machine design, Vol.5(2013) No.

1, ISSN 1821-1259

pp. 37-42
Preliminary note

THE INFLUENCE OF THE INJECTION PROCESSING TEMPERATURE ON THE THERMAL STABILITY OF POLYMERS USED IN THE MANUFACTURE OF ITEMS IN THE AUTOMOTIVE AND SPORTS INDUSTRY
Gheorghe Radu Emil MRIE 1, *
1

University of Oradea, Faculty of Fine Arts, Oradea, Romania

Received (21.01.2013); Revised (18.02.2013); Accepted (28.02.2013) Abstract: The object of the present study is the analysis of the variation in thermal stability (the vitrification temperature, the melting point, the flowing temperature) depending on the processing temperature for polymers used in the manufacture of various technical items in the automotive and sports industry. The studied polymers were polyamide (PA), thermoplastic polyurethane (TPU), polyoxymethylene (POM) and polypropylene (PP). Key words: polymers, thermal stability, differential scanning calorimetry (DSC)

1. INTRODUCTION 1.1 Generalization

Polyamides, thermoplastic polyurethanes, polyoxymethylenes and polypropylene are macromolecular composites frequently used in the manufacture of various technical items in the automotive and sports industry. In the automotive industry, polyamides are used for casings, ventilators, complicated construction parts, fuel tanks, bushes, pivots, flexible wiring, floats and brake fluid reservoirs. Polyoxymethylenes are used for cogwheels, slideways, active parts of oil or diesel pumps, etc. Thermoplastic polyurethanes are used in the automotive industry for air grilles, sealing rings, side skirts, connecting bellows, flexible and resistant air cooling systems, oil- and vaseline-resistant protective rings for anti-roll bar ends, protective bellows; polypropylene is used in the manufacture of bumpers and car door guards. In the sports industry, polyamides are used in the manufacture of inline skates, tents, ropes used in climbing and speleology, crash helmets, etc. [1]. POM is used in the manufacture of rear derailleur jockey wheels, inline skates parts, etc. Thermoplastic polyurethanes are used in the manufacture of sports equipment (ski boots, ski tip protectors, sledges, crossbows, etc.)[1,2,3]. Polypropylene is used in the manufacture of sports shoes innersoles [4], football boots crampons, bicycle pedals, height adjustment elements in push scooters, etc. All these polymers are used both as standalone materials and reinforced with various reinforcing agents: glass fibre, carbon fibre, molybdenum disulfide, silicon dioxide, metallic fibres, mica, etc. [5-8]. Polyamides, thermoplastic polyurethanes, polyoxymethylenes and polypropylene are often used in the automotive and sports industry due to the following properties [1,9-23]: good dimensional stability;

good mechanical resistance; good rigidity; excellent fatigue resistance; great impact strength; abrasion and wear resistance; good balance between rigidity and elasticity; easy to process; their fine surface.

1.2. Thermal analysis methods

The terminology recommended by the International Confederation for Thermal Analysis and Calorimetry (ICTAC) [24] is used further on. According to this terminology, thermal analysis refers to a group of techniques by means of which, dependent on time or temperature, a physicochemical property of the investigated sample is monitored, when the temperature of the sample, in a certain atmosphere, is programmed. The programming may imply the increase or decrease of the temperature according to a variation function during a period of time (temperature programme) or maintaining the temperature constant. An extensive enumeration of the thermal analysis techniques is given in Table 1 [25]. The most frequently used techniques are TGA, DTA, DSC and DMA. These techniques are used for characterizing technical polymers [26,27,28]. The differential thermal analysis (DTA) consists of measuring and recording the difference T between the temperature of the sample to be investigated and the temperature of an inert reference material, given that the oven temperature observes a certain programme. The DSC technique is similar to the DTA technique, with the exception that this technique measures the difference in heat flux between the sample to be investigated and the reference sample. The main physical and chemical processes detected by the DTA and DSC techniques are summarised in Table 2. Moreover, the DTA and DSC techniques can also signalize processes of thermal and thermo-oxidative degradation of organic and inorganic materials. Thermal

*Correspondence Authors Address: University of Oradea, Faculty of Fine Arts, Str. P-ta Independentei nr. 39, 410067, Oradea, Bihor, Romania, [email protected]

Gheorghe Radu Emil Mrie: The Influence of the Injection Processing Temperature on the Thermal Stability of Polymers Used in the Manufacture of Items in the Automotive and Sports Industry; Machine Design, Vol.5(2013) No.1, ISSN 1821-1259; pp. 37-42

degradation is the decomposition of a material in composites with a smaller molecular mass and it is characterized by endothermic peaks. Thermo-oxidative degradation refers to the materials interaction with oxygen and it is characterized by exothermic peaks. Through DTA and DSC, one can evaluate the domain of chemical stability of a material, i.e. the domain of temperature in which, by means of a rapid analytical technique (such as DTA and DSC), a process of thermal or thermo-oxidative degradation is not outlined. Each material has a specific DTA and DSC curve. That is why each of these materials may be regarded as a thermal spectroscopy used to identify a certain material. Applying this method of material identification requires a standardization of the thermal analysis methods [25]; this task proves to be quite difficult because of the influence of operational factors on the results of the DTA and the DSC. The present study aims to analyse, by means of the DSC thermal analysis method, the variation in thermal stability (the vitrification temperature, the melting point, the flowing temperature), depending on the injection processing temperature, for polymers which are frequently used in the manufacture of various technical items in the automotive and sports industry.

variation on the vitrification temperature, the melting point and the flowing temperature of the polymer.

Fig.1. Injection machine ENGEL VC 500/110 TECH

3. RESULTS AND DISCUSSION 3.1. The differential scanning calorimetry (DSC) of polyamide 6.6, type TECHNYL A 221 (Dry)
The following real injection temperatures were used in order to obtain the specimens: 270C, 285C, 300C, 315C, 330C and 345C. All other parametres which influence the injection cycle remained constant throughout the injection of the specimens. The specimens obtained this way were subjected to the DSC thermal analysis. In some cases, unprocessed granules were used for the measurements, in order to trace the changes in the material during the injection. The DSC measurements were recorded in a nitrogen atmosphere, using the following temperature scheme: temperature increase from 0 to 270C by 10 K/min, temperature decrease to -100C by 10 K/min, isothermal mode at -100C for 5 minutes, temperature increase to 400C by 5 k/min. Table 3 shows the values of the vitrification temperature Tv (inflection point on the DSC curve) and the melting point Tm (the endothermic peak on the DSC curve) depending on the six processing temperatures. It can be observed that Tv varies between 59.6C and 60.6C, and Tt varies between 261.1C and 262C, the modifications are therefore non-essential, having the same value as those of the unprocessed granules. In conclusion, the processing temperature does not influence the transition temperatures of polyamide 6.6, type Technyl A 221.

2. THE EXPERIMENTAL PART 2.1. The polymeric materials used

The following types of polymers were used in the injection of the samples necessary to the experimental part: Polyamide 6.6, type TECHNYL A 221 (Dry), Thermoplastic polyurethane, type Desmopan KA 8377, Polyoxymethylene, type Tenac 2013A, Polypropylene, type Homopolymer Resin 100-GBO6. All four types of technopolymers are polymers without fillers.

2.2. Equipment
The equipment used in the processing of the polymers was a horizontal injection machine (fig.1). Name of the machine: ENGEL Version: G/11/10/116/3 Manufacture year: 2002 Type: VC 500/110 TECH Manufacturer: Engel Maschinenbau Gesellschaft m.b.h A-4311 Schwertberg [29]. The temperature measurement of the flowing material was recorded by means of a DYNISCO thermocouple, model Ti422J, installed in the nozzle of the injection cylinder so as to record the real temperature of the melted polymer flux. The equipment used for the differential scanning calorimetry (DSC) analysis of the four technopolymers (PA 6.6, TPU, POM and PP) was: a type NETZSCH DSC 204 device, manufacturing company: NETZSCH, manufacture year: 2000 The differential scanning calorimetry (DSC) showed, for each polymer, the influence of the processing temperature 38

3.2. The differential scanning calorimetry (DSC) analysis of thermoplastic polyurethane, type Desmopan KA 8377
The following real injection temperatures were used in order to obtain the specimens: 200C, 210C, 220C, 230C and 240C. . All other parametres which influence the injection cycle remained constant throughout the injection of the specimens. The specimens obtained this way were subjected to the DSC thermal analysis. In some cases, unprocessed granules were used for the measurements, in order to trace the changes in the

Gheorghe Radu Emil Mrie: The Influence of the Injection Processing Temperature on the Thermal Stability of Polymers Used in the Manufacture of Items in the Automotive and Sports Industry; Machine Design, Vol.5(2013) No.1, ISSN 1821-1259; pp. 37-42

material during the injection. The DSC measurements were recorded in a nitrogen atmosphere, using the following temperature scheme: temperature increase from 20 to 200C by 10 K/min, temperature decrease to -100C by 10 K/min, isothermal mode at -100C for 5 minutes, temperature increase to 400C by 5 k/min. Table 4 shows the values of the vitrification temperature Tv and the flowing temperature Tf (the endothermic peak on the DSC curve) depending on processing temperature. It can be observed that Tv increases very little with the increase in processing temperature, and Tf is insignificantly influenced by the processing temperature.

It can be observed that Tv varies between 144.6C and 147.4C, and Tt varies between 174.5C and 177.3C, the modifications are therefore non-essential. In conclusion, the processing temperature has very little influence on the transition temperatures of the polyoxymethylene, type Tenac 2013 A.

3.4. The differential scanning calorimetry (DSC) analysis of the polypropylene homopolymer, type INNOVENE 100-GBO6.
The following real injection temperatures were used in order to obtain the specimens: : 220C, 240C, 260C, 280C i 300C. All other parametres which influence the injection cycle remained constant throughout the injection of the specimens. The specimens obtained this way were subjected to the DSC thermal analysis. In some cases, unprocessed granules were used for the measurements, in order to trace the changes in the material during the injection. The DSC measurements were recorded in a nitrogen atmosphere, using the following temperature scheme: temperature increase from 20 to 220C by 10 K/min, temperature decrease to -100C by 10 K/min, isothermal mode at -100C for 5 minutes, temperature increase from -100 to 400C by 5 k/min. Table 6 shows the values of the melting point Tm (the endothermic peak on the DSC curve) for PP homopolymer, type INNOVENE 100-GBO6, depending on the processing temperature. It can be observed that Tt varies between 162.2C and 163.6C, the modifications are therefore non-essential. In conclusion, the processing temperature has very little influence on the melting point of polypropylene homopolymer, type INNOVENE 100-GBO6.

3.3. The differential scanning calorimetry (DSC) analysis of polyoxymethylene, type Tenac 2013A
The following real injection temperatures were used in order to obtain the specimens: 180C, 190C, 200C, 210C, 220C, 230C i 240C. All other parametres which influence the injection cycle remained constant throughout the injection of the specimens. The specimens obtained this way were subjected to the DSC thermal analysis. In some cases, unprocessed granules were used for the measurements, in order to trace the changes in the material during the injection. The DSC measurements were recorded in a nitrogen atmosphere, using the following temperature scheme: temperature increase from 0 to 180C by 10 K/min, temperature decrease to 0C by 10 K/min, isothermal mode at 0C for 5 minutes, temperature increase to 400C by 5 k/min. Table 5 shows the values of the vitrification temperature Tv (inflection point on the DSC curve) and the melting point Tm (the endothermic peak on the DSC curve) depending on the processing temperature.

4. TABLES
Table 1. Thermal analysis techniques [25] Crt. no. 1. 2. 3. 4. 5. 6. 7. 8. Technique Thermogravimetric analysis Differential thermal analysis Differential scanning calorimetry Abbreviation Property Mass Difference in temperature Heat flux Deformation Modulus Permittivity Gas Optical properties Use Chemical decompositions Oxidations Dehydrations Phase transitions Chemical reactions Heat capacity Phase transitions Chemical reactions Calorimetry Mechanical changes Expansion, contraction Phase transitions Polymer reticulation Phase transitions Polymer transformations Decompositions Catalytic reactions or reactions on surfaces Phase transitions Reactions on surfaces Colour changes 39

TGA DTA DSC TMA DMA DETA EGA

Thermomechanical analysis Dynamic mechanical analysis Dielectric thermal analysis Exhaust gas analysis Thermophotometry

Gheorghe Radu Emil Mrie: The Influence of the Injection Processing Temperature on the Thermal Stability of Polymers Used in the Manufacture of Items in the Automotive and Sports Industry; Machine Design, Vol.5(2013) No.1, ISSN 1821-1259; pp. 37-42

Crt. no. 9. 10. 11. 12. 13. 14.

Technique Thermosonimetry Thermo-magnetometry Thermoluminescence Emanation thermal analysis Simultaneous thermal analysis Controlled rate thermal analysis

Abbreviation TS TM TL ETA STA CRTA

Property Sound Magnetic Light emission Gas emissions Constant variation rate of the properties

Use Mechanical and chemical processes Variation of the magnetic properties Curie points Material flaws Structural changes One or several simultaneous techniques The kinetics of the chemical processes

Table 2. Physical and chemical processes detected by DTA and DSC [25] Phenomenon Physical Melting Crystallisation Vaporisation Sublimation Glass transition Crystalline transitions Chemical Dehydration Decomposition Oxidative degradation Solid phase reactions Combustion Polimerization Reticulation Endothermic heat effect + + + + There is no heat effect, only a change in baseline + + + + Exothermic heat effect

There is no heat effect, only a change in baseline +

(+) + + + + +

Table 3. The vitrification temperature and the melting point of PA processed at various temperatures The processing temperature of PA [C] Granules 270 285 300 315 330 345 Tv [C] 60.2 59.9 60.4 59.6 60.1 60.2 60.6 Tm [C] 262.0 261.3 261.1 261.3 261.6 261.3 261.1

Table 4. The vitrification temperature and the melting point of TPU processed at various temperatures Processing temperature of TPU [C] Granules 200 210 220 230 240 40 Tv [C] 56.2 56.5 57.0 57.8 58.7 59.8 Tf [C] 207.4 206.4 206.6 204.4 205.5 205.5

Gheorghe Radu Emil Mrie: The Influence of the Injection Processing Temperature on the Thermal Stability of Polymers Used in the Manufacture of Items in the Automotive and Sports Industry; Machine Design, Vol.5(2013) No.1, ISSN 1821-1259; pp. 37-42

Table 5. The vitrification temperature and the melting point of POM processed at various temperatures Processing temperature of POM [C] Granules 180 190 200 210 220 230 240 Tv [C] 144.6 145.5 145.2 147.4 147.0 144.9 147.4 145.7 Tm [C] 174.5 176.1 176.9 176.9 176.4 176.6 177.3 175.2

Table 6. Melting points of PP processed at various temperatures Processing temperature of PP [C] Granules 220 240 260 280 300 Tm [C] 162.9 162.2 162.2 163.5 163.1 163.6

5. CONCLUSION
The following polymers were analysed: Polyamide 6.6, type TECHNYL A 221 (Dry) Thermoplastic polyurethane, type Desmopan KA 8377, Polyoxymethylene, type Tenac 2013A, Polypropylene, type Homopolymer Resin 100-GBO6. Following the analysis, it can be stated that, for these four polymers, the injection processing temperatures do not influence the vitrification temperature, the melting point and the flowing temperature in a significant way. The largest variation in vitrification temperature and melting point (from 2C to 3C) is recorded for the thermoplastic polyurethane, type Desmopan KA 8377.

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