Compounding Processes

Polymer products are rarely pure materials. Most often they are mixtures, or compounds: Additives are routinely added to modify or improve properties. These additives must be incorporated into the polymer prior to the final shaping operation. Polymer blends and alloys, produced by mixing together two or more polymers to generate a material with a wider range of properties, are finding increasing use. Mixing (or compounding) is a vital step in polymer processing, as the mechanical, physical and chemical properties, as well as the appearance of the final product depend strongly on attaining a uniform composition.
Mixing and Composites Chee 490 18.1

Types of Mixing Process

Based on 2 basic mixing functions; Blending Compounding
Blending mixing is used when the fabrication process will be followed by compounding process (pigments must be mix into granules/powder followed by injection molding process), thermosetting powders and fillers are often blends which disperse upon fusion of the resin during molding Compounding mixing is used when accurate distribution & dispersion of ingredients is required (e.g. in rubber compounding, 4-5 additives have to act together for efficient cross-linking of the rubber)

Blending
Stirring together/blending of a number of solids, e.g.polypropylene powder, pigment, antioxidant, etc. The results is a mixture of powders; the individual powder remain and can be separated (in principle)

Compounding
Involves more intimate dispersion of the additives into the polymeric matrix It requires;
A physical change in the component High shear force to bring about the change The polymer to be in the molted or rubbery state during mixing

Some Processes and Machine (Blending)

Vary from the simplest to sophisticated high speed machine The simplest- is to tumble together dry ingredients, e.g. using a twin-drum tumbler

Twin-drum tumbler

Some Processes and Machine (Blending)

Ribbon-blender

A tumbling action takes place The chamber is stationary and the ribbons rotate constantly scooping the material from the outside to the centre

Ribbon blender

Some Processes and Machine (Blending)

High speed mixer More sophisticated & rapid machine for blending Widely used for PVC dry blends, drying, incorporated pigments, antioxidant, etc. Run at several thousand rpm, and form a circulating powders which becomes heated by friction (150-200C) Mixing tank can be single wall or jacketted for temp. control

Mixing tank High Speed Mixer

Some Processes and Machine (Blending)

Dough Moulding Compound Dough-like blend, e.g. DMC are made in Z-blade (The name comes from the shape of the mixing blade) The mixer itself comprises twin stainless steel bowls in each of which is a mixing blade. The blades rotate in opposite directions (and rarely at different speeds).

Some Processes and Machine (Blending)

Ball Mill
Comprises of cylindrical vessel containing large number of steel or ceramic balls It rotates, the balls tumble inside together with the powder Agglomerates of powder are broken down by the grinding action of the tumbling balls

Ball Mill

Aim of Mixing
Reduce composition non-uniformity Increase the probability of finding volume element of the minor at any point in the blend (acceptable probability distribution) Decrease the size of the domain Break agglomerated particles The mixing of two or more fluids or solid particles in a fluid consist of two process, dispersive (intensive) mixing and distributive mixing.

Mixing
In almost all cases, good distribution AND good dispersion are required.
Distributive mixing can be achieved by providing convoluted flow paths that split and reorient the flow repeatedly Dispersive mixing can be achieved by passing the mixture through small regions of intense deformation.

Mixing and Composites

Chee 490

18.10

Polimer mixing
Dispersive (Intensive) Mixing Process whereby the solid particles or the minor fluid phase are broken into smaller sizes. Distributive Mixing Process wheres the broken up domains distributed into space and homogenized the the mixture.

Distributive vs. Dispersive Mixing

1. Distributive mixing increases only the degree of randomness of the dispersed phase

2.

Dispersive mixing increases the degree of randomness and decreases size of the dispersed phase by deagglomerization

Dispersive Mixing
Dispersive mixing involves generating high stresses (shear and elongational) in the material to break down dispersed particles. These particles may be insoluble fillers (composites) or a second polymer melt (blend).

Dispersive mixers force the material to flow over barriers that form narrow clearances between mixing elements (i.e. between extruder wall and a screw element).
Mixing and Composites Chee 490 18.14

Dispersive Mixing
Concern in this process:
Droplet breakup Happen by Interfacial tension, which keeps droplets whole. Solid agglomerates breakup Happen by Internal force, which makes solid particles form an aggregates. Particulates are used as fillers, color additives, modifiers and reinforcing agent in polymers. Because of electrostatic force etc. between primary particles of the particulates, they form an agglomerates. To get homogeneous mixture, its necessary to get the agglomerates be broken, to their primary particles if possible

Dispersive Mixing
Break these agglomerates by using stresses generated by the flowing fluid component. Consider that force used to break the agglomerates = result of the flow of the surrounding fluid. Assume that the particles will break away as soon as the force exceed the internal force (electrostatic, etc.) Then assuming that the particle do not disturb the fluid flow field, the flow field is homogeneous everywhere , making the deformation is the same everywhere.

Forces in Mixing
How the force transmitted, to break down agglomerates of additive particles?
By fluid mechanical stress in the mixer

Less energy is needed Under high viscosity conditions To achieve good dispersion WHY?

Routes for Mixing

Route 1: with well distributed but poorly dispersed additive, will entail lower viscosity than route 2. Previous equation suggest that Route 1 will require more energy than Route 2

Why distributive mixing is difficult to achieve in melts? For example low viscosity system exhibits turbulent mixing

The boundry between laminar flow and turbulent flow is described by Reynolds equation V= velocity of the fluid, = density, = viscosity, D = diameter of circular channel Renolds Number must exceed 2000 for turbulence flow Based on Reynolds equation, three viscosity regimes are seen to be;
At low viscosity, turbulence results in efficient distribution At high viscosity (as found in polymer melts), turbulence cannot occur & dispersion is poor At very high viscosity (as in rubber), there is sufficient shear to break down agglomerates & efficient distribution and dispersion can occur.

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Consider a channel where, D = 0.5 cm = 0.005 m = 150 Pas = 1000 kg m-3 Q = 250 cm3 s-1 (Q is the amount of materials put through a process/volume throughput) Find velocity from the volume throughput
Low value of Re indicates that turbulent flow cannot occur in polymer melts.

Distributive Mixing
Not concerned with interfacial energy, Particle breakup or domain size reduction. Not concerned with level of stress. Concerned with rapidity and uniformity. Application: Miscible system (no interfacial tension) Immiscible systems during initial stages (large domains) or after domain breakup

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Distributive Mixing
Distributive mixing involves stretching, dividing and reorientating the flow of the polymer melt compound in order to eliminate local variations in material distribution and produce a more homogeneous mixture.

Distributive mixers must impose high strain on the material together with splitting and reorienting the flow.
Achieved by introducing barriers with large clearances that generate a long, convoluted flow path.

Distributive Mixing
Distributive mixing involves stretching, dividing and reorienting the flow of the polymer melt compound in order to eliminate local variations in material distribution and produce a more homogeneous mixture.

Distributive mixers must impose high strain on the material together with splitting and reorienting the flow.
Achieved by introducing barriers with large clearances that generate a long, convoluted flow path.

Mixing and Composites

Chee 490

18.24

12

Mixing Devices
Mixers can be classified into two categories:
Batch mixers: They are the oldest type of mixing equipment and are still widely used. They are versatile units, because operating conditions and the time at which the additives are incorporated can be varied during a cycle to achieve optimum mixing. Continuous mixers: They include single and twin-screw extruders, and modified variants. Continuous mixing offers higher throughputs, reduced manpower requirements and greater product uniformity, leading to easier quality control. Disadvantages include less processing flexibility, requirement for expensive feeding equipment and generally lower dispersive mixing quality

Mixing and Composites

Chee 490

18.25

Batch Mixing Devices

A two-roll mill consists of a parallel pair of counter-rotating, heated metal rolls that turn at a slightly different rate (roll ratio), and provide an adjustable gap (or nip) between them.

The shear stresses generated in the gap are substantial, and provide further compound mixing while shaping the compound into a sheet.

Temperature control is more easily affected in a mill, when compared to a Banbury-type mixer that completely encloses the compound.
Mixing and Composites Chee 490 18.26

13

Batch Mixing Devices

Internal mixers are high intensity mixers that work especially well in the dispersion of solid particle agglomerates. The dispersion of agglomerates depends strongly on mixing time, rotor speed, temperature and rotor blade geometry. The tangential rotor design, or Banbury is shown here, but several variations exist, including the interlocking rotor design known as the Intermix type.
Mixing and Composites Chee 490 18.27

Continuous Mixing Devices

Single Screw Extruders: The SSE is a relatively poor mixing device, and specialized screw sections are needed to improve the mixing efficiency of this apparatus.

Distributive mixing can be improved using static mixers or mixing heads such as the pineapple configuration shown here.

Kenics Static Mixer

Mixing and Composites Chee 490

Pineapple Mixing Section

18.28

14

Continuous Mixing Devices

Dispersive mixing is more difficult, as it requires that high shear stresses be generated. There are numerous designs for mixing sections, which can improve dispersive mixing (Maddock or Union Carbide mixing section, Egan section).

These devices force the melt to flow over barriers, which form narrow clearances between the screw and the barrel, thus improving dispersive mixing.
Mixing and Composites Chee 490 18.29

Extrusion :Reciprocating
Control suhu mixing yang akurat Shear stress secara relatif lebih rendah dari Twin Screw Head pressure lebih rendah dibanding Twin Screw Untuk Compound Foam.

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Continuous Mixing Devices

Twin Screw Extruders: TSEs have two screws within the barrel, and can be co-rotating or counter-rotating, intermeshing or non-intermeshing. They are favoured for Mixing and compounding Chemical reactions / reactive extrusion Devolatilization

Mixing and Composites

Chee 490

18.31

Twin Screw Extruder

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Komponen screw

Extrusion: Continous Mixer

High Ouput High Shear Untuk mendispersikan filer dengan ukuran partikel mikroskopis dan low aspek rasio seperti carbon black, pigment TiO2

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Continuous Mixing Devices

Mixing and Composites

Chee 490

18.35

Continuous Mixing Devices

Twin-screw extruders use modular screws that are assembled from screw segments fitted onto a common shaft. Conveying segments can provide pumping, mixing and devolatilization, while non-conveying elements such as discs and rotors are designed for kneading and mixing.

Thus, screws are easily optimized for a wide range of applications, making twin-screw extruders extremely versatile.
Mixing and Composites Chee 490 18.36

18

Dough Moulding Compound

Compone nt PHR Note

Resin

100

The powders are charged first and blended for about a minute. The resin (containing catalyst) and shrinkage control additive are added and mixing is continued for between 15 and 30 minutes. During this time the mixer is stopped occasionally and the walls of the bowl scraped clean. Once the slurry is homogeneous the reinforcing fibres are added gradually. These are blended into the slurry until they are just distributed throughout the mix - a time of about 5 minutes, typically.
Lubricant Catalyst Shrinkage Control Additive 40-65

High reactivity resin having a maleic : phthalic ratio around 2 : 1 and an alkyd : styrene ratio of about 70 : 30 by weight. The resin viscosity is in the order of 10Pas.
Also called a low profile additive. The material is a solution of a thermoplastic polymer such as polystyrene, polymethyl methacrylate, polyvinyl acetate or polycaprolactone in styrene. The solution contains about 30% polymer by weight. Used at ratios of 40:60 or 30:70 by weight on the host resin. General purpose fillers include calcites and dolomites. Effects fillers include alumina trihydrate. The mean particle size of all fillers used in DMC is in the range 5mm-20mm with an oil absorption between 20-30. Exceptionally larger fillers or fillers having higher oil absorptions (up to 45) are used but at relatively lower levels. Zinc Stearate, Calcium Stearate A relatively stable peroxide having a half-life of a few minutes in the temperature range 100oC 130oC is used. Commonest materials are t-butyl perbenzoate, peroctoate or dicumyl peroxide. Combinations of peroxides are used to fine-tune the rate of crosslinking.

Fillers

150-25 0

3-5 1-2

Pigment

5-10

Polyethylene-Nanosilica Composites
Transmission electron microscopy (TEM) images of 13 wt% SiO2/PE-g-PA 5 wt% SiO2/HDPE

(scale bars correspond to 200 nanometres).

Mixing and Composites Chee 490 18.38

19

Polyethylene-Nanoclay Composites
Transmission electron microscopy (TEM) images of 40 wt% NR4+-MM/PE-g-PA 5 wt% NR4+-MM/HDPE

(scale bars correspond to 200 nanometres).

Mixing and Composites Chee 490 18.39

Polyolefin Blends - Nanocomposites

Idea to locate fillers preferentially in one phase, to selectively reinforce it. This can be accomplished by adding functional groups having better affinity with the filler, so that it will migrate and exfoliate to the preferred phase.

Mixing and Composites

Chee 490

18.40

20

Some Processes and Machine (Compounding)

Involve high shear process & much more powerful machinery The simplest technique is two-roll mill

Two-roll mill
Pair of rollers with a vertical nips between them The polymer and additives are subjected to high shear in the nip as the rolls rotate in opposite directions Two-roll mill mixing started with rubber processing, now exist for various function Mixing on two-roll mill is time consuming, 2 h for a 200 kg mix on a 84 wide mill, and depends on the skill of mill operator

Schematic illustration of two-roll mill

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Banbury Mixer
2 rotors-counter-rotating within a chamber Each has two or four blades which mix by smearing the materials against the chamber wall A weighted ram keeps the mix in place inside the chamber

Banbury Mixer vs. Two-roll Mill

The rate of output (200 kg batch of rubber compound would take 2 h- two-roll mill. A number 11 Banbury mixer produce 350 kg in 15 min or less)

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