modifier was also introduced into the nanocomposites through preparing CPE/nano‐CaCO₃ master batch. The mechanical properties, morphology, and rheology were studied. A moderate toughening effect was observed for PVC/nano‐CaCO₃ binary nanocomposites. The elongation at break and Young's modulus also increased with increasing the nano‐CaCO₃ concentration. Transmission electron microscopy (TEM) study demonstrated that the nano‐CaCO₃ particles were dispersed in a PVC matrix uniformly, and a few nanoparticles agglomeration was found. The toughening effect of the nano‐CaCO₃ particles on PVC could be attributed to the cavitation of the matrix, which consumed tremendous fracture energy. The notched Izod impact strength achieved a significant improvement by incorporating CPE into the nanocomposites, and obtained the high value of 745 J/m. Morphology investigation indicated that the nano‐CaCO₃ particles in the PVC matrix was encapsulated with a CPE layer through preparing the CPE/nano‐CaCO₃ master batch. The evaluation of rheological properties revealed that the introduction of nano‐CaCO₃ particles into PVC resulted in a remarkable increase in the melt viscosity. However, the viscosity decreased with addition of CPE, especially at high shear rates; thus, the processability of the ternary nanocomposites was improved. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2714–2723, 2004     

CaCO3 as a new member of high solar-reflective filler on the cooling property in polymer composites

Calcium carbonate (CaCO₃) is the most commonly used inorganic filler in polymer materials to improve the mechanical properties and reduce the costs. However, there are few reports on the preparation of cooling materials using CaCO₃. In this study, CaCO₃ was introduced into the polymer matrix as a solar reflective filler to prepare passive cooling materials. Specifically, the influences of CaCO₃ content on the structure and performances of polyvinyl chloride (PVC)/CaCO₃ composite films were characterized by scanning electron microscope (SEM), contact angle test, surface roughness and glossiness, solar reflectivity, thermal emissivity, temperature test and mechanical property characterization. When the volume fraction of CaCO₃ reaches 67%, the total solar reflectance of PVC/CaCO₃ composite films is 80.8%, which is 351.4% higher than that of PVC films. CaCO₃ powder has little influence on the thermal emissivity of the atmospheric window (3-5 μm and 8-13 μm) of the composite films, which remains at a high level about 0.86. In temperature test, the final temperature of sample 67 v% is only 26.8°C, which is only 2.8°C higher than the room temperature and 22.2°C lower than that of PVC films. For comparison, the cooling performance of PVC/titanium dioxide (TiO₂) composite films with 10 v% TiO₂ was also measured, and the final temperature is 29.1°C, even 2.3°C higher than that of PVC/CaCO₃ composite films with 67 v% CaCO₃. In this study, the cost-effective and solar-reflective PVC/CaCO₃ composites have potential application in cooling material field.     

Rheological and mechanical properties of PVC/CaCO3 nanocomposites prepared by in situ polymerization

Poly(vinyl chloride) (PVC)/calcium carbonate (CaCO₃) nanocomposites were synthesized by in situ polymerization of vinyl chloride (VC) in the presence of CaCO₃ nanoparticles. Their thermal, rheological and mechanical properties were evaluated by dynamic mechanical analysis (DMA), thermogravimetry analysis (TGA), capillary rheometry, tensile and impact fracture tests. The results showed that CaCO₃ nanoparticles were uniformly distributed in the PVC matrix during in situ polymerization of VC with 5.0 wt% or less nanoparticles. The glass transition and thermal decomposition temperatures of PVC phase in PVC/CaCO₃ nanocomposites are shifted toward higher temperatures by the restriction of CaCO₃ nanoparticles on the segmental and long-range chain mobility of the PVC phase. The nanocomposites showed shear thinning and power law behaviors. The ‘ball bearing’ effect of the spherical nanoparticles decreased the apparent viscosity of the PVC/CaCO₃ nanocomposite melts, and the viscosity sensitivity on shear rate of the PVC/CaCO₃ nanocomposite is higher than that of pristine PVC. Moreover, CaCO₃ nanoparticles stiffen and toughen PVC simultaneously, and optimal properties were achieved at 5 wt% of CaCO₃ nanoparticles in Young's modulus, tensile yield strength, elongation at break and Charpy notched impact energy. Detailed examinations of micro-failure micromechanisms of impact and tensile specimens showed that the CaCO₃ nanoparticles acted as stress raisers leading to debonding/voiding and deformation of the matrix material around the nanoparticles. These mechanisms also lead to impact toughening of the nanocomposites.     

Effects of poly(1,2‐propylene glycol adipate) and nano‐CaCO3 on DOP migration and mechanical properties of flexible PVC

Nano‐CaCO₃ was used as nano‐scale filler and poly(1,2‐propylene glycol adipate) (PPA) was used as polymeric plasticizer in flexible poly(vinyl chloride) (PVC) sheets for the partial replacement of di(2‐ethyl hexyl) phthalate (DOP) in this paper. The effect of PPA and nano‐CaCO₃ on restraining DOP migration was evaluated via extraction tests. The results showed that the introduction of nano‐CaCO₃ can decrease the extraction rate of DOP in the PVC matrix. The tensile strength and elongation at break of CaCO₃‐1/PPA‐20/DOP‐30/PVC were similar to those of DOP‐50/PVC, and CaCO₃‐1/PPA‐20/DOP‐30/PVC exhibited the superior suppression of DOP migration compared with DOP‐50/PVC. Thermogravimetry analysis (TGA) indicated that the addition of nano‐CaCO₃ effectively improved the thermal stability of the nanocomposites. Therefore, the combination of PPA and nano‐CaCO₃ is an effective approach to suppress the migration of DOP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Investigation of the addition of nano‐CaCo3 at dry mixing or onset of fusion on the dispersion,torque, and mechanical properties of compounded PVC

A Brabender torque rheometer equipped with an internal mixer was used to study the influence of compounding method on the properties of (rigid PVC)/(treated and untreated nano‐CaCO₃) nanocomposites. Two different methods were studied for the addition of surface treated and untreated nano‐CaCO₃ during the melt mixing of rigid PVC. Direct dry mixing of rigid PVC and nano‐CaCO₃, and addition of nano‐CaCO₃ at the onset of PVC fusion were investigated. Dispersion of treated and untreated nano‐CaCO₃ was studied by X‐ray diffraction and scanning electron microscopy. Results showed that using direct dry mixing improved the dispersion of nano‐CaCO₃ in the PVC matrix by lowering the fusion time. The mechanical properties of the nanocomposite samples such as impact strength, tensile strength, and elongation at break were improved by using this method. The addition of treated nano‐CaCO₃ at the onset of fusion caused a simultaneous decrease in torque. Also, rigid PVC nanocomposites prepared with treated nano‐CaCO₃ showed better mechanical properties than those of nanocomposites prepared with the untreated nano‐CaCO₃. J. VINYL ADDIT. TECHNOL., 18:153–160, 2012. © 2012 Society of Plastics Engineers     

Interaction effects and property retention in poly(vinyl chloride) compounds

The influence of thermodynamic interactions among the components of a polymer system on mechanical properties and their retention on aging has been investigated. The systems considered involve plasticized poly(vinyl chloride)(PVC), and CaCO₃ fillers. Inverse gas chromatography was used to measure interaction parameters, and to express these in terms of acid-base concepts. Interaction data were obtained over a wide temperature range. It was shown that the volume of plasticizers retained by the PVC correlates with the measured interaction parameters. Similarly, the interaction parameters identify a CaCO₃ filler preferred for reinforcing rigid PVC, and a different CaCO₃ filler for use in given PVC-plasticizer combinations. The mechanical properties of filled PVC (up to 40 phr CaCO₃), and particularly the ultimate properties of the compounds, correlate with interaction concepts, as do property retention data after accelerated aging of the compounds at 100°C. It is concluded that component interaction parameters may provide useful guidelines to the formulation of compounds with superior properties and reduced property losses due to aging.     

Effect of High‐Energy Vibromilling on Interfacial Interaction and Mechanical Properties of PVC/Nano‐CaCO3 Composites

Summary: The effects of interfacial interaction between nano‐CaCO₃ and PVC on mechanical properties and morphology of PVC/nano‐CaCO₃ composites were studied. Nano‐CaCO₃ was treated with vibromilling in the presence of PVC and coupling agents. The mechanical properties of PVC/treated nano‐CaCO₃ are remarkably improved. Transmission electron microscopy results revealed that vibromilled nano‐CaCO₃ particles are well dispersed in PVC matrix with good homogeneity and well adhered to PVC matrix. Molau test indicated that chemical reaction between newly formed surface of nano‐CaCO₃ and PVC or coupling agent took place. Theoretical calculation results show that the interfacial interaction between PVC and nano‐CaCO₃ are substantially improved through vibromilling treatment of nano‐CaCO₃ in the presence of PVC and coupling agent.

Molau test results of the samples in THF.     

Mechanical properties of talc‐ and (calcium carbonate)‐filled poly(vinyl chloride) hybrid composites

The main objective of this study was to investigate and compare the mechanical properties of poly(vinyl chloride) (PVC) composites filled with calcium carbonate (CaCO₃), talc, and talc/CaCO₃. Talc and CaCO₃ with different grades were incorporated into the PVC matrix. To produce the composites, the PVC resin, fillers, and other additives were first dry‐blended by using a laboratory mixer before being milled into sheets in a two‐roll mill. Test specimens were prepared by compression molding, after which the mechanical properties of the composites were determined. Single and hybrid filler loadings used were fixed at 30 phr (parts per hundred parts of resin). Talc‐filled composite showed the highest flexural modulus and the lowest impact strength, whereas uncoated, ground, 1‐μm CaCO₃ (SM 90) showed optimum properties in terms of impact strength and flexural modulus among all grades of CaCO₃. It was selected to combine with talc at different ratios in the hybrid composites. The impact strength of the hybrid composites gradually increased with increasing SM 90 content, but the flexural and tensile properties showed an opposite behavior. Hybrid (10 phr talc):(20 phr SM 90)‐filled PVC composite reached a synergistic hybridization with balanced properties in impact strength, as well as flexural and tensile properties. J. VINYL ADDIT. TECHNOL., 2012. © 2012 Society of Plastics Engineers     

A novel method to prepare zinc hydroxystannate-coated inorganic fillers and its effect on the fire properties of PVC cable materials

Fire-retardant (FR) properties, including limiting oxygen index, peak rate of heat release, and smoke parameter have been measured and compared for unfilled and filled polyvinyl-chloride (PVC)-based cable formulations, containing 15 wt% amounts of uncoated and zinc-hydroxystannate (ZHS)-coated magnesium hydroxide (MH) and calcium carbonate (CaCO₃) fillers at the same addition level. Of the uncoated fillers, MH was more effective at lowering flammability than CaCO₃. When the ZHS coating was applied to MH and CaCO₃, CaCO₃ became the most effective additive at lowering PVC flammability and smoke output. POLYM. ENG. SCI., 47:1163–1169, 2007. © 2007 Society of Plastics Engineers     

Tin dioxide coated calcium carbonate as flame retardant for semirigid poly(vinyl chloride)

The flame retardant and smoke suppressant properties of semirigid PVC treated with calcium carbonate (CaCO₃), tin oxide (SnO₂), the mixture of CaCO₃/SnO₂ and SnO₂‐coated CaCO₃ have been studied through the limiting oxygen index, char yield, and smoke density rating (SDR) methods. The thermal degradation in air of the treated semirigid PVC was studied by thermogravimetry (TG) and differential thermal analysis (DTA) from ambient temperature to 1073 K. The morphologies of the additives and the char formation were studied through SEM. The mechanical property was also studied. The results showed that the semirigid PVC treated with SnO₂‐coated CaCO₃ has a higher limiting oxygen index and char yield, lower SDR and MSDR, a more compact structure of char formation than the semirigid PVC without flame retardant and the semirigid PVC with the equivalent CaCO₃, or SnO₂, or the mixture of CaCO₃/SnO₂, a similar tensile property and greatly improved impact strength compared with that of the semirigid PVC without flame retardant. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 731–738, 2006     

Effect of nanocalcium carbonate on the impact strength and accelerated weatherability of rigid poly(vinyl chloride)/acrylic impact modifier

Poly(vinyl chloride) (PVC) composites filled with nano‐ and micro‐CaCO₃ particles were prepared via a melt blending method. Transmission electron microscopy images revealed better dispersion of nano‐CaCO₃ than micro‐CaCO₃ in the PVC matrix. With more than 5 phr (parts per 100 parts of resin) of nano‐CaCO₃ content, both impact strength and heat stability were improved. Accelerated weathering tests were performed to investigate UV stability. The impact strength and white index obtained upon weathering exposure of PVC/(80 μm CaCO₃) nanocomposites showed a significant improvement upon incorporating nano‐CaCO₃. J. VINYL ADDIT. TECHNOL., 2011. © 2011 Society of Plastics Engineers     

The preparation of core‐shell CaCO3 particles and its effect on mechanical property of PVC composites

In this study, a novel mechanochemical route to prepare core‐shell structured particles was introduced. XPS, TEM, and dissolving experimental results indicate the formation of [(inorganic particle)/(elastomer)] core‐shell structured particles, and several kinds of calcium carbonate (nano‐CaCO₃) particles with various interfaces were obtained. The mechanical properties and morphological results indicate that the surface treatment of nano‐CaCO₃ particles and the existence of outer elastic layer will strengthen the interfacial interaction between nano‐CaCO₃ particles and PVC matrix, which results in improvement of mechanical properties of PVC/CaCO₃ composites. The theoretical calculations of the interfacial interaction and DMA results confirm these especially when the surface of nano‐CaCO₃ particles was treated by MMA and coated in succession by ACR through vibro‐milling. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1084–1091, 2006     

Flame‐retardant properties of magnesium hydroxystannate and strontium hydroxystannate coated calcium carbonate on soft poly(vinyl chloride)

The flame‐retardant and smoke‐suppressant properties of soft poly(vinyl chloride) (PVC) treated with zinc hydroxystannate (ZHS), calcium carbonate (CaCO₃), magnesium hydroxystannate [MgSn(OH)₆], strontium hydroxystannate [SrSn(OH)₆], ZHS–MgSn(OH)₆, ZHS–SrSn(OH)₆, MgSn(OH)₆‐coated CaCO₃, SrSn(OH)₆‐coated CaCO₃, ZHS–MgSn(OH)₆‐coated CaCO₃, and ZHS–SrSn(OH)₆‐coated CaCO₃ were studied with the limited oxygen index, char yield, and smoke density rating methods; the mechanical properties were also studied. The results showed that, with the equivalent addition of the corresponding hydroxystannate, the soft PVC treated with hydroxystannate‐coated CaCO₃ had a higher limited oxygen index than the corresponding hydroxystannate, and the soft PVC treated with the agents containing magnesium had a higher limited oxygen index than the soft PVC treated with the agents containing strontium, except for ZHS–MgSn(OH)₆‐coated CaCO₃. The improvement in the char formation of the hydroxystannate‐coated CaCO₃ was better than that of the corresponding hydroxystannate in most cases, and the aforementioned agents reduced the smoke density rating, decreased the tensile strength, and increased the elongation and impact strength basically. Thermal analysis showed that the additives promoted the evolution of hydrogen chloride, early crosslinking, and rapid charring through the strong catalyzing effect of Lewis acids. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009