Cure Rheometer

Properties are obtained from a cure rheometer at 150°C. Minimum torque to maximum torque. 

In the third chapter, the methods used for evaluating the kinetics of the cure of rubbers are described and studied on the basis of either the heat evolved from the cure reaction (calorimetry) or the change in the mechanical properties during the cure (rheometers). Theoretical studies are made so as to improve either the isothermal MDR, or even the MDR in scanning mode, by considering different temperature-time relationships. 

Cure of rubber vulcanizates is commonly measured using a Monsanto cure rheometer, which plots the change in torque as a function of time as is shown in Figure 1. From the percentage rise of the graph, the percent cure can be calculated. 

Figure 1. Cure rheometer trace for rubber vulcanization.

Scorch is a property of the rubber compound that relates to the proportion of available cross-links that have been used up at any particular point in the process. When 5% of available cross-links have been completed, the rubber is said to be 100% scorched. If the rubber has reached this level before the mould is completely filled, no satisfactory bond is possible. Experimental work has shown that for consistent zero-defect production, the scorch level should not exceed 20% (1% cross-linked) before the rubber has been fully consolidated against the prepared surface to which it is to be bonded. The derivation for cross-link density from a cure rheometer trace is shown in Fig. 1. 

In bromobutyl/chlorobutyl rubber blends, both elastomers have the polyisobutylene backbone and halogen reactive functionality. These polymers, being molecularly miscible, constitute an ideal system for co-vulcanization. Bromobutyl and chloro-butyl can be used interchangeably without significant effect on state of cure as measured by extension modulus, tensile strength, and cure rheometer torque development. Bromobutyl will increase the cure rate of a blend with chlorobutyl. However, where bromobutyl is the major part of the blends, chlorobutyl does not reduce scorch tendencies because the more reactive halogen unit can dominate. 

L-value Parameter obtained from cure-rheometer... 

Fig. 3. Fate of accelerator components during cure, where A is TBSI B, MBTS C, development of cross-links (rheometer) D, MBT and E, BtS Bt (13).

Fig. 2. Cure curve from oscillating disk rheometer where A represents scorch safety B, cure rate C, state of cure D, optimum cure time and E, reversion.

MHR = maximum stiffness during cure minus minimum stiffness, both in a rheometer. To convert /cm to Ibfin., divide by 0.0175. Too = Scorch time. 

Vulcanization was carried out in one and two stages with and without carbon black. In one-stage vulcanization, all the ingredients were mixed and the compound was vulcanized in the mold for optimum cure time as shown by Monsanto rheometer curves. In the two-stage vulcanization process, all the ingredients except XNBR were mixed and heated for a short time, followed by mixing with required amount of XNBR and heating for rest of the time required for optimum vulcanization. 

In order to test this concept a series of compounds was prepared in a 5 L Shaw Intermix (rubber internal mixer, Mark IV, Kl) with EPDM (Keltan 720 ex-DSM elastomers an amorphous EPDM containing 4.5 wt% of dicyclopentadiene and having a Mooney viscosity ML(1 +4) 125°C of 64 MU 100 phr), N550 carbon black (50 phr), diisododecyl phthalate (10 phr), stearic acid (2 phr), and l,3-bis(tert-butylperoxy-isopropyl)benzene (Perkadox 14/40 MB ex Akzo Nobel 40% active material 6 or 10 phr). A polar co-agent (15 phr) was admixed to the masterbatch on an open mill and compounds were cured for 20 min at 180°C in a rheometer (MDR2000, Alpha Technologies). The maximum torque difference obtained in the rheometer experiments was used as a measure of... 

In all of the rheometer testing of the uncured compounds, the commercial silica AZ showed the highest values with the B1 and B3 samples having the highest values among the B-series silica samples. The Mooney viscosity at 100°C increases as the number of particles in the aggregates increases. The same compounds were cured and tested, measuring tensile properties, tear resistance. 

The specimen was prepared by the following method. After mixing HAF carbon black (50 phr) with natural rubber (NR) in a laboratory mixer, carbon gel was extracted from unvulcanized mixture as an insoluble material for toluene for 48 h at room temperamre and dried in a vacuum oven for 24 h at 70°C. We made the specimen as a thin sheet of the carbon gel (including carbon black) by pressing the extracted carbon gel at 90°C. The cured specimen was given by adding sulfur (1.5 phr) to the unvulcanized mixture and vulcanized for 30 min at 145°C. The dynamic viscoelastic measurement was performed with Rheometer under the condition of 0.1% strain and 15 Hz over temperatures. 

A development of the moving die rheometer where the operation of the unit is fully computer controlled. The rate of oscillation, temperature and level of strain can all be run through a series of options. The torque measurements are also highly sophisticated. As a consequence, the unit can be set up to monitor processing parameters, then the cure behaviour and finally the finished dynamic properties of the cured material. It is manufactured by Alpha Technologies. 

The degree of vulcanisation of a rubber compound is assessed technically by the indefinite terms of undercure, correct cure, optimum cure and overcure. It may be given precision by (a) measurement of stress-strain relationship of a range of cures, (b) measurement of the modulus at 100% elongation, (c) measurement of the volume swelling in benzene, or (d) by the use of instruments such as the oscillating disc rheometer and the moving die rheometer. 

An early cure instrument which combined in one operation the functions of a Mooney viscometer and of a curometer or vulcameter, i.e., it measures in one quick test the plasticity (viscosity) of the (uncured) mix, its scorch time and cure rate. Now superseded by instruments such as the moving die rheometer. 

The influence of ZnCFO concentration (3,0 5,0 7,0 phr) on formation of properties complex of the unfilled rubber mixes and their vulcanizates on the basis of isoprene rubber of the following recipe, phr isoprene rubber - 100,0 sulfur - 1,0 di - (2-benzothiazolyl) -disulfide - 0,6 N, N -diphenylguanidine - 3,0 stearic acid - 1,0, was carried out in comparison with the known activator - zinc oxide (5,0 phr). The analysis of Rheometer data of sulfur vulcanization process of elastomeric compositions at 155°C (fig. 5) shows, that on crosslink density and cure rate, about what the constants of speed in the main period (k2) testify, they surpass the control composition with 5,0 phr of zinc oxide. Improvement of the complex of elastic - strong parameters of rubbers with ZnCFO as at normal test conditions, and after thermal air aging (tab. 1), probably, is caused by influence of the new activator on vulcanization network character. So, the percent part of polysulfide bonds (C-Sx-C) and amount of sulfur atoms appropriating to one crosslink (S atoms/crosslink) in vulcanizates with ZnCFO are decreased, the percent part of disulfide bonds (C-S2-C) is increased (fig. 62). 

Measuring Vulcanization. The formation of a three-dimensional structure during vulcanization increases the stiffness (modulus) of the compound. Therefore, following the modulus increase versus cure time provides a continuous picture of the vulcanization process. Oscillating disk rheometers provide a useful method to do this (17). In this test, a preweighed sample of uncured mbber is placed into a preheated cavity containing a conical rotor. The cavity is closed and the rotor is set to oscillate within the mbber sample. As vulcanization proceeds, the compound s resistance to rotor movement increases and this resistance is followed as a function of time, thereby generating a continuous profile of cure behavior. These cure curves,... 

ASTM D3795, Test Methodfor Thermal Flow/ Cure Properties of Thermosetting Plastics by Torque Rheometer, Vol. 8.02, ASTM, Philadelphia, Pa., 1993. 

If a fully compounded thermosetting rubber is subjected to a plasticity measurement at a high enough temperature and for long enough, it will cure and, consequently, there is not always a clear distinction between a plasticity test and a test for scorch or rate of cure. For example, the Mooney viscometer is used to measure scorch, i.e. the onset of vulcanisation, and an oscillating disc rheometer will measure the plasticity of the compound before the onset of cure as well as the increase in stiffness as curing takes place. 

ASTM D6601, 2002. Measurement of cure and after cure dynamic properties using a rotorless shear rheometer. 

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