DIFFERENTIAL SCANNING CALORIMETRY(DSC) AND TORQUE RHEOMETRY: A VIABLE COMBINATION FOR DETERMINING PROCESSING PARAMETERS OF THERMOSETTING PLASTICS

Christopher C. Ibeh, Associate Professor Plastics Engineering Technology Pitttsburg State University, Pittsburg, KS 66762 Abstract
The crosslinking (cure) profile is a common feature of thermosetting plastics but each material has unique cure characteristics such as gel point, peak cure temperature, cure time and cure exotherm. Hence, understanding the cure profile is the key to determining the optimal, cost-effective processing parameters of thermosetting plastics. Using a DSC and a Torque Rheometer, a typical SPI RAMP cure scan can provide the peak cure temperature, and subsequent isothermal cure scans at and around the peak cure temperature can be used to establish the optimal processing window of a given material. only causes degradation of property and excessive processing cycle. It is customary to delay cure of thermosets via BStaging, Pre-Polymerization, Adducting and use of inhibitors, at a point just before the gel point. Cure delay is used to prevent pre-mature or unwanted crosslinking and consequent loss/waste of thermosetting polymeric materials since once they cure, they become set and cannot be re-used (3)(4). Crosslinking as a process is influenced by mass (concentration of reactants), temperature, time and pressure. Hence, for cure (process) optimization, the processing window (mold residence time, processing temperature and pressure) must correspond to the maximum cure point E or to a point less than point E. With respect to time, crosslinking is not a linear process; it is logarithmic (5). Attainment of 50% cure in 2 minutes for example, does not imply 100% cure in 4 minutes. In actuality, a thermosetting polymeric material can achieve 80% cure in 4 minutes and 100% cure in 30 minutes or 1 hour or 24 hours etc. as the case might be. Therefore, good cure (process) optimization practice necessitates the achievement of partial cure in the mold or reactor, and completion of cure outside the mold, preferably in an oven, thereby reducing mold residence time (process cycle). The effect of this post-curing practice is to free the mold for more products and increased productivity without compromising product quality. Increased productivity is tantamount to higher profits and cost-effective processing. The objectives of this paper are to: explore the: (1) use of the Differential Scanning Calorimetry (DSC) and/or Torque Rheometry as simulation tools for determining processing parameters of thermosetting plastics and (2) use of the concepts of cure exotherm and total exotherm as correlation tools for cure optimization.

Introduction
Thermosetting plastics derive their strength and characteristics (1)(2) from crosslinking. Crosslinking has two main stages, Gelation and Curing. Figure 1 (and also Figures 2 and 3) is representative of the crosslinking process of thermosets; it shows the hump-type, exothermic profile that is typical of thermosetting polymeric materials crosslinking process. Point A is the start of the crosslinking process; the reactive component(s) have just been mixed together or/and subjected to heat and/or pressure. Point B is the instantaneous and temporary drop in viscosity (properties) due to the effect of applied heat. Point C is gradual rise in viscosity due to the effect of crosslinking overtaking the effect of heat. Point D is the Gel Point, and marks the point of irreversibility. Beyond the gel point, the material continues to cure until all the properties and characteristics have been attained. Point E is the Maximum Cure Point. At the maximum or peak cure point, all the properties and characteristics have been attained, and further processing

DSC and Torque Rheometry Cure Techniques for Thermosets

An SPI RAMP crosslinking profile of a thermosetting polymeric material can be easily obtained using a DSC scan. The DSC heats the sample at a o o specified rate ( 5 C/min, 10 C/min etc) to a specified upper temperature limit depending on the material under study. Figures 1 and 2 show the typical SPI RAMP crosslinking profile obtained from such a DSC scan. The relevance of the SPI RAMP scan is that it pinpoints the maximum or peak cure temperature; a suggested processing temperature of the material under study. The implication or importance of the peak cure temperature is that it is, as afore mentioned, the upper limit temperature beyond which you do not want to process the material. If the material is processed at a temperature beyond the peak cure temperature, it will be subjected to property degradation, and the result will be poor quality product. The time profile of the SPI RAMP cure profile has little or no relevance because most processes are carried out isothermally (at constant temperature). From Figures 1 and 2, one can deduce that the peak cure o temperature of Diallyl Phthalate, for example, is 175 C. Knowing the upper limit temperature, one then carries out a series of isothermal cure scans, using the DSC, at specific temperatures, at the peak cure temperature and below. The isothermal cure scan gives a relevant cure time. Analyses and comparison of the cure times and cure exotherms of the different cure temperatures will help determine the optimal processing window. The cure exotherm represents the strength level of the thermosetting material; heat is given off due to the conversion of double bonds of the monomeric reactants to single, network structure bonds of the crosslinked material. The analyses can be substantiated and verified by carrying out cure runs using a Torque Rheometer. The validity of the Torque Rheometer is that it simulates the actual mold or reactor conditions with respect to residence time and processing speed (RPM). The Torque Rheometer has a mixing chamber comparable to the barrel and mold of injection molding, extrusion, compression molding processes. The total processing time of the Torque Rheometer should correspond to the actual residence time in the mold.

2. HaakeBuchler Rheocord Computer-Operated Torque Rheometer

System

40,

3. Mettler AE 100 Analytical Balance 4. TA instruments Aluminum Sample Pans and Covers Materials Used: 1. Durez 22761 Blue Diallyl Phthalate (DAP) in Granular Form 2. Nitrogen Gas

Procedure For The DSC Experiments

The DAP was ground into powder form and all experiments were conducted with powder DAP. About 10 mg of DAP was weighed out in the aluminum sample pan using the Mettler AE 100 Analytical Balance. The aluminum pan with sample was covered and placed on the frontside sample port of the DSC cell, with an empty, covered aluminum pan on the backside port as reference. The Nitrogen inert gas was turned on and run at a rate low enough not to displace the sample and reference materials from the DSC cell port. The DSC cell port thermocouple transmits the responses of the sample and reference to applied heat to the computer. The TA Analyst 2000 computers Instrumentation menu was accessed and a file created for the experiment. The file contained the samples identification and the test method. The test method used o for the SPI RAMP cure scan was: RAMP is 10 C/min to o 200 C and the test method used for the ISOTHERMAL cure scan was in two segments: o o I). RAMP is 50 C/min to 165 C II). ISOTHERMAL for 20 minutes At the end of the experiment, the experimental data was analyzed using TA Analyst 2000s General Analysis Utility V4.1 software, to yield such parameters as peak cure temperature, cure exotherm etc. The Print Report/Data menu options of the V4.1 software were used to generate the heat flow data (not shown) and cure parameters of Table 1. A 0.2 minute increment was used for the time-based data of the isothermal scan of DAP and 5 degree incremement was used for the temperaturebased scan of the five thermosets studied (Figure 2).

Experimental Section
Equipment Used: 1. TA Instruments Thermal Analyst 2000, Computer-Operated Differential Scanning Calorimeter (DSC 10)

Torque Rheometer Experiments

The rear plate, mixing section and front plate temperature zones were set at the desired temperature, o o o 155 C, 165 C , 175 C etc. as the process temperature dictated. 40 grams of DAP was charged into the mixing

chamber of the Torque Rheometer, and Torque data obtained are as per Table 4.

Results
The crosslinking profile plots of Figures 1 and 2 are as per the heat flow versus temperature data (not shown), and are of materials chosen to represent the three main categories of thermosets. P-F Resins (Phenolics) are general purpose or commodity thermosets, high temperature curing but average mechanical properties, and are popular matrix materials for composite wood products (plywood, particle board, wafer board etc.) and laminates. Epoxy Resins are engineering Thermosets. Notice the difference in characteristics between Hardman Epoxy (Figure 2) and West System Epoxy (Figure 1); West System Epoxy is a high strength (Exotherm = 1804 J/g), high temperature curing resin for coating and structural bonding applications whereas the Hardman Epoxy is a low temperature curing, average strength (Exotherm = 156 J/g) resin for general purpose bonding and adhesive applications. DAP is a specialty thermoset that is high temperature curing, with dimensional and thermoxidative stability; it is actually dormant below 150 o C even in the presence of a catalyst. DAP is favored by the aerospace and electronic industries for applications requiring reliability, longevity and weatherability, inspite of its relatively high cost ($2.00 - $7.00 /Ib). Thermosets in general are very good electrical and thermal insulation materials because of their very low dissipation factors and k-factors (thermal conductivities) respectively. Figure 3 is per the heat flow versus time data, and represents the isothermal crosslinking profile diallyl phthalate (DAP) at 155 oC, 165 oC, 170 oC, 175 oC, 180 oC and 185 oC. The cure parameters of DAP on Table 1 were generated by the analyses of the isothermal cure profiles Figure 3. The analyses were performed using the General Analysis Utility V4.1 software of TA Analyst 2000. The total exotherm values of Table 1 were generated by integrating over the whole area under the exotherm whereas the cure exotherm values were generated by integrating over the area from the apparent gel point to the peak cure point. The V4.1 software was also used to pinpoint the exact coordinates of the peak cure point before the integration was carried out. The difference between the peak cure point and the apparent gel point was used as the cure time. Figure 4 is the cure profile of DAP as per data generated by the Torque Rheometer. Notice the similarity of the cure profile of DAP via the Torque

Rheometer (from point A2 to Ei and beyond) to those of Figures 1, 2 and 3 via the Differential Scanning Calorimeter. Points A to A2 represent the Load or Mixing Torque and simulates the shearing action of the screw and barrel of the injection molding machine. Mt is the Minimum Torque and Ei is the Maximum or Peak Cure Point. The time from the zero to Mt is the Fusion Time (4.50 minutes) and the time from zero to Ei is the Total Processing Time (5 minutes). The difference between the processing time and fusion time is the Cure Time (0.50 minute).

Discussion of Results
The results of Tables 1 and 2 (Figure 4) are used to establish the processing window for DAP. The cure exotherm obtained by integrating from the gel point to the peak cure point is a more useful parameter than the o total exotherm. The cure exotherm is highest at 175 C, o o higher than the exotherm values at 180 C and 185 C, and reinforces the concept that the peak cure temperature o of DAP is at 175 C, as previously determined using the SPI RAMP scan of Figure 2. However, taking process optimization and the pressure factor into consideration, o choice of 165 C as the process temperature would not compromise part or product quality. It is customary to process DAP at 4000 - 6000 psi (DUREZ). The processing time as per the Torque Rheometer cure scan is 5 minutes. Hence, the recommended processing window for DAP is: Processing Pressure = 4000 - 6000 psi; Process Cycle (Residence Time) = 5 - 6 minutes; o Processing Temperature = 165 - 175 C.

Conclusion
This paper has demonstrated the viability of Differential Scanning Calorimetry-Torque Rheometry combination for the pre-determination of processing parameters of thermosets. The concepts of cure exotherm and total exotherm were used to establish the optimum processing window of thermosetting plastics. It is recommended that such in-lab, simulation practices be carried out especially for high volume (mass) production schedules to reduce the trial and error schedules currently used by some processors and manufacturers.

References
1. Creedon, J. P.,The Characterization of Thermosetting Polymers (Degree of Cure), E. I. Dupont Inc., Analytical Instruments Division, 1970.

2. Ibeh, C. C., Thermosets: Why They Behave The Way They Do -- Unpublished, 1990 3. Ibeh, C. C., and Goodman, S., Phenolics, Handbook Of Thermoset Plastics, Second Edition, Noyes Publication, 1996, Chapter 2. .

4. Ibeh, C. C., and Goodman, S., Aminos, Handbook Of Thermoset Plastics, Second Edition, Noyes Publication, 1996, Chapter3. 5. Goodman, S., Handbook Of Thermoset Plastics, First Edition, Noyes Publications, 1986, Chapter 1

Table 1:

Cure

Parameters

Of Diallyl

Phthalate

(DAP)

Temperature (oC)

155 165 170 175 180 185

Gel Time Gel Time (Minutes (Minutes) ) (G) (P) 2.29 2.48 2.79 2.79 2.51 2.90 2.57 3.11 3.11 2.99 2.90 2.99

Peak Cure Time (Minutes) 2.94 3.52 3.52 3.44 3.75 3.60

Total Exotherm (J/g) 35.8 52.4 56.96 57.2 64.7 70.1

Cure Exotherm (J/g) ** 2.15 8.325 6.49 18.47 16.26 11.65

Cure Time (Minutes)

0.46 0.41 0.41 0.45 0.85 0.61

Table 1: Cure Parameters Of DAP ** = Relevant Exotherm; Gel Time (P): Used To Determine Peak Cure Point; Gel Time (G): Gel Point Suggested By V4.1 Software

Table 2: Time (Mins.) 0 Torque (m-g) 0 Time (Mins.) 1.75 Torque (m-g) 1000 Time (Mins.) 3.75 Torque (m-g) 1450 Time (Mins.) 5.50 Torque (m-g) 2205 Time (Mins.) 7.50 Torque (m-g) 1610 Time (Mins.) 10.3 Torque (m-g) 1360

Torque 0.25 225 2.0 1600 4.0 1350 5.75 2050 8.0 1571 11.0 1348

Data Of 0.5 800 2.25 1100 4.30 1234 6.0 2011 8.30 1532 11.30 1316

Diallyl 0.75 910 3.0 1080 4.50 1200 6.30 1856 8.50 1515 12.0 1311

Phthalate 1.0 2025 3.25 1275 4.75 1900 6.50 1800 9.0 1465 13.0 1268

(DAP) 1.25 2250 3.40 1650 5.0 2238 7.0 1748 9.30 1429 14.0 1229 1.50 2250 3.50 1575 5.30 2210 7.30 1650 10.0 1376 15.0 1241

Table 2: Torque Data Of DAP

Fig.1: Cure Profile of Thermosets 14 12 10 8 6 4 2 0 20 45 70 95 120 145 -2 -4 D C 170 A EPOXY(WS105 ) E

-->Temperature (oC)

Figure 2: Crosslinking Profile Of Thermosets

1.2 1 0.8 0.6 P-F Resin 0.4 0.2 0 0 15 30 45 60 75 90 105 120 135 150 165 180 195 -0.2 -0.4 --> Temperature (oC) 210 Epoxy (HM) DAP (DUREZ)

Figure 3: Isothermal Cure Of DAP At Selected DAP @ 155 Temperatures oC 1 0.5 0 0 2 4 6 8 -0.5 -1 -1.5 -2 --> Time (Minutes) 10 DAP @ 165 oC DAP @ 170 oC DAP @ 175 oC DAP @ 180 oC DAP @ 185 oC DAP @ 175 oC

Figure 4: Torque Rheometer Cure Profile Of Diallyl Phthalate (DAP)(RPM=39) 2500 2000 1500 1000 500 0 0 5 8 2.5 13 A A1 Eii A2 Mt Torque(mg)

Time (Minutes)