Handbook of Plastics, Elastomers and Composites Part 3 docx

80
Table 1.15 Bonding for Thermoplastic Combinations in Multicomponent Injection Molding
458
Material
ABS
ASA
CA
EVA
PA6
PA6,6
PC
HDPE
LDPE
PMMA
POM
PP
PPO mod.
PS–GP
PS–HI
PBTP
TPU
PVC (soft)
SAN
TPR
PETP
PVAC
PSU
PC–PBTP
PC–ABS
ABS +++++++––+–––NN++++N+ +++
ASA +++++++––+–––N–++++N+ +++

CA +++N –– –––––++++–
EVA ++N+ ++ + ++ –+
PA 6 ++ +++NN –N–––++ +–– ++
PA 6,6 ++ ++NNN –––––++ +–+ ++
PC ++ +N+–– –––––++ +–– +++
HDPE – – – + N N – + + N N ––––––––N– –––
LDPE – – – + N N – + + N N + – N – – – – – N – – – –
PMMA + + N N + N – – – – + + – + +
POM ––– –––NN +––––– – – ––
PP –––+––––+N–+–––––––+ –––
PPO mod. – – – ––––––––+++–––N+– –––
PSGP N N – + ––––N–––+++–––––– –––
PS–HI N – – + ––––––––+++––––N– –––
PBTP + + + + + + ––––––––++++–+ +++
TPU +++ +++––
––––++++–+ ++
PVC (soft) + + + – – – + ––––++++ ++
SAN +++++++––+ –N––+ ++
++
TPR NN– – – –NN
++–N +– –––
PETP + + + –––– –––+ –+ +++
PVAC
+
PSU ++ +–– ––––+
–+ +++
PC–PBTP + + + + + – – + –––––++++–+ +++
PC–ABS + + + + + – – + –––––++++–+ +++
+ = good bonding, – = poor bonding, N = no bonding, blank = not evaluated.
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Thermoplastics 81
■
Free blowing
■
Matched die molding
Drape forming, as shown in Fig. 1.69, involves the either lowering the heated sheet
onto a male mold or raising the mold into the sheet. Usually, either vacuum or pressure is
used to force the sheet against the mold. In vacuum forming (Fig. 1.70), the sheet is
clamped to the edges of a female mold, then vacuum is applied to force the sheet against
the mold. Pressure forming is similar to vacuum forming, except that air pressure is used
to form the part (Fig. 1.71). In free blowing, the heated sheet is stretched by air pressure
into shape, and the height of the bubble is controlled using air pressure. As the sheet ex-
pands outward, it cools into a free-form shape as shown in Fig. 1.72. This method was
originally developed for aircraft gun enclosures. Matched die molding (Fig. 1.73) uses
Figure 1.69 Drape forming process.
469
Figure 1.70 Vacuum forming process.
469
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82 Chapter One
two mold halves to form the heated sheet. This method is often used to form relatively
stiff sheets.
Multi-step forming is used in applications for thicker sheets or complex geometries
with deep draw. In this type of thermoforming, the first step involves prestretching the

sheet by techniques such as billowing or plug assist. After prestretching, the sheet is
pressed against the mold. Multi-step forming includes
438
■
Billow drape forming
■
Billow vacuum forming
■
Vacuum snap-back forming
■
Plug assist vacuum forming
■
Plug assist pressure forming
■
Plug assist drape forming
Billow drape forming consists of a male mold pressed into a sheet prestretched by the
billowing process (Fig. 1.74). A similar process is billow vacuum forming, wherein a fe-
male mold is used (Fig. 1.75). In vacuum snap-back forming, vacuum is used to prestretch
the sheet, then a male mold is pressed into the sheet, and, finally, pressure is used to force
Figure 1.71 Pressure forming.
470
Figure 1.72 Free-blowing process.
470
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Thermoplastics 83
the sheet against the mold as seen in Fig. 1.76. In plug assist, a plug of material is used to
prestretch the sheet. Either vacuum or pressure is then used to force the sheet against the

walls of the mold as shown in Figs. 1.77 and 1.78. Plug assist drape forming is used to
force a sheet into undercuts or corners (Fig. 1.79). The advantage of prestretching the
sheet is more uniform wall thickness.
Materials suitable for thermoforming must be compliant enough to allow for forming
against the mold yet not produce excessive flow or sag while being heated.
439
Amorphous
materials generally exhibit a wider process window than semicrystalline materials. Pro-
cessing temperatures are typically 30 to 60°C above T
g
for amorphous materials, and usu-
ally just above T
m
in the case of semicrystalline polymers.
440
Amorphous materials that
are thermoformed include PS, ABS, PVC, PMMA, PETP, and PC. Semicrystalline materi-
als that can be successfully thermoformed include PE and nucleated PETP. Nylons typi-
cally do not have sufficient melt strength to be thermoformed. Table 1.16 shows
processing temperatures for thermoforming a number of thermoplastics.
1.6.4 Blow Molding
Blow molding is a technique for forming nearly hollow articles and is very commonly
practiced in the formation of PET soft-drink bottles. It is also used to make air ducts, surf-
boards, suitcase halves, and automobile gasoline tanks.
441
Blow molding involves taking a
parison (a tubular profile) and expanding it against the walls of a mold by inserting pres-
surized air into it. The mold is machined to have the negative contour of the final desired
finished part. The mold, typically a mold split into two halves, then opens after the part has
cooled to the extent that the dimensions are stable, and the bottle is ejected. Molds are

Figure 1.73 Matched die thermoforming.
471
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84 Chapter One
Figure 1.74 Billow drape forming.
472
Figure 1.75 Billow vacuum process.
473
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Thermoplastics 85
commonly made out of aluminum, as molding pressures are relatively low, and aluminum
has high thermal conductivity to promote rapid cooling of the part. The parison can either
be made continuously with an extruder or it can be injection molded; the method of pari-
son production governs whether the process is called extrusion blow molding or injection
blow molding. Figure 1.80 shows both the extrusion and injection blow molding pro-
cesses.
442
Extrusion blow molding is often done with a rotary table so that the parison is
extruded into a two-plate open mold; the mold closes as the table rotates another mold un-
der the extruder’s die. The closing of the mold cuts off the parison and leaves the charac-
teristic weld-line on the bottom of many bottles as evidence of the pinch-off. Air is then
blown into the parison to expand it to fit the mold configuration, and the part is then cooled
and ejected before the position rotates back under the die to begin the process again. The
Figure 1.76 Vacuum snap-back process.

473
Figure 1.77 Plug assist vacuum forming.
474
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86 Chapter One
blowing operation imparts radial and longitudinal orientation to the plastic melt, strength-
ening it through biaxial orientation. A container featuring this biaxial orientation is more
optically clear, has increased mechanical properties, and has reduced permeability, which
is important in maintaining carbonation in soft drinks.
Injection blow molding has very similar treatment of the parison, but the parison itself
is injection molded rather than extruded continuously. There is evidence of the gate on the
bottom of the bottles rather than having a weld line where the parison was cut off. The par-
ison can be blown directly after molding while it is still hot, or it can be stored and re-
heated for the secondary blowing operation. An advantage of injection blow molding is
that the parison can be molded to have finished threads. Cooling time is the largest part of
this cycle and is the rate-limiting step. HDPE, LDPE, PP, PVC, and PET are commonly
used in blow molding operations.
1.6.5 Rotational Molding
Rotational molding, also known as rotomolding or centrifugal casting, involves filling a
mold cavity, generally with powder, and rotating the entire heated mold along two axes to
uniformly distribute the plastic along the mold walls. This method is commonly used for
Figure 1.78 Plug assist pressure forming.
475
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Thermoplastics 87
making hollow parts, like blow molding, but is used either when the parts are very large
(as in the case of kayaks, outdoor portable toilets, phone booths, and large chemical stor-
age drums) or when the part requires very low residual stresses. Also, rotomolding is well
suited, as compared with blow molding, if the desired part design is complex or requires
uniform wall thicknesses. Part walls produced by this method are very uniform as long as
neither of the rotational axes corresponds to the centroid of the part design. The rotomold-
ing operation imparts no shear stresses to the plastic, and the resultant molded article is
therefore less prone to stress cracking, environmental attack, or premature failures along
stress lines. Molded parts also are free of seams. Figure 1.81 shows a diagram of a typical
rotational molding process.
443
This is a relatively low-cost method, as molds are inexpensive, and energy costs are
low, thus making it suitable for short-run products. The drawback is that the required heat-
ing and cooling times are long, and therefore the cycle time is correspondingly long. High
melt flow index PEs are often used in this process.
1.6.6 Foaming
The act of foaming a plastic material results in products with a wide range of densities.
These materials are often termed cellular plastics. Cellular plastics can exist in two basic
structures: closed-cell or open-cell. Closed-cell materials have individual voids or cells
that are completely enclosed by plastics, and gas transport takes place by diffusion
through the cell walls. In contrast, open-cell foams have cells that are interconnected, and
fluids may pass easily between the cells. The two structures may exist together in a mate-
rial so that it may be a combination of open and closed cells.
Blowing agents are used to produce foams, and they can be classified as either physical
or chemical. Physical blowing agents include
■
Incorporation of glass or resin beads (syntactic foams)
■
Inclusion of an inert gas, such as nitrogen or carbon dioxide, into the polymer at high

pressure, which expands when the pressure is reduced
■
Addition of low-boiling liquids, which volatilize on heating, forming gas bubbles when
pressure is released
Figure 1.79 Plug assist drape forming.
475
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88 Chapter One
Chemical blowing agents include
■
Addition of compounds that decompose over a suitable temperature range with the evo-
lution of gas
■
Chemical reaction between components
The major types of chemical blowing agents include the azo compounds, hydrazine de-
rivatives, semicarbazides, tetrazoles, and benzoxazines.
444
Table 1.17 shows some of the
common blowing agents, their decomposition temperature, and primary uses.
A wide range of thermoplastics can be converted into foams. Some of the most com-
mon materials include polyurethanes, polystyrene, and polyethylene. Polyurethanes are a
popular and versatile material for the production of foams and may be foamed by either
physical or chemical methods. In the physical reaction, an inert low-boiling chemical is
Figure 1.80 Extrusion and injection blow molding processes.
442
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Thermoplastics 89
added to the mixture, which volatilizes as a result of the heat produced from the exother-
mic chemical reaction to produce the polyurethane (reaction of isocyanate and diol).
Chemical foaming can be done through the reaction of the isocyanate groups with water to
produce carbamic acid, which decomposes to an amine and carbon dioxide gas.
445
Rigid polyurethane foams can be formed by pour, spray, and froth.
446
Liquid polyure-
thane is poured into a cavity and allowed to expand in the pour process. In the spray
method, heated two-component spray guns are used to apply the foam. This method is
suitable for application in the field. The froth technique is similar to the pour technique,
except that the polyurethane is partially expanded before molding. A two-step expansion is
used for this method using a low-boiling agent for preparation of the froth and a second
higher-boiling agent for expansion once the mold is filled.
Polyurethane foams can also be produced by reaction injection molding or RIM.
447
This process combines low-molecular-weight isocyanate and polyol, which are accurately
metered into the mixing chamber and then injected into the mold. The resulting structure
consists of a solid skin and a foamed core.
Polystyrene foams are typically considered either as extruded or expanded bead.
448
Ex-
truded polystyrene foam is produced by extrusion of polystyrene containing a blowing
agent and allowing the material to expand into a closed cell foam. This product is used ex-
tensively as thermal insulation. Molded expanded polystyrene is produced by exposing
polystyrene beads containing a blowing agent to heat.
449

If the shape is to be used as
loose-fill packaging, then no further processing steps are needed. If a part is to be made,
the beads are then fused in a heated mold to shape the part. Bead polystyrene foam is used
in thermal insulation applications, flotation devices, and insulated hot and cold drink cups.
Polyethylene foams are produced using chemical blowing agents and are typically
closed cell foams.
450
Cellular polyethylene offers advantages over solid polyethylene in
terms of reduced weight and lower dielectric constant. As a result, these materials find ap-
plication in electrical insulation markets. Polyethylene foams are also used in cushioning
applications to protect products during shipping and handling.
Figure 1.81 The rotational molding process.
443
Thermoplastics
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90 Chapter One
References
1. F. W. Billmeyer, Textbook of Polymer Science, 2/e, John Wiley & Sons, Inc., New
York, 1971.
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8. Brydson, J.A., Plastics Materials, 6/e, Butterworth-Heinemann, Oxford, 1995, p.
122.
TABLE 1.16 Thermoforming Process Temperatures for Selected Materials
459
Material
Mold and set
temperature,
°C
Lower
processing
limit, °C
Normal forming
temperature,
°C
Upper
temperature
limit, °C
ABS 85 127 149 182
Acetate 71 127 149 182
Acrylic 85 149 177 193
Butyrate 79 127 146 182
Polycarbonate 138 168 191 204
Polyester (PETG) 77 121 149 166
Polyethersulfone 204 274 316 371
Polyethersulfone-glass filled 210 279 343 382
HDPE 82 127 146 182
PP 88 129 154–166 166
PP-glass filled 91 129 204+ 232
Polysulfone 163 190 246 302

Polystyrene 85 127 149 182
FEP 149 232 288 327
PVC–rigid 66 104 138–141 154
Thermoplastics
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Thermoplastics 91
9. A.W. Bosshard and H.P. Schlumpf, Fillers and Reinforcements, in Plastics Additives
2/e, R. Gachter and H. Muller, Eds., Hanser Publishers, New York, 1987, p. 407.
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518.
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519.
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521.

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TABLE 1.17 Common Chemical Blowing Agents
460
Blowing agent
Decomposition
temp., °C
Gas yield,
ml/g Polymer applications
Azodicarbonamide 205–215 220 PVC, PE, PP, PS, ABS, PA
Modified azodicarbonamide 155–220 150–220 PVC, PE, PP, EVA, PS, ABS
4,4´–oxybis (benzenesulfohydrazide) 150–160 125 PE, PVC, EVA
Diphenylsulfone–3,3´–disulfo-
hydrazide
155 110 PVC, PE, EVA
Trihydrazinotriazine 275 225 ABS, PE PP, PA
p-toliuylenesulfonyl semicarbazide 228–235 140 ABS, PE, PP, PA, PS
5-phenyltetrazole 240–250 190 ABS, PPE, PC, PA, PBT, LCP
Isatoic anhydride 210–225 115 PS, ABS, PA, PPE, PBT, PC
Thermoplastics
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92 Chapter One
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Thermoplastics 93
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94 Chapter One
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