Extrusion Anomalies Plate - Out

By: Dwight A. Holtzen and J. A. Musiano DuPont White Pigment and Mineral Products Chestnut Run Technical Service Laboratory Wilmington Delaware Abstract: Relentless deposition of debris on extruder die surfaces negatively affect productivity during extrusion processes. Removal of these unwanted deposits is often the source of much down time. This paper will review previously published reports(1, 2) and present new data regarding the accumulation of compound remains on extrusion dies and extruder screws. A proposal of how these relate to simple rheological properties of the materials being processed will be given. Deposition of residues on extruder screws will also be discussed and possible mechanisms proposed for the deposits accumulated in the melting zone of the machine.

Introduction: Imperfections affecting film smoothness, gauging or appearance are often caused by unwanted die deposits. How these deposits form has been the subject of a number of works which were reviewed in a recent publication(3). In these works two suspected mechanisms are elucidated showing how die deposits can result from mismatches of rheology or because of inherent rheological properties of the material bulk being extruded through changing geometry. One common factor in both of these mechanisms is that the debris adhering to the die lands and eventually exuding from the exit almost always shows evidence of oxidative degradation. These two mechanisms cause different plate-out composition and rate. Die plate-out can occur in a very short time frame and may be of a composition that is similar to only one component of a complex blend of materials being extruded. However, plateout resulting from another mechanism may require a long induction period and be of a composition similar to the bulk of the material(s) being extruded. The first mechanism we will explore simple mixing of a multi-component system, it concerns the degree of mixing and relative viscosity and other parameters such as component viscous flow and activation energy (Ea) that can be related to unwanted die deposits. This mechanism usually causes appearance defects rather than gauging. The second mechanism assumes that the mixture is homogeneous. It relates plate-out formation to the relative time constant for the fluid being extruded through changing geometry relative to the time the fluid is exposed to the changing conditions. This second mechanism can be related to the ratios of these times which is a dimensionless quantity named the Deborah number (De). The Deborah number is usually written as: De =
/ t Where "
" is defined as a characteristic (maximum) time constant for the fluid being extruded and "t" is the time over which flow occurs through a particular geometry. As the De number increases magnitude so does the possibility of unstable flow and die deposit accumulation. Experimental: To investigate the formation of plate-out due to rheological differences and inadequate distributive mixing a number of commercial concentrates containing 50% by weight of rutile Pigment White 6 (CI# 77891) were obtained. The carrier resin in all concentrates was high pressure low density polyethylene (LDPE). These concentrates were let down into LDPE in a 2.54 cm single screw extruder fitted with an 24:1 L/D Maddock mixing screw. Film was cast from a 10 cm wide "coat hanger" type die. Rheological properties of the materials was measured in a capillary rheometer. Details of the resin properties and rheological results are contained in reference (2). Extruded films were examined visually under low power magnification to identify several different types of inclusions and plate-out debris. SEM images and EDXA were used in some cases for more conclusive identification and determination of pigment concentration within the imperfections. Experimental details of investigations relating die lip plate out related to polymer relaxation phenomena are covered in a previously published report (1). Again the rheological data was obtained from a capillary rheometer,

however, special dies were constructed to study the effects of relaxation. Results of this investigation demonstrate the pronounced effect of Deborah number on plate-out. Extruder screw plate-out was investigated by mechanically removing the unwanted deposits and microscopic examination. SEM was the primary mode of analysis coupled with Energy Dispersive X-ray Analysis (EDXA). Results and Discussion: If complete mixing of all phases, e.g. letdown resin and concentrate is not completed in the screw section of an extruder, flow in transfer piping and dies can result in phase segregation. This is especially true if there is a great disparity in rheology (and compatibility) of the phases. Thus, two separate issues need to be addressed; A) mixing of all individual phases in the extruder and B) separation of those phases in a Poisseuille flow regime. Complete mixing of all components in the extruder is key to producing homogeneous film. However, operation of extrusion equipment beyond its design limits sometime results in insufficient residence time in the extruder barrel to thoroughly homogenize all of the components of a blend. Mixing components of different viscosity have been studied by a number of researchers (4,5,6). While most of the systems we work with are nonNewtonian, how rapidly two phases will mix while under simple shear can be visualized by examination of a plot, Figure I, of equation 11.4-1 from reference (4). A similar analysis is given in an earlier reference (6). This Newtonian approximation must be used with caution, however, it does show the importance of relative viscosity and volume fraction on the degree of mixing. While one would assume that a very low viscosity pigment concentrate would mix easily into a higher viscosity let down resin this is not always true. Relative volume fractions of each phase must be considered. Optimization of the relative viscosity of phases is good practice and the value of this practice will explained in the discussion that follows. If all phases are not completely mixed when the material exits the extruder and flows into the die the possibility of radial segregation exists. As multiple phases are pumped into the transfer piping and ultimately to the die by pressure flow alone, phases begin to separate. Lower viscosity components migrate toward the region of highest shear rate (the tube wall or die land) while the higher viscosity material will move toward the region of lowest strain and center itself in the tube or channel. This is shown diagrammatically in figure II. To further support this mechanism Figure III shows the appearance of an elongated "football" shaped inclusion centered in the film. The viscosity (measured at 500 sec.-1 at 180C) of the inclusion was about 5 times higher than the surrounding material. Figure IV shows a high concentration of pigment in a thin layer at the surface of a similar film. In this case the relative viscosity of the pigment concentrate to the letdown resin is the reverse of that shown in the previous figure. More detailed studies are to be found in reference (2). Because polymer melts typically do not flow as Newtonian fluids, consideration of other rheological properties must be taken into account. It is well known that relaxation characteristics of polymers can cause flow anomalies in dies (7) and it is proposed that these may be responsible for certain types of die lip plate-out (1). A convenient dimensionless number, the Deborah number (De), can be related to flow anomalies. Increasing De leads to more pronounced vortex formation in converging flow, it was found that die lip plate-out increased as D e increased. Figure V shows the effect of De number on vortex formation in a converging capillary die. Plate-out related to this mechanism has several characteristics; A) a relatively long induction time was observed before plateout appeared at the die exit as a chain of droplets, B) exuded material is highly degraded, and C) the composition of the droplets is very near that to the bulk material being extruded. Tests show that increasing the De will result in more pronounced plate-out. The De number can be increased by either more rapid extrusion or by selecting a different molecular weight and/or architecture. Figure VI shows the results of extruding equal quantities of a pigmented Low Density Polyethylene through a slot die. Photos of the die exit clearly show increasing plate-out vs. rate of extrusion. In figure VII a higher molecular weight resin was substituted resulting in a higher De and the resulting plate-out is readily apparent. Figure VII diagrammatically shows the proposed mechanism. Extruder screw plate-out is most prevalent in the melting zone of the extruder. In this zone all of the components of the final composition are expected to melt and mix. Two mechanisms are responsible for build up of hard residues on the root of the extruder screw. These are: Condensation of melt on the screw root and by thermophoresis causing resin and particles of fillers and pigments to migrate toward the (cooler) screw. Deposition

of materials can leave a detailed record of what has been run through the extruder. Figure VIII shows a cross section of the layer deposited on the screw from an extruder that alternately processed unpigmented and TiO2 pigmented compositions. The image in the figure is SEM / EDXA showing alternate layers of carbonized resin and a composite of carbonized resin and pigment. Pigment concentration in the layers was found to be near 85% weight, not typical of actual concentration that was being extruded. As the TiO2 layer is deposited, any excess resin is being ejected leaving a random densely pack layer of pigment. As the cake of residue increases in thickness, it grows weaker in physical strength and can fail under the stress found in the melting section. When this occurs a packet of debris is transported down stream and can appear as a mass of small unwanted fragments.

Conclusions: Relatively simple rheological properties such as viscosity and activation energy of viscous flow have been found to correlate to the appearance of certain types of imperfections in extruded film including "streaking" and "specking" (2). Streaking is caused by one or more of the components in a blend being forced to the die land. Specking results from a component aligning in the center of the flowing resin. Once the material arrives at the die land it slowly creeps toward the exit and can appear an elongated surface imperfection. A mechanism involving a relationship between relaxation properties of a composition to plate-out has been shown. In some cases fillers and pigments have been shown to change plate-out potential and the reader is referred to reference (1) for more detailed information. Condensation of material and / or thermophoretic transport of particles to the screw root in the melting section can explain the build up of layers of debris. This cake of degraded materials periodically breaks free resulting in packets of imperfections in the final product.

References: (1) Dwight A. Holtzen & J. A. Musiano "Die Lip Plate-Out, A Proposed Mechanism", Conference Proceedings, SPE RETEC, St. Louis, 1996. Dwight Holtzen "Mixing Masterbatch and Resins - Rheological Implications", Conference Proceedings, SPE, RETEC, New Orleans LA, 15 - 17 October, 1991. Jesse D. Gander and A. Jeffery Giacomin "Review of Die Lip Buildup in Plastics Extrusion", Polymer Engineering and Science, July 1997, Vol. 37, No. 7, pp 1113-1126. Z. Tadmor and C. G. Gogos, Principles of Polymer Processing , John Wiley & Sons, 1979, Chapt. 11. H. F. Mark et.al. ed., Encyclopedia of Polymer Science, Supplement Volume , John Wiley & Sons, NY, 1989, pp 481-492. James M. McKelvey, Polymer Processing, John Wiley and Sons, Inc. NY, 1962, Chapter 12. Arthur S. Lodge, Michael Renardy and John A. Nohel Ed., Viscoelasticity and Rheology, Academic Press, Inc. NY, 1985. (see: K. Walters, "Overview of Macroscopic Viscoelastic Flow", pp 47 - 79)

(2)

(3)

(4) (5)

(6) (7)

Figure I: Relative Strain of Minor Phase vs. Total Strain and Volume Concentration of Minor Phase
10

5 Relative Strain 3

2
0

3 4 5 8
1.0 0.8 0.6
2

-2

0.4

0.2

Relative Viscosity of Minor to Major Phase

Note: contours ploted at one unit intervals between 2 and 9

0.0

0.5 0.4 0.3 0.2 Volume Fraction 0.1 of 0.0 Minor Phase

        

         
  
  
 

   

      

   
 

    

 

     
  
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Figure III: Inclusion of Unmixed Resin in Multi-Layer Film

Film Layer A

Elongated High Viscosity Inclusion Film Layer B

Film Layer C

Inclusion has a higher viscosity than the bulk of resin in layer B

Figure IV: Bi-Layer Film with Top Layer Pigmented via Concentrate

Film Layer A Pigment Concentrate at surfaces of layer A

Film Layer B Layer B pigmented with regrind

Figure V: Vortex Formation in a Converging Die for High and Low Deborah Number Fluids








Die Exit

         
  

Figure VI: Die Plate-Out With Increasing De Number

180 grams of 12 MI LDPE + 5% Pigment White 6 Extruded at 190 C

800 psi. ~ 0.5 De

1600 psi. ~1.0 De

2050 psi. ~ 1.5 De

2700 psi ~2.0 De

Figure VII: Plate-Out with Higher Molecular Weight Resin

98 Grams of 2 MI LDPE with 5% Pigment White 6. Extruded at 190 C at 3000 psi. Estimated De of > 3

Figure VIII: Residue Removed from Melting Zone of The Extruder Screw

Carbonized Resin Layers

Pigment Layers

Figure shows the alternating layers of pigmented (white) and un-pigmented (black) layers