Processing Techniques for Reinforced Thermosetting Urethane Composites Presented by: Harry Coffee & Dr.

Mark Perry Resin Systems Inc.

Thermosetting urethane resins have been in use for many years in a variety of applications such as paints and coatings, seat cushions, running shoes, automotive interior surfaces, and a variety of cast parts such as bowling balls and skateboard wheels. Their exceptional toughness and resistance to UV degradation have been important factors in most of these applications. Processing and material handling technologies for these applications are mature and comparatively inexpensive. Until recently, however, urethanes had not found their way into any significant continuous filament reinforced applications, particularly applications requiring high fiber loadings to achieve the required performance levels. In the last 24 months, thermosetting urethane resins have been developed and introduced to the market that have been tailored to the specific requirements of these applications, and to the lowest conversion cost technologies used to produced high-strength, lightweight structures: pultrusion and filament winding. The chemistry and rheology of thermosetting urethane resins have both similarities and differences when compared to other thermosetting resins used in these processes today. The similarities allow the use of most of the equipment and tooling associated with the existing resins. The differences force some changes in that equipment, but they also permit thermosetting urethane resins to be processed at exceptionally high speeds, with better process stability than the existing resins, and with virtually no VOC emissions. In this paper the chemistry of thermosetting urethane resins, and how their rheology has been tailored for pultrusion and filament winding, will be reviewed. The resulting processing differences from, and similarities to, currently used resins will also be discussed. Finally, some experimentally-developed guidelines for achieving high-speed productivity, structural integrity and a high quality surface finish in a pultrusion application will be presented.. The Chemistry and Rheology of Thermosetting Urethane Resins All urethane resins, both thermosetting and thermoplastic, depend on the cyanide backbone for their properties. Thermosetting urethanes differ from thermoplastic urethanes in only one essential way: the urethane polymers are cross-linked. While this limits the ability to melt and re-shape them, it significantly increases the glass transition temperature, the elastic moduli and the ultimate strengths of the resin significantly, although the strain to failure is decreased. Further, it is relatively simple to control the degree of cross-linking and thereby balance the various properties achieved.

The most common method employed to create a thermosetting urethane resin is to combine an isocyanate with a polymer alcohol, or polyol. Polyols are relatively inert; however, isocyanates are very active chemically. They have a particular affinity for the OH- radical, and will rapidly attach to as many OH- as they can find. Depending on the particular isomers involved in the reaction, both on the polyol and isocyanate side, a wide range of physical properties can be obtained.
H H H H C C N C H C O C N C H C H H H H O C C O H H C H H O C H C H

isocyanate
H

+
H H C C N C O C C H C O

polyols

H C

H C H

O H H C H C O C N C

urethane

Urethane formation in this manner is an addition reaction there are no by products such as carbon dioxide or water. Heat is released during the reaction, however, the exotherm is relatively small for most of the commercial isocyanate/polyol materials in use today far smaller than the exotherm that occurs in the most common polyester or epoxy chemistry.

T e m p e r a t u r e

M o l e c u l a r W t

Time

There are wide ranges of isocyanates and polyols that are used to make thermosetting urethanes. Most of these urethane precursors have very high molecular weights and very low vapor pressures at normal factory temperatures. The particular isocyanates and polyols that have been successfully used in reinforced composites to date essentially do not volatilize at all at temperatures below 100oF. The industrial hygiene and environmental impacts of thermosetting urethane resins are minimal, and are being discussed in another session at this conference by Dr. Ravi Joshi of Huntsman Polyurethanes. The isocyanate-polyol reaction is initiated simply by mixing, and will continue to completion even at low temperatures. At room temperature, the currently available thermosetting urethanes have an uncatalyzed pot life of 20 to 25 minutes. This is usually accelerated somewhat with a catalyst to a pot life of 12 to 15 minutes at room temperature. Addition of heat accelerates the reaction further. So far, it has been very difficult to obtain a runaway situation where the exotherm and the speed of the reaction drive each other up precipitously. This makes the urethane reaction a stable, manageable one for the typical factory environment. Similarities and Differences There are similarities between thermosetting urethanes and existing polyester resins, as well as differences. The effects of these similarities and differences on processing equipment and procedures can best be illustrated in a comparison table.

Characteristic Viscosity Wetting Ability Cure Temperature Effects Reaction Dynamics Thermal Behavior

Polyester 1000-6000 cps 20-30 sec residence time required Temperature dependent & unstable Reaction initiates along die surface and moves toward center Resin shrinks 56% after cure & cool-down Can be stored for extended periods without reacting

Thermosetting Urethane 3500-4500 cps 10-15 sec residence time required Stable, accelerated by catalysts and/or temperature Reaction progresses throughout cross-section Resin shrinks approx. 1% after cure & cool-down Reaction begins when mixed & cant be stopped Compatible with inert fillers up to 30% (fillers added to polyol precursor) No limited VOCs; standard emission reporting required No odor, low exposure limits almost impossible to exceed

Consequence Urethanes can use existing pumping & mixing equipment Smaller bath or injector system required at same speed Urethanes can be run at high speeds & temps without concern for system crashes Urethane less prone to cracking in thick sections Dies can be made closer to net dimensions; trial-anderror die making not reqd Urethane precursors must be stored separately and mixed at the point of application to fiber a small bath or resin injection system is required Urethanes not currently suitable for applications requiring high filler loads or chemically active fillers Urethanes can be made at full machine capacity without regard to emissions Plant odors are eliminated from personnel clothing & hair

Shelf Stability

Compatible with a wide variety of fillers at loadings up to 60% Styrene emisEnvironmental sions monitored Issues and limited by EPA Filler Compatibility Personnel Hazards Intense styrene odor personnel irritant

Thermosetting Urethanes in a Production Environment Thermosetting urethane resins have been in use in production settings for nearly a year now. The production envelope is being explored carefully, and there is still quite a bit to be done. Several milestones have been achieved, however. Sections as thick as 0.875 inches have been pulled at speeds of over 6 feet per minute, with high surface gloss and no internal cracking. Complex thin-wall shapes have been run for extended periods at over 10 feet per minute in multi-cavity dies.

It is premature to draw conclusions about the productivity potential of thermosetting urethane resins. However preliminary indications are that, when properly set up, a thermosetting urethane pultrusion system is dynamically stable, and is probably overdamped because of the thermal mass of the die. When the system is at a set speed and temperature regime, it tends to stay at that set point, and when it is perturbed from that set point for example if the temperature or speed is adjusted the system moves to the new set point without overshooting or running away. This allows the machine operator to make adjustments in speed and temperature, allow the system to stabilize, observe the quality of the material exiting the die, and make additional adjustments, without fear of causing a system crash and a machine shut-down. Production Guidelines for Thermosetting Urethanes Successful pultrusion of thermosetting urethane resins requires different approaches and equipment. We have developed a set of guidelines for equipment and operations that will put the operators and engineers on the right track. Those guidelines are provided below: Resin Supply and Metering and Mixing Once mixed, thermosetting urethanes have a pot life of 10 to 25 minutes depending on temperature and catalyst level, so mixing must be delayed until just before the resin meets the fiber. The ratio of isocyanate to polyol effects the physical properties of the resin, so reasonably precise metering of the components is important. It is very important to keep moisture away from both the polyols and the isocyanates, so a closed resin supply system and a source of dry make-up air are also necessary. A typical production setup configuration is shown on the following page. To date, only air-driven piston metering pumps have been used, but a gear pump systems are available, and one is in design. Static mixers have given satisfactory results in all testing that has been conducted so far, with both neat and heavily filled resins. Permanent and singleuse disposable static mixers have both been used successfully. Some care should be taken to make sure that a high enough Reynolds number is achieved in the static mixer to reach turbulent flow. A smaller diameter mixer will generally produce better results. Isocyanates have an affinity for water: they react with it to form urea crystals and carbon dioxide. In addition, polyols tend to be hygroscopic. So far, the best results have been obtained when both the polyol and isocyanate reservoirs are closed, and make-up air is dry. If fillers or other additives are used, it is advisable to add these to the polyol blend, to avoid moisture or other reactivity with the isocyanate. It is a good

practice to keep the polyol blend well mixed, to avoid stratification and settling. In most production setups, 55-gallon drums suffice well for day tanks. There is a wide variety of closure systems, desiccants, pumps and mixers designed to fit them.

Typical Production Setup

Shop Air

Metering Pump

Mixing Box

Static Mixing Tube

Heat Zone

Die

Roving Card

Injector Box

Cooling Zones

Injector Box Design Two types of injector boxes have been used successfully: a low or ambient pressure type and a high pressure type. The selection of low or high pressure injection depends on the type of reinforcement. Low pressure injection is most suitable for all-roving constructions; high pressure injection is necessary to achieve good fiber wet-out when fiber mats are required. Low Pressure Injection Box
Top Injection Port

Die

Holes for Roving Bottom Face Plate

High Pressure Injection Box

Top Injection Port Die

Pressure Channel Bottom

For low pressure injection, a simple funnel-shaped box is all that is necessary. The shape of the exit end of the injector should roughly match the radiused entrance to the die. This creates a slight pressure increase when the system is moving. Injection should occur somewhere between the midpoint of the box and the die entrance. A cavity taper of 6o has been used successfully, but this has not been explored greatly. A high pressure injector box incorporates a larger injection chamber at the die face. Successful high-pressure injection has been demonstrated using an injection chamber that has a cross-sectional area of 4-6 times that of the part. Injector box volume is an important consideration, and should determine the length of the injector box. At 70oF, the gel time of the catalyzed resin 12-15 minutes. This decreases to 9-10 minutes at 90oF. The total volume of mixed resin, including the mixing hardware and the injector, should turn over every 4 to 5 minutes at start-up speeds. Fiber Guidance The proximity of the mats and rovings at the injector entrance make it important that there be good fiber separation just before it enters the injector. A polymer roving card 8 to 12 inches from the face of the injector box, spreading the rovings, mats and veils well out of contact with each other has been used successfully for this. Die Temperature Regimes To manage the cure rheology of thermosetting urethane resins, a typical pultrusion die of 36 inches in length can be set up with a single heat zone in the first 12 to 18 inches of the die. The actual resin temperature at the exit of this section can range up to 400 degrees F without causing a die lock-up. As temperatures are increased, cooling the entrance of the die will prevent acceleration of the cure into the injector box. At die temperatures above 350F, full polymerization takes a short distance into the die; however, there is still quite a bit of cross-linking required to achieve the full mechanical properties and glass transition temperature of the

resin. The speed of the cross-linking reaction is constrained by the fact that the resin is no longer as mobile after gel. Additional heat increases the speed of cross-link formation, but the loss of mobility is a stronger influence. In addition, the temperature of the die at the point of gel is well above the Tg of the resin at that point, and added heat will keep the resin above its Tg. To achieve dimensional fidelity and a glossy surface finish, it is necessary that the die temperature fall below the Tg of the partially cross-linked resin before it exits the die. To achieve high speed, high temperatures in the first 1/3 of the die are required to achieve a rapid resin gel; this mandates active cooling of the exit end of the die. Hollow Parts and Mandrels Several hollow cross-sections have been run successfully, but there is still work to be done. Urethane resins shrink very little, but pull forces become unreasonable when straight mandrels are used. Some taper is required, but the point where the taper should start has not been definitively determined. We have theorized that the gel should take place and the resin should go below its Tg on a parallel mandrel surface to maintain dimensional integrity. VOC Control The polyol blends, including their additives, that have been used to date pose no VOC threat. Isocyanates can create problems in some circumstances. A paper on controlling VOC emissions in a production pultrusion setting is being presented by Dr. Ravi Joshi in another venue at this conference. To summarize the practical aspects, normal plant ventilation is sufficient to prevent TOV limit exceedence for most operator situations. Within a few inches of the exit end of the die, it is possible to generate isocyanate concentrations that exceed the TOV limit. A technician would have to spend his entire shift with his nose within inches of the die exit to receive a dose that was unhealthy. This problem can be easily overcome by installing a vent over the die exit and extracting the fumes. This extracted air can be legally vented to the atmosphere with no special reporting requirements to EPA.

In summary, thermosetting urethane resins are becoming available for composites applications. Their properties indicate that they should be able to outperform existing resins in many applications. There are aspects to their use that require processes and procedures new to the composites industry, but they are based on processes and procedures used in other industries for many years. Early results indicate that thermosetting urethanes may offer the industry much higher productivity from its investment than the currently used resins. Also, importantly, they offer the industry the opportunity to avoid limitations imposed by environmental regulations on the emission of styrene.