EXPERIMENT 4: RUBBER VULCANIZATION

4.1 Objectives: 4.1.1 4.1.2 4.1.3 To use compression molding for rubber vulcanisation process. To prepare test pieces for physical testing. To investigate the defects that may occur during molding process and the factor that causes them. 4.2 Introduction The green stock of rubbers needs to shape into blanks of suitable dimensions after compounding. At this stage the stock will retain the shape imposed on it because it is predominantly plastic. The basic processing machines used for forming rubber stock are the calenders and extruders. Calendering process is compressing a material by passing a single continuous sheet through a number of pairs of heated rolls whereas extrusion is a process used to create objects of a fixed and cross-sectional profile by pushing material through a die of the desired cross-section. (Nagdi, 1992)

After rubber compounds have been properly mixed and pre-shaped, they must be vulcanized in order to solidify the shape of molded compounds. This is accomplished by the process of vulcanization, which usually takes place under pressure at elevated temperature, using different techniques. The treatment accomplishes cross-linking of elastomer molecules to form 3-D network structures, so that the rubber becomes stiffer and stronger but yet retains extensibility. The rubber loses its tackiness and more resistant to degradation caused by heat, light and aging process. (Nagdi, 1992)

There are mainly three types of molding: compression, transfer, and injection molding. Compression molding is the classic rubber vulcanization method. In compression molding, the rubber stock is placed between the stationary and movable members of mold. The mold is closed, and the heat and pressure are applied so that the material becomes plastic, flows to fill the mold, and becomes a homogeneous mass. For a typical compression molding, the material may be as near as 150 c and 1000-300psi. A slight excess of material is usually placed in the mold to insure its being completely filled. The rest of the polymer is squeezed out between the mating surfaces of the mold in a thin and easily removed film known as flash. Molds are relatively simple and help in studying 1

shrinkage of rubber and producing first samples of various rubber compounds. This method is generally the most suitable method for low and medium sized serial production. (Billmeyer, 1984)

Figure 1: Compression molding Injection molding involves preheating the rubber compound while it's being processed through an extruder. Using high pressure, the compound is injected into the mold cavity for a certain time, pressure and temperature. Typical items include high quantity small products weighing between a few grams to several kilograms. Cycle time is relatively short and the injection presses and the molds are relatively expensive. (Crawford, 1998)

Figure 2: Injection molding

Transfer molding is similar to compression moulding except instead of the moulding material being pressurized in the cavity, it is pressurized in a separate chamber and then forced through an opening into a closed mould. Transfer moulding usually have multicavities. The advantages of transfer moulding are that the preheating of the material and injection through a narrow orifice improves the temperature distribution in the material and accelerate the cross linking reaction. As a result the cycle times are reduced and there is less distortion of the moulding. However, transfer mouldings are more expensive than the ones used in compression moulding. (Crawford, 1998)

Figure 3: Transfer molding 2

4.3 Equipments: Hot press, Moulds, Stop watch, Weight balance, Cutter, Gloves, Transparent sheet 4.4 Materials:

Compound A, B and C from Experiment 2

4.5 Procedures: 1. The testing specimens for tensile, tear, resilience, abrasion, and compression set were prepared by using a right mould to cure the compounds. 2. Before the molding process was done, the standard procedure for hot press operation was familiarized. 3. The hot press temperature was set to 160oC with the optimum cure time obtained from the rheograph in experiment 3 with force of 10 MPa as shown in table 1. 4. A bumping was done for 3 to 5 times to avoid bubble in the rubber sheets before compressed. 5. Each molded rubber sheet was cut to 4 dumbbell test pieces for tensile test and 4 trouser test pieces for tear test from compound A, B and C respectively. 6. Same procedure was repeated for hardness button, compression set disc, abrasion and resilience test pieces. 3 test pieces were chosen for each physical testing.

Table 1: Molding time for test pieces compound A, B, and C Compound t90 from rheograph (min) Tensile & Tear Hardness& Resilience Compression set Abrasion A 1.60 2.63 4.63 5.63 8.63 B 3.61 5.61 6.61 9.61 C 1.71 10.82 12.82 13.82 16.82

Cure time (min)

Table 2: Quantity of each types of testing specimen for compound A, B and C Test Piece Shape Weight, g A B C Tensile & Tear Sheet 35 4 4 4 Hardness & Resilience Plate 11 3 3 3 3 Compression Set Button 11 4 4 4 Abrasion Cylinder 55 2 2 2

4.6 Result and Discussion 4.6.1 Observation made during experiment There is a change in colour for all rubber compounds after undergoing hot press. The colour changes from white to light brown for compound A and B. While for Compound C, it changed into semi transparent with dark brown in colour. Besides, excess flash can be observed at the edge of the product and trimming process is required. This is because the pressure and heat developed inside the mould can cause some material to squeeze out of the mould when the split moulds are enclosed by hydraulic press.

Before undergoing hot press, the rubber compound is very tacky and soft. However, after undergoing vulcanization process by using hot press, all compounds shown a decrement in tackiness. This is because the crosslink between chains was generated and was hard to undergo deformation. However, different result can be observed in compound B (CV system). Compound B still feel sticky and soft when touched by bare hand. This is because the reversion occurs in compound B that constitute mainly of polysulphidic linkage that tend to undergo chain scission on prolonged heating. This means that the compound B is over cured. The compound was over cured because the cure time provided by rheograph is not accurate since the rubber compound probably not homogenous mixed as discussed in Experiment 3.

The most obvious observation that can be made is compound B has fail to maintain its shape in the mould. One of the reason is the over curing the compound B that cause the rubber to melt again and overflow along outside and the edge of the mould. That is why the test specimens from rubber compound B have become doughnut shape after subjecting to moulding. Besides, the samples also fail to retain its shapes after the test specimen has taken out from the mould. The test specimens become swell (at this stage, the test pieces is hot) after taken out from the mould and once again undergo dimensionally change (shrink a bit) in the process of cooling. A rubber compound with satisfaction vulcanization reaction will show lowest dimension change and can retain its dimensions when they taken out from the mould and undergo cooling. This can be occurred if the curatives are all homogenously mixed and all rubber chains are tightly bonded (but the crosslink density is not that high and yet retain its extensibility) by the curatives in 3-D network structure so there are no or little plastic flow available. The

plastic flow is available if the rubber chains are not fully bonded to each other and distribution of cross linking not in normal way.

4.6.2 Problems arise during moulding process and its factor Contamination Dirt that sticks on the rubber compound shows the contamination occurred. This may cause by the dirty mould. When the plate of the clamp the compound, the dirt that still remain on the plate or the mould will directly stamped onto the compound. In addition, contamination might also occur when we hold the rubber sample by using the gloves. The fibre of the gloves will definitely stick on the rubber compound since the rubber compounds are still soft and tacky. Dirt that present in the test pieces will probably affect the accuracy of result that obtained in the coming laboratory.

Excessive flash During hot press, the stock will flow and completely fill the mold cavity under the applied pressure and heat. The slight excess flows out through special grooves which are known as mold flash. It can be observed that when the moulded compound are done, too much material exiting at the edge of the mold. It can be a consequence of using excessive loading of compound. The dosage of compound did not estimate well causing a waste. Improper mould aligning or mould design also can cause this problem. Moreover, not properly adjusted mold clamping pressure and temperature will also cause flash produced. It affects the mold deflection, thus shear edge clearance. (Bruce, 2003)

In compound B (CV system), the mould flash are excess than the expected. The surface of mould edges are covered fully by the flash material. The flash material might probably be the over cured rubber stock due to prolonged heating. The prolonged heating is due to the error made during made when determine the scorch time and cure time of rubber compound by using the rheometer and Mooney viscometer. When determining the cure characteristics of rubber compound, it is recommended to take the sample from different portion of rubber compound because the ingredients incorporated into the raw rubber might not homogenously mixed. Then, the cure time are statistically calculated to avoid the broad standard deviation and get the average cure time. Five sample (7 g) are recommended to determine the cure characteristics of rubber compound and taking the average by considering the standard deviation. However, there are only one sample 5

taken to determine the cure behaviour of the rubber compound and that might cause difficulty to get the central tendency of cure time if the rubbers are not well dispersive and distributive mixed.

Blister When high pressure is applied, a large quantity of gas is forced into the mould area. If a rapid depressurization occurs, trapped gas will expand violently and try to escape to the lower external pressure. The explosive expansion of gas within the elastomer can cause blister to the rubber compound. Besides that, especially when de-freeze it out of the freezer, condensation of water droplet on the rubber compound surface occur. If the moisture is subjected to high temperature and pressure in the mold, it will become steam and form blister inside the molded compound. (Nagdi, 1999)

Slippage of mould plate The plate unable to stay in horizontal condition cause the plate to slip during clamping process due to the uneven shape of rubber compound. Eventually the shear friction occurs where the both mould plate move in opposite way. This may cause some part of the compound are not covered and shaped. This will cause the unwelcome flow when the mould and the plate are not clamped well. Tearing When the molded compounds are taken out from the mould, tearing can occur. This usually occur for the sample likes sheet which it has a small thickness. This is a common careless mistake done by the removal. The hardly removed flash that attaching to the side of mould increase the difficulty of removing the molded compound. Besides that, an over cured or under cured state of compound also will cause tearing to occur due to the low strength of the compound. The over cured or under cured thin compound do not have a stable cross-link formation to withstand the removal force.

Porosity Cured rubber articles sometimes show a certain porosity meaning that small cavities are found in the rubber matrix. This problem happens in the abrasion test pieces. The porosity problem is caused by air or volatile materials such as water within the uncured compound that evaporate and subsequently expand under the high temperature curing condition if the applied pressure is too low to keep them from blowing. Especially in 6

under cured compounds these gaseous materials can expand when the mold pressure is released at the end of the cure cycle.

4.6.3 Troubleshooting To reduce and solve problems in the manufacturing process, corrective and preventive actions can be taken. Preventive actions are preferred over corrective actions. Corrective actions, since they are not planned, can stop production, take longer to solve and more expensive than planned preventive actions. (Bruce, 2003)

Contamination Before start the molding process, check for settling dirt on moulds or compound before processing. Make sure the handling equipment such as the mould is cleaned or polished. Try to use a tool instead of direct contact with the compound with bare hand or gloved hands.

Excessive flash Decrease the initial charge weight and make sure a correct weight of blanks to use. This can helps to prevent waste of source. Apart of that, the clamp pressure, mold clamping pressure, mold closing speed have to be decreased to ensure the compound do not forced to flow under high pressure and speed before it can entirely fill up the cavity. The mold temperature also can be increased to enhance the flow of the compound in the cavity. The shear edge or vents clearance also crucial to be checked to maintain a good cavity filling.

Slippage of mould plate To overcome this problem, the rubber compound should be cut into the may fit the cavity of the mould. For making a sheet, the thickness of the compound should be as uniform as possible so that the plate can stay horizontally. The rubber compound should be distributed uniformly in the cavity to make sure the rubber flow into entire cavity. For the case like making a button or cylindrical shape, the compound should be cut into pieces that can fit into the cavity and this can help to cavity filling more effectively.

Blister This can be overcome by doing bumping process. Several times of bumping process win some extra time for the air to escape from the mould by the pressure applied. It also helps the compound to fit into the cavity. For the moisture problem, after the compound are warmed to ambient temperature after taken out from freezer, air-blower can be used to dry out the moisture on the compound surface. It also helps to blow away some debris that stay on the compound surface.

Tearing As this problem more to cause by individual error done, extra care and attention should be paid when removing the molded compound from the mould. Some tools can be used to aid the removal of the molded compound in order to reduce the formation of little crack at the edge that may lead to tearing.

Porosity To overcome such problem, it is advised that the bumping process must be one at least 3 times and the rate of must as fast as possible. This will reduce the possibility that the moisture bubble do not attached on the surface of the rubber compound and only blow when its already cured. Furthermore, additive that retarded the air bubble formation can be added to avoid porosity. 4.7 Conclusion Hot press process is the compression type molding process where shaping and vulcanization of rubber compound take place simultaneously since the temperature introduce is very high suitable for crosslink formation. It is considered a simple and easy molding. It is highly dependence on manual operating where the unloading and loading of mould need to be carried out individually. During molding process, there are a lot of problems occur such as contamination, blister, tearing, excessive flash and porosity. Pre-caution steps have to be taken in order to minimize the occurrence of these problems. Good instrumentation is critical because most troubleshooting actions are related to temperature, pressure and velocity, among others. It is important to ensure that the instruments are in good condition and well calibrated so that there is confidence in the measurements. Suitable corrective and preventive actions must be taken to troubleshoot and maintenance. 8

Reference 1. Crawford, R.J (1998). Plastic Engineering: 3rd edition. New York: ButterworthHeinemann 2. Billmeyer, F.W. (1984). Textbook of Polymer Science. USA: John Wiley& Sons 3. Khairi Nagdi. (1992). Rubber as an engineering material: guideline for users. Munich: Hanser Verlag. Appendix

Figure 4: The typical example of test specimen due to over cured