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José Luis Feijoo-Gómez, Sergio Torres-Giner, Carlos Vázquez-Torner FERRO SPAIN, Specialty Plastic Division (PCEM), Almassora, Castellón, 12550, Spain Abstract
In the present paper a new masterbatch technology for the use in XPS foam insulation panels is described. These new special additives make possible to obtain XPS insulation panels with lower values in thermal conductivity (λ value), increase in compressive strength properties and a better density profile across their thickness. All these properties are achieved by means of a reduction of the average cell size in the 25-65 % range as a consequence of the use of novel nucleating/reinforcing clay particles, which have a favorable interaction with CO2 blowing agent. Additionally, a new synergistic effect of a flame retardant organic molecule/clay is presented as a REACH compliant alternative to hexabromocyclododecane (HBCD). This new family of masterbatches is presented under the INNOVEX® trade registered name. The products here described are particularly focused on the insulation materials industry. literature it is possible to find some new examples of improved cellular structures by means of smaller amounts of well dispersed ultrathin (below the micron) inorganic fillers (2). Such reduced particles are also suitable for microscaled reinforcement, and can lead to the achievement of better mechanical properties and enhanced thermal stability than conventional foams. The goal of this paper is to describe a novel nucleating agent for the XPS insulation industry based on natural clays with ultrathin fibrillar morphology. The use of these novel fillers originally influences a high impact on the resultant cellular morphology of the polystyrene foams that makes possible to obtain insulation panels with lower thermal conductivity values and increased compressive strength. Additionally, favorable results of the interaction of these particles with CO2 are presented. Finally, the inorganic particles, when blended with non-PBT (persistent, bioaccumalative and toxic) halogenated flame retardant (FR) organic molecules, exhibited a synergistic fire retardant behavior that offers the possibility of replacing current HBCD molecules.
Because of the favorable combination of properties, price, and ease of processing, styrene polymers, and especially polystyrene, are widely used in preparing foam sheets, films and slabs for divergent end uses such as packaging, pipe and tubing, construction and insulation. Polystyrene foams, either extruded (XPS) or expanded (EPS), play an important role as insulating materials in the building industry contributing to increase the energy efficiency and lower the reduction of CO2 emissions (1). Insulation materials, however, also increase the fire load, which makes flame-retardant systems indispensable for such applications. Mineral fillers are usually added as nucleating agents to provide a large number of nucleation sites to facilitate the bubble nucleation process. Among them, the inorganic oxides, such as talc, titanium dioxide and kaolin, are the most commonly used. The size, shape, particle size distribution and surface chemistry of the nucleating agents used to form foam will play an important role in the average cell size and the final size distribution. Conventional foams have a mean cell size of more than 150 microns produced by using conventional inorganic nucleating agents such as talc (1). However, in the
INNOVEX® FR masterbatches were fabricated using a styrenic-based carrier. This recipe includes the clay particles and the flame retardant organic compound (proprietary technology), in which the organic molecules used are non-PBT. FERRO commercial masterbatch based on talc (CFSB-0016AX) and HBCD (FFSB-0133) were also used to compared the foaming/fire retardant behavior against INNOVEX® FR. All them were fabricated using twin screw technology extruders at FERRO’s facilities (Castellón, Spain). The INNOVEX® commercial grades are FFSB-0388 (Euroclass E) and FFSB-0352 (DIN B1). In Table 1 a brief description of the masterbatches used are given, including FERRO standard masterbatches of Talc and HBCD. Table 1. Detailed of MB materials used. Materials Formulation CFSB 0016AX Talc MB INNOVEX®0388 FR MB INNOVEX®0352 FR MB FFSB--0133 FR MB
*1 Proprietary composition
Description 60% Talc -*1 -*1 50% HBCD
The mean cell size and the cell size distribution were obtained using image processing software Image J from at least 75 cells in different micrographs from the same specimen. 35% in the cell size that gives. SEM micrograph XPS with INNOVEX® (XY plane). In these figures it is possible to observe the lower cell size obtained with INNOVEX® MB when compared to talc. Cellular morphology. The heat flux and conductivity were obtained by the Fourier method. Foam Characterization Density of the samples was measured by Archimedes principle using a METTLER AE240 balance with accuracy of ±10 micrograms.2. SEM micrograph of XPS with talc (XY plane). Table 2 presents the influence of the clay particles used in INNOVEX® on the cell size compared with talc. The cellular morphology was characterized by scanning electron microscopy (SEM) with a JEOL JSM820 microscope. Rheological behavior was studied by means of an AR200EX TA instruments rheometer with an extensional fixture at a temperature of 190ºC and a strain rate of 1 s-1. CO2 was used as physical blowing agent combined with ethanol as a co-blowing agent. XPS foams rods were obtained in a single/single screw tandem extruder foamed with pure CO2 (AIMPLAS/Valencia). as a result of this. Spain) following ISO 11925-2. With these three images it was possible to measure the cell size distribution in three different directions. Solid state foaming (3) was carried out at laboratory scale at CellMat (University of Valladolid.Experimental Foaming Industrial scale XPS foamed panels were obtained using a Berstoff ZE 110 / KE 400 with a capacity of 1500 Kg/h. An industrial grade of carbon dioxide was used as physical blowing agent. Fig. the second one was perpendicular to the gravity (plane XZ). The standards on which the measure is based are ASTM C518 and ISO 830 and the measurements were taken after 90 days. This shows that it is possible to obtain a reduction of c. To reconstruct the 3D structure of the foams 3 different planes of each sample were observed. thermal insulation and rheological behavior were also conducted at CellMat. Flame retardant test Flame retardant test Euroclass E was carried out at AITEX (Alicante. a drop in . Spain).a. respectively. two of them in each image. Fig. 1. The first one was the plane perpendicular to the extrusion direction (plane XY). and the third one was perpendicular to the other two (plane YZ). Compressive strength measurements were done on XPS foams pieces of 10 cm x 10 cm using an INSTRON following UNE-EN ISO 3386. Samples were kept inside a pressure vessel at 8 MPa for 24 h at 60 ºC and immediately placed in an oven at 120º C for 3 min. Results XPS foam characterization Figure 1 and 2 present the cell morphology of XPS foams with talc and INNOVEX®.
This fact reflects a higher orientation of the cells in the gravity direction that corresponds with a higher orientation of the PS molecules in the cell walls and are responsible for the increase in the compressive strength.5% in the CO2 sorption when compared to talc at the same level of PS. It can be seen an increase of ca. 25% of Bromine content per Kg of XPS foam when INNOVEX® is added in comparison with HBCD. Table 3. This is a clear indication of the higher capacity/sorption handling of CO2 by the inorganic particles presented in INNOVEX®.2 123 5. which means a two-fold contribution: weight reduction with a higher efficiency in insulation. It can be seen a reduction of ca. This behavior is reflected in a lower density value of the INNOVEX® HBCD substitution One of the main benefits of the INNOVEX® FR technology is that it combines the nucleation and reinforcing capacity with a synergistic flame retardant behavior (4). Solid state foaming PS using autoclave.2 0. Melt foaming PS rods using only CO2 Material Tmelt CO2 (wt.8 440 1. Table 6.747 EUROCLASS E 0. XPS compressive stress (σ) and anisotropy index Materials σ (KPa) CAR*1 COR*2 CFSB 0016AX 350 1. Table 5. Synergistic behavior of INNOVEX® FR Material Br cont.6 INNOVEX®0388 *1 Cell Anisotropy Ratio: Dgrav/ (Dext + Dwide + Dgrav)/3 *2 Cell Orientation Ratio: Dext/Dgrav foam.K. XPS foam 50 mm characterization.the thermal conductivity of 3. with a 23% reduction in density.6-0.23 36 56 7. This also shows that the reduction in λ is achieved in parallel with a reduction in density.35 HBCD/Talc (C) 42 100 7. In Table 5 a similar trend in the density reduction can be observed when PS is foamed from the melt using a single/single screw tandem extruder and CO2 only The PS foamed rods obtained using INNOVEX® exhibited a reduction of 15 % in density when compared to talc at the same processing conditions and CO2 content.-%) (ºC) CFSB-OO16AX 123 5.1-1. Table 2.1 to 1.6 INNOVEX®0388 In table 3 it is reported the compressive stress values in the XPS foam boards (50 mm thickness) when INNOVEX® FR is used. This behavior can be only explained as a synergistic mechanism of the organic FR molecule with the clay (5).2 INNOVEX® Density (Kg/m3) 70 60 Foaming with CO2 In table 4 the solid state foaming results are presented in order to compare the foaming capacity of INNOVEX® with conventional talc masterbatch and neat PS using pure CO2 as a physical foaming agent.0323 33 87 0.3 PS foams obtained using solid state foaming. Table 6 presents typical values of Bromine content of each material in order to pass Euroclass E fire test.4-0.29 INNOVEX®/Talc (B) 32 69 7. (Kg Flame retardant Br/100 Kg XPS) Test HBCD 0.4. Material Cell size λ (W/m·K) Density (µm) (Kg/m3) CFSB 0016AX 132 0. Table 4.4 0. which particularly increases from 1.0291 30. Materials Density Cell size %CO2 (Kg/m3) (µm) PS N2380 67 112 7.2 mW/m. In Fig 3 it can be clearly seen the influence of INNOVEX® on the foaming capacity. These results are consistent with the decrease of the Cell Orientation Ratio (COR) that is also included in the table.544 EUROCLASS E INNOVEX® . Fig.3-1.35 INNOVEX® (A) It can be seen that the presence of INNOVEX® produced an increase of 1. 25% over XPS foams board foamed with talc. The table also show that the increase in the compressive stress is related to an increase in the Cell Anisotropy Ratio (CAR) using INNOVEX®.
X. eXPRESS Polym. D. US Patent 4473665 (1984). Z. INNOVEX®.. L. eds. Keywords: XPS. which makes difficult to achieve foams with a high volume expansion 4. Shen. HBCD replacement.Q. 100-125 (2009). These results clearly suggest that the difference in the cell size is due to a nucleation effect and they are not related to changes in the melt strength.. 65. C. Lee. Such improvement in the cellular structure produces a reduction in the thermal conductivity and density. Extensional viscosity for all studied materials. G. increases the mechanical performance.Rheological Behavior In order to relate the foaming capacity with the rheological behavior of each sample. 2344 (2005). J. From the figure it can be seen that there is not an important difference in the extensional viscosity of the INNOVEX® compared with talc and pure PS. Frisch. Klempner and K. LópezCuesta and Ph. Composite Science and Technology. Materials Science and Engineering R63. also presenting a lower amount of Bromine content. J. added particles introduce a reinforcing effect that. 5.E. M. This results in a REACH compliant alternative to HBCD. Acknowledgments We want to thank CellMat (University of Valladolid) and especially Dr Miguel Angel Prodríguez-Pérez for all the collaboration and the foam characterization of the XPS foam samples. J. Yi.00E+08 1. Finally. the particles included in INNOVEX® act as novel nucleating agent that improves the cellular structure in terms of reduction of the average cell size.. foams. On one hand. New York (1991). J. Cao. Munich.H.J. Letters. CO2 sorption.1 TIME (s) 1 10 References 1. X. 2.00E+06 1. the extensional viscosity was measured both in all the PS-based systems and the results are shown in Figure 4.J. 3. Oxford University Press. On the other hand. On account of all the above.00E+04 0.M. v=1s-1 T=160ºC 1. and Wang.00E+07 1. In this sense. Alexandre.01 N 2380 ratio. Moreover. Bonnaud. cell size. Shu. Han. Huang. C. Chen. N. Conclusions The current paper describes the main benefits of a new family of masterbatches under the trade name of INNOVEX® FR for the XPS insulation foams. Handbook of Polymeric Foams and Foam Technology. Martini-Vvendenskyand and N. Dubois. CO2 has higher diffusivity and lower solubility in the PS matrix than typical hydrocarbons for XPS such as butane.H. the INNOVEX® technology can be regarded as potential new platform for XPS thermal insulation and flame retardant industry. the INNOVEX® technology offers a higher capacity of handling CO2 that opens up a novel route for the use of a much more sustainable and safe gas. the particles presented in this masterbatch produce an increase in the CO2 sorption during extrusion when compared to pure PS or talc-based PS materials. M. 4. F. Laoutid. Fig 4.00E+05 1. Vienna. EXTENSIONAL VISCOISTY (Pa· s) PS-A(INNOVEX) PS-B(INNOVEX/TALC) PS-C(HBCD/TALC) 0.P. in combination with the increase in the cell anisotropy ratio. INNOVEX® FR includes non-PBT halogenated flame retardant organic molecules that present a fire retardant synergistic effect with the inorganic particles.Z. 227 (2010).C. . thermal insulation. Xu. resulting in a more efficient insulation structure. generation of a more homogenous cellular structure and increase of the anisotropy in the gravity direction. In particular..
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