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Reactive Roto Molding Process of PP-PA6 Bilayer System

Reactive Roto Molding Process of PP-PA6 Bilayer System

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Published by Prithviraj Daga
A reactive rotational molding process of PP/PA6 bilayer systems: experimental investigations
A reactive rotational molding process of PP/PA6 bilayer systems: experimental investigations

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Published by: Prithviraj Daga on May 20, 2009
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INTRODUCTIONRotational molding is a shear–free and pressure–freeprocess used to manufacture hollow plastic partswith a relatively low investment [1]. Since therotational molding industry is presently dominatedby powdered plastics, in particular polyethylene withlimited properties, molders are being forced to useother kinds of plastic processing. Other resinscurrently used by the industry, for instancepolycarbonate and nylon, offer better properties, butat a higher cost.Reactive rotational molding (RRM) is an importantway to overcome these problems. T. This processoffers numerous benefits over the conventionalpowder processes, e.g., shorter cycle times, lowerprocessing temperatures and improved materialproperties [2]. Additionally, the use of an RRMprocess allows to synthesize engineeringthermoplastic such as high molecular weightpolyamide 6 with a through anionic polymerizationof caprolactam by the aid of chain initiators and acatalyst. This advantageous anionic polymerizationof caprolactam has been put to use in severalreactive polymerization-molding processes, namelyreaction injection molding [3], rotational molding [4,5] and centrifugal molding [6,7]. It thus permits adirect manufacturing of large and complex-shaped
Rotational molding has been regarded as a plastic molding method with great potential. Theprocess offers virtually stress
free products without weld lines or material wastage, and utilizes relativelyinexpensive molds. Yet, its growth is hindered due to long production cycle times, which are limited by thetime, required to heat and cool the mold and the product. This study concerns the fabrication of multilayerPP/PA6 parts with a reactive rotational molding process. In the past, various investigations have already beenfocused on rotational molding or the reactive process of monolayer parts. The aim of this work is thus toreduce the cycle time by making a layer via anionic polymerization of caprolactam, and then to compare eachprocess. This presentation is divided into two parts: the first part deals with rheological, dieclectrical andthermal analysis for investigating the effect of mixtures and the crystallization/polymerization; the secondpart deals with the processing of bilayer parts. First, several mixtures of catalysts and activators (i.e., 2
2 (2%of activator and 2% of catalyst), 3
3, 4
4 and 6
6) were investigated by rheology and thermal analysis in orderto determine which mixture would be the most appropriate for the rotational molding process. In the secondstep, different processing investigations were carried out in order to study the influences of parameters suchas oven time or cooling time. An experimental analysis of heat transfer in a reactive rotational moldingprocess was also led. By using an instrumented mold, associated with a radio transmission data acquisitionsystem, it could be demonstrated that the rotational parts of the PP/PA6 bilayer (reactive route)could beobtained with optimized conditions in correlation with the results of rheology and dielectric measurements.Moreover, the results indicated that it was possible to fabricate reactive bilayer parts with the rotationalmolding process with less energy and in a smaller amount time.Key words: Rotational molding, reactive process, in situ polymerization, multilayer, PA6
A reactive rotational molding process of PP/PA6 bilayer systems:experimental investigations
N. Barhoumi
1, 2
, K. Lamnawar
, A. Maazouz
Ingénierie des Matériaux Polymères-(IMP/LMM), UMR-CNRS 5223, INSA-Lyon,Université de Lyon, 69621, 17 Avenue Jean Capelle, Villeurbanne Cedex, France
Corresponding author: Abderrahim.maazouz@insa-lyon.fr 
M. Jaziri
, R. Abdelhedi
Laboratoire d’Electrochimie et Environnement. ENIS- Sfax, 3038 Sfax – Tunisie.
 plastic parts with a high degree of surface finish andcontrol of the product characteristics. . There arenumerous problems in controlling the reactionviscosity and an uneven distribution of the materialwhich are inherent to the processing of reactivemonomers that have limited the development anduptake of the process in the rotational moldingindustry [2,8] On the other hand, the manufacturingof multilayer objects by rotomolding is a new andrelatively difficult technology; one of the difficultiesis to ensure a proper adhesion between the layers.There have been several studies on the interdiffusionand reaction at polymer/polymer interfaces usingrheological and morphological tools [9], and thesereports have indicated that the final propertiesbetween layers depends on various parameters suchas the reaction temperature, contact time, shear,etc… Therefore, to gain a fundamentalunderstanding of the RRM of caprolactam, themeans of controlling the viscosity during anionicpolymerization have to be investigated.This work deals with rheological, dieclectric andthermal analysis of the polymerization kinetics of caprolactam at various temperatures andconcentrations of catalyst/chain initiator. Theobjective was to investigate the effect of mixturesand of crystallization/polymerization mechanismsduring an RRM process. Moreover, the processingof PP/PA6 bilayer parts (through a reactive routeand a molten route) was investigated.2
The materials used in this study are reported inTable 1
Table 1. The characteristic of the used materialsMonomer (CL) Caprolactam(melts at 69°C) Activateur (C) Bruggolen C230 (Aliphatic polyisocyanatein N-methyl-2-pyrolene).Catalyst (C) Bruggolen C10 (17-19% caprolactamsodium in caprolactam), (melts at 68°C)Capron BASF grade 20 melts at 220°Ccopolymer E-P Borealis grade 18
The E-P copolymer was used for the first layer, andthe monomer, catalyst and activator were employedfor the second layer. The PA6 powder was used asreference (molten route).
Polymerization kinetics (by rheology, DSC, and dielectric characterizations)
The in-situ monitoring of the polymerization wascarried out in (i) a differential scanning calorimeter(DSC-200), and (ii) a dielectric analyzer. Inaddition, the measurements of the rheologicalproperties of the material formulations wereperformed with both parallel and cone plategeometries using an ARES strain controlledrheometer.The premix was prepared in an oil bath at80 °C under a nitrogen atmosphere. I. In one vessel,a monomer/activator-mixture was melted understirring, and in a second vessel, the catalyst wasmelted together with caprolactam. Subsequently, thecontents of both vessels were mixed together.Therheological test method was a dynamic time sweepin which a 0.5 ml sample of the reactive liquid wasloaded between the rheometer plates and a strain of 5% was applied. For the dielectric study, the in-situmonitoring of the caprolactam polymerization andcrystallization was done in the mold; a TMS sensorwas introduced in a specifically designed mold inorder to collect the dielectric signal. Theexperimental conditions were as follows: aC10/C230/CL, mixture (6/6/100) under a nitrogenatmosphere with mold temperatures of140, 150, 160,170, 180 and 190°C.
 Rotational molding (description of the processand equipment)
A Rotoline pilot-scale shuttle rotational moldingmachine with an aluminum cube mold (volume:25×25×10 cm
) was used to produce PP/PA6 bilayerparts. The Datapaq® Tracker Telemetry systemmeasured, in real time, the temperatures in the oven,along the outside wall of the mold, and also of theinternal air/nitrogen during the processing cycle.After loading the PP as a first layer in the mold, themold rotation speed and the thermal cycle werestarted. The reactive systems for the second layerwere poured in the mold throughout the
. The mold rotation speeds of the two axeswere 4 and 5 rpm.3
 Influence of the environment 
The anionic polymerization of caprolactam becomesinhibited in the presence of even small amounts of moisture, due to the anionic nature of the reaction
 [10]. Figure 1 shows the effect of the environmenton the reaction time and viscosity increase at 160°C. The polymerization reaction under the effect of moisture. Therefore, the storage and processing hadto be conducted in absolutely moisture-freeenvironments.
 Influence of the catalyst/activator concentration
Increasing the amount of activator resulted inadditional initiation points for chain growth. Also,with the increase of the catalyst concentration, moreanions were set free and more complexes could beformed. Consequently, the polymerization rateincreased [11]. Figure 2 shows the effect of varyingthe ratio of catalyst/activator on the induction timeand viscosity-time profile of the CL polymerizationat a test temperature of 160ºC. It can be seen thatwhen increasing the ratio from 2 to 4 the inductiontime was decreased by 300 s. It can also be notedfrom figure 2 that the rate of polymerizationincreased with the composition. Moreover, figure 3shows the connection between polymerization andcrystallization as observed by rheology and DSC.
CL/C10/C230(100/3/3) at 160°C
0 500 1000 1500
Time (s)
   E   T   A   *   (   P  a .  s   )
Premix under airPremix under N2
Fig. 1. The effect of the environment on the viscosity-timeprofile of CL/C10/C230 at 160 ºC.
 Influence of the polymerization temperature
The polymerization took place below the polymermelting and crystallization point (the z (thepolymerization and crystallization kinetics occurredsimultaneously), resulting in a solid and highlycrystalline (40–50%[10]) PA-6. Figure 4demonstrates the effect of an increasing thetemperature on the induction time and viscosityprofile of a 3/3 ratio formulation. It can be seen thatraising the temperature reduced the induction timeand increased the rate of polymerization.
Fig. 2. The effect of the concentration of the catalyst/activatoron the viscosity-time profile of CL/C10/C230 at 160 ºC.
4/4 Isotherme at 160°C
-0,1-0,10,00,10,10 5 10 15
Time (min)
   H  e  a   t   f   l  o  w   (   W   /  g   )
   E   T   A   *   (   P  a  -  s   )
Fig. 3. A superimposing of the viscosity-time and heat flowprofile.Fig. 4. The effect of the polymerization temperature on theviscosity-time profile of CL/C10/C230.
 Dielectric in-situ monitoring of caprolactam polymerization and crystallization
   L  o  g 
Time (min)
140 °C 170 °C150 °C 180 °C160 °C 190 °C
 Fig. 5. The in-situ monitoring of the electrical conductivity
Dielectric measurements were carried out to controlthe in-situ polymerization and crystallization of caprolactam at various temperatures. The results aredisplayed in figure 5, where, at higher temperatures(180 - 190°C), a two-step conductivity decrease canbe noticed corresponding to the CL polymerizingand then crystallizing (cycle time ~ 5 – 6 min). Atlower temperature (e.g., 140°C), the polymerizationand crystallization occurred simultaneously.
Preparation of PA6 as a second layer byrotational molding from caprolactam
0 500 1000 1500
Time (s)
   E   T   A   *   (   P  a .  s
180 °C160 °C140 °C
0,E+005,E+041,E+050 200 400 600 800 1000
   E   T   A   *   (   P  a .  s   )

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