Blends of poly(vinyl chloride) (PVC)/natural rubber‐g‐(styrene‐co‐methyl methacrylate) for improved impact resistance of PVC

To improve the mechanical properties of poly(vinyl chloride) (PVC), the possibility of combining PVC with elastomers was considered. Modification of natural rubber (NR) by graft copolymerization with methyl methacrylate (MMA) and styrene (St) was carried out by emulsion polymerization by using redox initiator to provide an impact modifier for PVC. The impact resistance, dynamic mechanical analysis (DMA), and scanning electron microscopy (SEM) of St and MMA grafted NR [NR‐g‐(St‐co‐MMA)]/PVC (graft copolymer product contents of 5, 10, and 15%) blends were investigated as a function of the amount of graft copolymer product. It was found that the impact strength of blends was increased with an increase of the graft copolymer product content. DMA studies showed that NR‐g‐(St‐co‐MMA) has partial compatibility with PVC. SEM confirmed a shift from brittle failure to ductility with an increase graft copolymer content in the blends. The mechanical properties showed that NR‐g‐(St‐co‐MMA) interacts well with PVC and can also be used as an impact modifier for PVC. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1666–1672, 2004     

Graft modification of highly chlorinated polyethylene (HCPE) with methyl methacrylate by the mechanochemistry reaction. I. Synthesis and characterization

Highly chlorinated polyethylene‐graft‐methyl methacrylate (HCPE‐g‐MMA; HCPE with chlorine contents > 60%), obtained by a mechanochemistry reaction, is discussed in detail. A two‐roll mill was used in the process. The reaction conditions affecting the structure of HCPE‐g‐MMA copolymers were measured in terms of calculation of graft efficiency (GE), graft degree (GD), and copolymerization rate/homopolymerization rate (R_c/R_h) by ¹H‐NMR spectroscopy. Based on these results, it is concluded that the chlorine contents of HCPE, the additional amount of MMA, and the mechanochemistry reaction time all have impacts on the structure of the polymer. The results also confirm that grafting is very much favored by the mechanochemistry reaction. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 811–816, 2003     

The dynamic mechanical analysis,impact, and morphological studies of EPDM–PVC and MMA‐g‐EPDM–PVC blends

The dynamic mechanical studies, impact resistance, and scanning electron microscopic studies of ethylene propylene diene terpolymer–poly(vinyl chloride) (EPDM–PVC) and methyl methacrylate grafted EPDM rubber (MMA‐g‐EPDM)–PVC (graft contents of 4, 13, 21, and 32%) blends were undertaken. All the regions of viscoelasticity were present in the E′ curve, while the E″ curve showed two glass transition temperatures for EPDM–PVC and MMA‐g‐EPDM–PVC blends, and the T_g increased with increasing graft content, indicating the incompatibility of these blends. The tan δ curve showed three dispersion regions for all blends arising from the α, β, and Γ transitions of the molecules. The sharp α transition peak shifted to higher temperatures with increasing concentration of the graft copolymer in the blends. EPDM showed less improvement while a sixfold increase in impact strength was noticed with the grafted EPDM. The scanning electron microscopy micrographs of EPDM–PVC showed less interaction between the phases in comparison to MMA‐g‐EPDM–PVC blends. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1959–1968, 1999     

Properties and morphology of poly(vinyl chloride) blends with solid‐state‐chlorinated polyethylene

Correlations of the stress‐strain behavior and impact strength of poly(vinyl chloride) (PVC) blends with different amounts and chlorine contents of solid‐state‐chlorinated polyethylene (CPE) were studied. The relationships between the morphology and properties of the PVC/CPE blends also were investigated. The results of dynamic mechanical analysis and transmission electron microscopy showed that PVC/CPE blends are partially compatible systems and that a certain interaction exists between the two phases. When the amount of CPE (chlorine content, 36–42%) was 7–15 phr (parts by weight per hundred parts of resin), an essentially perfect CPE network was formed, and the blends showed better impact resistance. A Brabender Plasticorder study revealed that CPE can promote the plasticity of PVC and improve its processability. J. VINYL ADDIT. TECHNOL., 2010. © 2010 Society of Plastics Engineers     

Miscibility in poly(vinyl chloride)/chlorinated poly(vinyl chloride) blends,and blends of different chlorinated poly(vinyl chlorides)

Blends of poly(vinyl chloride) with chlorinated poly(vinyl chloride) (PVC), and blends of different chlorinated poly(vinyl chlorides) (CPVC) provide an opportunity to examine systematically the effect that small changes in chemical structure have on polymer-polymer miscibility. Phase diagrams of PVC/CPVC blends have been determined for CPVC's containing 62 to 38 percent chlorine. The characteristics of binary blends of CPVC's of different chlorine contents have also been examined using differential calorimetry (DSC) and transmission electron microscopy. Their mutual solubility has been found to be very sensitive to their differences in mole percent CCl₂ groups and degree of chlorination. In metastable binary blends of CPVC's possessing single glass transition temperatures (T_g) the rate of phase separation, as followed by DSC, was found to be relatively slow at temperatures 45 to 65° above the T_g of the blend.     

The synthesis of poly(3‐hydroxybutyrate)‐g‐poly(methylmethacrylate) brush type graft copolymers by atom transfer radical polymerization method

Brush type of poly (3‐hydroxy butyrate), PHB, copolymer synthesis has been reported. Natural PHB was chlorinated by passing chlorine gas through PHB solution in CHCl₃/CCl₄ mixture (75/25 v/v) to prepare chlorinated PHB, PHB‐Cl, with the chlorine contents varying between 2.18 and 39.8 wt %. Toluene solution of PHB‐Cl was used in the atom transfer radical polymerization (ATRP) of methyl methacrylate, MMA, in the presence of cuprous bromide (CuBr)/2,2′‐bipyridine complex as catalyst, at 90°C. This “grafting from” technique led to obtain poly (3‐hydroxybutyrate)‐g‐poly(methylmethacrylate) (PHB‐g‐PMMA) brush type graft copolymers (cylindrical brush). The polymer brushes were fractionated by fractional precipitation methods and the γ values calculated from the ratio of the volume of nonsolvent to volume of solvent of brushes were ranged between 2.8 and 9.5 depending on the molecular weight, grafting density, and side chain length of the brushes, while the γ values of PHB, PHB‐Cl, and homo‐PMMA were 2.7–3.8, 0.3–2.4, and 3.0–3.9, respectively. The fractionated brushes were characterized by gel permeation chromatography, ¹H‐NMR spectrometry, thermogravimetric analysis (TGA), and differential scanning calorimetry techniques. PHB‐g‐PMMA brush type graft copolymers showed narrower molecular weight distribution (mostly in range between 1.3 and 2.2) than the PHB‐Cl macroinitiator (1.6–3.5). PHB contents in the brushes were calculated from their TGA thermograms and found to be in range between 22 and 42 mol %. The morphologies of PHB‐g‐PMMA brushes were also studied by scanning electron microscopy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Single phase polymer systems: CPVC/styrene copolymer alloys

Random copolymers of styrene and maleic anhydride are miscible with chlorinated poly(vinyl chloride) [CPVC] in all blended proportions. Miscibility was evident in a single glass transition temperature investigated by thermal and mechanical studies. This degree of miscibility differs from the partial miscibility obtained with PVC/styrene copolymers reported previously, where single phase morphology was present only at low blend proportions. Tailoring of physical properties such as heat resistance, flamability resistance, and processability are achieved by varying the relative proportions of CPVC and styrenic copolymer in this miscible alloy system.     

Processing aids for chlorinated polyvinyl chloride

Comparative studies of melt processability showed that chlorinated polyvinyl chloride (CPVC) had low melt index and high Brabender melt temperature and torque, as compared with conventional rigid polyvinyl chloride (PVC). Of 3 processing aids at 10 percent concentration, triphenyl phosphate increased melt index 30-fold, fusion rate 10-fold, melt temperature 20°C, and torque 31 percent in CPVC. Two other processing aids, an acrylic and a styrene/acrylonitrile copolymer, were less effective. Improvements in PVC were less dramatic than in CPVC. Overall, use of processing aids made CPVC processability equal or even superior to conventional rigid PVC.     

Effects of acrylic‐based processing aids on processibility,rheology, thermal and structural stability,and mechanical properties of PVC/wood–sawdust composites

Methyl methacrylate and ethylacrylate (MMA‐co‐EA) and methyl methacrylate and butylacrylate (MMA‐co‐BA) copolymeric processing aids were introduced into poly(vinyl chloride) (PVC)/33.3 wt % wood–sawdust composites containing 0.6 and 2.4 phr of calcium stearate lubricant. The properties of the composites were monitored in terms of processibility, rheology, thermal and structural stability, and mechanical properties. It was found that the mixing torque, wall shear stress, and extrudate swell ratio increased with increasing processing aid content because of increased PVC entanglement. MMA‐co‐BA (PA20) was found to be more effective than MMA‐co‐EA (K120 and K130), this being associated with the flexibility of the processing aids, and the dipole–dipole interactions between sawdust particles and polymeric processing aids. The sharkskin characteristic of the composite extrudate at high extrusion rate was moderated by the presence of processing aids. Adding the acrylic‐based processing aids and lubricant into PVC/sawdust composites improved the thermal and structural stability of the composites, which were evidenced by an increase in glass transition and decomposition temperatures and a decrease in polyene sequences, respectively. The changes in the mechanical properties of the composites involved a composite homogeneity, which was varied by degree of entanglement and the presence of wood sawdust, and un‐reacted processing aids left in the composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 782–790, 2004     

Improvement in the heat resistance of poly(vinyl chloride) profile with styrenic polymers

The styrenic polymers poly(α‐methylstyrene‐acrylonitrile) (α‐MSAN) and poly(acrylonitrile‐butadiene‐styrene) (ABS) and (three types) were used to improve the heat resistance of poly(vinyl chloride) (PVC). The glass transition temperature (T_g) and miscibility were analyzed by dynamic mechanical thermal analysis (DMTA). Effects of composition on heat distortion temperature (HDT) were investigated with the different styrenic polymers. Other physical properties such as mechanical properties and melt flow rate (MFR) were also determined. Morphology was observed by scanning electron microscopy (SEM) in order to support the mechanical property results. The PVC was miscible with α‐MSAN but partially miscible with the ABS series, and α‐MSAN was much more effective in enhancing the T_g and HDT of rigid PVC than the ABS series as for mechanical properties, the addition of α‐MSAN could improve the tensile strength, bending strength, and bending modulus but decrease the impact strength of the materials compared with the addition of the ABS series. Improvement in processability was observed in the MFR results with the addition of the styrenic polymers. On the basis of all the properties, the formulation with an α‐MSAN content of 30 phr (parts per hundred parts of resin) was superior for heat‐resistant PVC profile. The HDT of PVC could be increased from 76.9°C to 85.4°C (measured under the maximum bending stress of 0.45 MPa) and combined with good mechanical properties and processability by the addition of 30 phr of α‐MSAN. Also, a heat‐resistant PVC profile was successfully fabricated. J. VINYL ADDIT. TECHNOL., 2011. © 2011 Society of Plastics Engineers     

Synthesis of a new compatibilisant agent PVC‐g‐MA and its use in the PVC/alfa composites

The main objective of this research was to synthesize a new compatibilisant agent (PVC‐g‐MA), which was grafted from the maleic anhydride on the PVC chains. The presence of maleic anhydride grafting on PVC was made evident by infrared analysis. PVC‐g‐MA was used like compatibilisant to solve the problem of the incompatibility between the hydrophobic polymeric matrix (PVC) and hydrophilic fiber (alfa). Composites samples were prepared with different alfa fiber loading (10, 20, and 30 wt %) and incorporating PVC‐g‐MA (1, 3, and 5 wt %) or PP‐g‐MA (3 wt %). The tensile properties, the thermal stability and the morphology of the composites were investigated. The result indicated that the PVC‐g‐MA increased the interfacial adhesion between the fibers and the polymer matrix and this effect was better than that obtained for the maleated‐polypropylene‐coupled composites. Microstructure analysis of the fractured surfaces of MAPP modified composites confirmed improved interfacial bonding. The addition of alfa and PVC‐g‐MA increased the thermal stability of the composites. The temperature of degradation of the polymer matrix increased about 16°C in comparison to the noncoupled composite, indicating that PVC‐g‐MA improved the thermal stability of the polymer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Mechanical and thermal properties of poly(vinyl chloride)/α‐methyl‐styrene‐acrylonitrile blends prepared by melt extrusion

In this article, we have examined the physical and mechanical properties of poly(vinyl chloride) (PVC)/α‐methyl‐styrene‐acrylonitrile (αMSAN; 31 wt % AN concentrations) blends with different blend ratios. And, we also examined the effect of the molecular weights of PVC on the miscibility and material properties of the blends prepared by melt extrusion blending. Our results showed that the PVC/αMSAN blends have good processing properties and good miscibility over all blend ratios because of the strong interaction between PVC and αMSAN. And, the blends showed enhanced mechanical and thermal properties. In addition, high molecular weight PVC showed reasonable processability when melt blended with αMSAN, which resulted in enhanced mechanical and physical properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Poly(dl‐Lactic Acid)‐Based Linear Polyurethanes Capable of Forming Physical Crosslinking via UPy Quadruple Hydrogen Bonding Assembly

Linear shape memory polyurethanes based on poly(dl ‐lactic acid) (PDLLA) macrodiol (PDLLA‐SMPUs) have various advantages such as good processability, biodegradability, shape memory effect, and biocompatibility, yet the insufficient mechanical properties prevent their effective applications in bone repair. 2‐Ureido‐4[1H]‐pyrimidone (UPy) can form strong quadruple hydrogen bonding. Here, a new linear PDLLA‐SMPU containing pendant UPy units (UPy‐p‐PDLLA‐SMPU) is designed and synthesized. The pendant UPy units may dimerize to form physical crosslinking among UPy‐p‐PDLLA‐SMPU chains. As a result, UPy‐p‐PDLLA‐SMPU demonstrates both good processability and significantly higher mechanical properties than the corresponding linear PDLLA‐SMPU without pendant UPys. In addition, UPy‐p‐PDLLA‐SMPU shows excellent shape memory effect near body temperature, with a shape fixity ratio of up to 98.6% and a recovery ratio of up to 92.9%. This work provides a new strategy to design SMPUs integrating the merits of linear and crosslinked polyurethanes, and the obtained UPy‐p‐PDLLA‐SMPU is a promising material for bone tissue repair in view of the mechanical, thermal, and shape memory properties.     

Morphologies and dynamic mechanical properties of core‐shell emulsifier‐free latexes and their copolymers for P(BA/MMA)/P(MMA/BA) and P(BA/MMA)/PSt systems in the presence of AHPS

Different poly(methyl methacrylate/n‐butyl acrylate)/poly(n‐butyl acrylate/methyl methacrylate) [P(BA/MMA)/P(MMA/BA)] and poly(n‐butyl acrylate/methyl methacrylate)/polystyrene [P(BA/MMA)/PSt] core‐shell structured latexes were prepared by emulsifier‐free emulsion polymerization in the presence of hydrophilic monomer 3‐allyloxy‐2‐hydroxyl‐propanesulfonic salt (AHPS). The particle morphologies of the final latexes and dynamic mechanical properties of the copolymers from final latexes were investigated in detail. With the addition of AHPS, a latex of stable and high‐solid content (60 wt %) was prepared. The diameters of the latex particles are ～0.26 μm for the P(BA/MMA)/P(MMA/BA) system and 0.22–0.24 μm for the P(BA/MMA)/PSt system. All copolymers from the final latexes are two‐phase structure polymers, shown as two glass transition temperatures (T_gs) on dynamic mechanical analysis spectra. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3078–3084, 2002     

Dynamic mechanical properties of semi‐interpenetrating polymer network‐based on nitrile rubber and poly(methyl methacrylate‐co‐butyl acrylate)

In this article, semi‐interpenetrating polymer network (Semi‐IPNs) based on nitrile rubber (NBR) and poly(methyl methacrylate‐co‐butyl acrylate) (P(MMA‐BA)) were synthesized. The structure and damping properties of the prepared Semi‐IPNs blends were characterized and by fourier transform infrared spectrum (FTIR), dynamic mechanical analysis (DMA), scanning electron microscopy (SEM), thermogravimetric analysis (TGA/DTG), and tensile mechanical properties. The results showed that interpenetrating network based on P(MMA‐BA) and NBR was successfully obtained, which showed the improved thermal stability compared to NBR/P(MMA‐BA)‐based two‐roll mill blends. Furthermore, Semi‐IPNs showed significantly better the dynamic mechanical properties than that of the two‐roll mill system. With the increasing feed ratio of BA and MMA during the preparation of Semi‐IPNs, the loss peak position for P(MMA‐BA) in NBR/PMMA IPNs shifted to a lower temperature from 20°C to ?17°C, and when NBR in Semi‐IPNs was accounted for 40 wt %, the dynamic mechanical thermal analysis showed that much more advanced damping material with wider temperature range (?30°C < T < 80°C) as tan δ > 0.45 can be achieved. Therefore, it was expected as a promising way to obtain the excellent damping materials with good oil‐resisted properties according the Semi‐IPNs system. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40217.     

Thermal and mechanical properties of wood flour–polystyrene blends from postconsumer plastic waste

Polystyrene (PS) from packing materials and plastic cups was reinforced with 30 and 50% wood flour through a blending process with and without a commercial compatibilizing agent. The processability of the pure recycled polystyrene (rPS) and wood–rPS composites was studied in terms of the torque of the mixing process; this was then compared with that of a commercial virgin multipurpose PS. The physical and mechanical properties were compared with those of the virgin PS reinforced with 30 and 50% wood flour. The results show that the mechanical properties of the pure and reinforced rPS did not decrease with respect to the virgin PS, and in terms of the impact strength, the rPS was superior to the virgin plastic. The mechanical properties were not affected by the commercial compatibilizing agent, but the torque of the blends was significantly lower with the compatibilizer. Differential scanning calorimetry (DSC) and dynamic mechanical analysis were used to study the glass‐transition temperature (T_g) of both the pure virgin PS and pure rPS and the wood flour–PS composites. The T_g values of the rPS and wood–rPS composites were higher than those of the virgin PS and wood–virgin PS composites. The use of rPS increased the stiffness and flexural modulus of the composites. Thermogravimetric analysis revealed that the thermal stability of rPS and its composites was slightly greater than that of the virgin PS and its composites. These results suggest that postconsumer PS can be used to obtain composite materials with good mechanical and thermal properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Dielectric analysis of α‐relaxation process of chlorinated poly(vinyl chloride) stabilized with nitro‐phenyl maleimide

Nitro‐phenyl maleimide (NPM), is the organic stabilizer for poly (vinyl chloride) (PVC), has been investigated as thermal plasticization for rigid chlorinated poly (vinyl chloride) (CPVC). Dielectric relaxation of CPVC stabilized with 10 wt% of NPM has been studied in temperature and frequency ranges of 300–450 K and 10 kHz–1 MHz, respectively. An analysis of the dielectric constant, ε′ and dielectric loss index, ε″, was performed assuming a plasticization effect of NPM molecules. The plasticization effect of NPM molecules was confirmed by the behavior of the dielectric modulus M′ and M″ spectra. A clear dielectric α‐relaxation process has been obtained in the studied temperature range. The results showed that NPM reduce the glass transition temperature, T_g, of CPVC by about 20 K. This effect has been assigned to the plasticization effect of NPM. At lower temperatures, dielectric modulus spectra reveal that there is a role of the effect of the electrode polarization in the relaxation process. The behavior AC conductivity, σ_ac, indicated that the conduction mechanism in all CPVC samples is hopping type conduction. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

The influence of Ni/Nd‐based Ziegler–Natta catalyst on microstructure configurations and properties of butadiene rubber

Neodymium (Nd)‐based Ziegler–Natta catalyst has been well known for preparing polybutadiene rubber (BR) containing high, about 98%, cis−1,4 configuration with extremely low gel content providing superior resistance to low‐temperature fatigue and abrasion. However, its cost is more expensive than a conventional nickel (Ni)‐based catalyst. The Nd‐BR has poor processability with high cold flow due to its high linearity and molecular weight. To compare with a traditional process, the BR produced by Ni‐based catalyst has higher level of branching resulting in the better processability, but it contains medium amount of gel. To balance the catalyst cost and the BR properties, this article reported the influence of a solution containing Ni‐ and Nd‐based Ziegler–Natta catalyst (Ni/Nd) using diethyl aluminum chloride and triethyl aluminum as co‐catalysts on 1,3‐butadiene (BD) conversion and physical properties of the elastomeric materials based on obtained rubber (Ni/Nd‐BR). In the presence of toluene, the increase in the Ni/Nd molar ratio from 0.0/1.0 to 0.4/0.6 yielded Ni/Nd‐BR containing cis−1,4 units of 95%–96% with significantly decreasing both levels of vinyl−1,2 and trans−1,4 configurations from 0.26% to 0.13% and 4.44% to 3.07%, respectively. When cyclohexane was applied as the reaction media, 100% BD conversion was achieved and the Ni/Nd‐BR had very low content of vinyl−1,2 unit (0.07%). The mechanical properties in terms of tensile properties and abrasion resistance of the elastomer based on Ni/Nd‐BR having high cis‐1,4 and relatively higher trans−1,4 configurations were superior to elastomers based on commercial BRs produced by using Ni‐ and Nd‐based catalyst systems. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41834.     

Preparation and properties of compatibilized PVC/SMA‐g‐PA6 blends

The morphology and mechanical properties of PVC/SMA‐g‐PA6 blends were investigated in this paper. Graft to polymer SMA‐g‐PA6 was prepared via a solution graft reaction between SMA and PA6. FTIR test evidences the occurrence of the graft reaction between SMA and PA6. DSC analysis shows that SMA‐g‐PA6 has a lower melting point of 187°C, which may result in a decrease in crystallinity of PA6 and thus enable efficient blending of SMA‐g‐PA6 and PVC. Compatibilization was evidenced by the dramatic increase in mechanical properties, the smaller particle size and finer dispersion of PA6 in PVC matrix, and, further, a cocontinuous morphology at 16 wt % SMA‐g‐PA6 content. SMA‐g‐PA6 from the solution graft reaction can toughen and reinforce PVC material. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 432–439, 2004     

Preparation of chlorinated poly(vinyl chloride)‐g‐poly(N‐vinyl‐2‐pyrrolidinone) membranes and their water permeation properties

Chlorinated poly(vinyl chloride) (CPVC) membranes for microfiltration processes were prepared with the combined process of a solvent evaporation technique and the water‐vapor induced‐phase‐inversion method. CPVC membranes with a mean pore size of 0.7 μm were very hydrophobic. These membranes were subjected to surface modification by ultraviolet (UV)‐assisted graft polymerization with N‐vinyl‐2‐pyrrolidinone (NVP) to increase their surface wettability and decrease their adsorptive fouling. The grafting yields of the modified membranes were controlled by alteration of UV irradiation time and NVP monomer concentration. The changes in chemical structure between the CPVC membrane and the CPVC‐g‐poly(N‐vinyl‐2‐pyrrolidinone) membrane and the variation of the topologies of the modified PVC membranes were characterized by Fourier transform infrared spectroscopy, gel permeation chromatography, and field emission scanning electron microscopy. According to the results, the graft yield of the modified CPVC membrane reached a maximum at 5 min of UV exposure time and 20 vol % NVP concentration. The filtration behavior of these membranes was investigated with deionized water by a crossflow filtration measurement. The surface hydrophilicity and roughness were easily changed by the grafting of NVP on the surface of the CPVC membrane through a simultaneous irradiation grafting method by UV irradiation. To confirm the effect of grafting for filtration, we compared the unmodified and modified CPVC membranes with respect to their deionized water permeation by using crossflow filtration methods. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3188–3195, 2003