scholarly journals CHARACTERIZATION OF THE MULLINS EFFECT OF CARBON-BLACK FILLED RUBBERS

2011 ◽  
Vol 84 (3) ◽  
pp. 402-414 ◽  
Author(s):  
Yannick Merckel ◽  
Julie Diani ◽  
Mathias Brieu ◽  
Pierre Gilormini ◽  
Julien Caillard

Abstract Several carbon-black filled styrene-butadiene rubbers showed different sensibilities to the Mullins softening when submitted to cyclic uniaxial tension. In order to quantify this softening, a damage parameter was introduced. It is defined by using a classic damage approach and can be estimated by using either the strain amplification factor method or the tangent modulus at zero stress. The proposed parameter is used to study the effects of crosslink density and filler amount on the Mullins softening. The latter is shown to remain unaffected by a change of crosslink density and to increase with an increase of filler amount. The damage parameter exhibits mere linear dependences on the maximum Hencky strain applied and on the filler volume fraction. A simple linear expression is given finally to predict the Mullins softening of filled rubbers. The parameter also provides an objective analysis for the Mullins softening that supports comments on a better understanding of this effect.

2013 ◽  
Vol 86 (2) ◽  
pp. 218-232 ◽  
Author(s):  
Y. Fukahori ◽  
A. A. Hon ◽  
V. Jha ◽  
J. J. C. Busfield

ABSTRACT The modulus increase in rubbers filled with solid particles is investigated in detail here using an approach known widely as the Guth–Gold equation. The Guth–Gold equation for the modulus increase at small strains was reexamined using six different species of carbon black (Printex, super abrasion furnace, intermediate SAF, high abrasion furnace, fine thermal, and medium thermal carbon blacks) together with model experiments using steel rods and carbon nanotubes. The Guth–Gold equation is only applicable to such systems where the mutual interaction between particles is very weak and thus they behave independently of each other. In real carbon black–filled rubbers, however, carbon particles or aggregates are connected to each other to form network structures, which can even conduct electricity when the filler volume fraction exceeds the percolation threshold. In the real systems, the modulus increase due to the rigid filler deviates from the Guth–Gold equation even at a small volume fraction of the filler of 0.05–0.1, the deviation being significantly greater at higher volume fractions. The authors propose a modified Guth–Gold equation for carbon black–filled rubbers by adding a third power of the volume fraction of the blacks to the equation, which shows a good agreement with the experimental modulus increase (G/G0) for six species of carbon black–filled rubbers, where G and G0 are the modulus of the filled and unfilled rubbers, respectively; ϕeff is the effective volume fraction; and S is the Brunauer, Emmett, Teller surface area of the blacks. The modified Guth–Gold equation indicates that the specific surface volume ()3 closely relates to the bound rubber surrounding the carbon particles, and therefore this governs the reinforcing structures and the level of the reinforcement in carbon black–filled rubbers.


2018 ◽  
Vol 197 ◽  
pp. 12006 ◽  
Author(s):  
Indra Surya ◽  
Hanafi Ismail

By using a semi-efficient sulphur vulcanisation system, the effects of alkanolamide (ALK) addition on cure characteristics, crosslink density and tensile properties of carbon black (CB)-filled styrene-butadiene rubber (SBR) compounds were investigated. The ALK was prepared from Refined Bleached Deodorized Palm Stearin and diethanolamine and added into the CB-filled SBR compounds. The ALK loadings were 1.0, 3.0, 5.0 and 7.0 phr. It was found that ALK decreased the scorch and cure times of the CB-filled SBR compounds. ALK also improved the tensile modulus and tensile strength; especially up to a 5.0 phr of loading. The crosslink density measurement proved that the 5.0 phr of ALK exhibited the highest degree of crosslink density which caused the highest in tensile modulus and tensile strength. Due to its plasticity effect, ALK increased the elongation at break of the CB-filled SBR vulcanisates.


1967 ◽  
Vol 40 (3) ◽  
pp. 866-882 ◽  
Author(s):  
M. Porter

Abstract The degree to which HAF black restricts the swelling of natural rubber vulcanizates in n-decane has been determined using a vulcanizing system in which the stoichiometry of crosslinking is unaffected by the carbon black. The dependence of the degree of restriction, as measured by the ratio of the volume fractions of rubber in the filled and unfilled vulcanizates swollen to equilibrium, on the concentration of carbon black follows an exponential relationship previously proposed by Lorenz and Parks. This is found to be equivalent to a simple linear relationship between the apparent and actual crosslink concentrations: napparent/nactual=1+Kϕ, where K is a constant characteristic of the filler and φ is its volume fraction in the vulcanizate. The relation has been used to determine actual crosslink concentrations in filled natural rubber vulcanizates. HAF black is found to cause increases of up to 25 per cent in the yield of polymer to polymer crosslinks in conventional sulfur vulcanizing systems, accompanied by changes in rate of cure and of crosslink reversion. All these are small compared with the effect of the filler on many physical properties.


2013 ◽  
Vol 812 ◽  
pp. 236-240
Author(s):  
Mohd Zaki Nurul Ayunie ◽  
Ahmad Zafir Romli ◽  
M.A. Wahab ◽  
Mohd Hanafiah Abidin

The effects of epoxidized palm oil (EPO) content in carbon black filled styrene butadiene rubber (SBR) on tensile strength, elongation at break and crosslink density were investigated. Five different loadings of EPO in parts per hundred rubbers (phr) were used to test the tensile strength of the carbon black filled SBR which showed a decreasing trend as the content of EPO in the vulcanizates increased. In contrast, elongation at break showed the opposite trend where the elongation at break increased as the content of the EPO increased. The SBR vulcanizates with the highest content of EPO gave the highest value of elongation at break which is 2393.56%. In the case of swelling index, it was found to increase as the amount of EPO increased.


1990 ◽  
Vol 63 (1) ◽  
pp. 32-45 ◽  
Author(s):  
Siegfried Wolff ◽  
Jean-Baptiste Donnet

Abstract 1. Up to now, the application of the Einstein-Guth-Gold equation seemed to be limited to inactive fillers. 2. However, in the form of Equation (6), it describes with high accuracy the moduli of vulcanizates containing active fillers as a function of the filler volume fraction at least up to ϕ=0.22 at uniaxial elongations and for any given value of λ. 3. The effectiveness factor ƒ is independent of crosslinking density, but is dependent on deformation, temperature, and the surface activity of the filler. 4. If ƒ as a function of elongation is known, the respective stress-strain curves of filled networks can be calculated in advance for any given crosslinking density. 5. The interpretation of the effectiveness factor will require further investigations, especially with regard to the influence of the structure and surface activity of the filler.


2005 ◽  
Vol 78 (1) ◽  
pp. 76-83 ◽  
Author(s):  
J. Wang ◽  
G. R. Hamed ◽  
K. Umetsu ◽  
C. M. Roland

Abstract Double network elastomers were prepared by curing under strain previously-crosslinked natural rubber or styrene-butadiene copolymer. The rubbers were reinforced with carbon black, so that the conventional (singly-cured) materials exhibited a substantial Payne effect, reflecting agglomeration of the filler particles. This effect was much reduced in the double networks - the storage modulus varied more weakly with strain amplitude, and the mechanical hysteresis was substantially smaller. Comparable results were obtained for dynamic mechanical measurements employing different test geometries; that is, the effect is independent of the direction of the strain relative to the orientation of the double network. These results indicate that deformation during the imposition of a second network disrupts the carbon black agglomerates, and this deflocculated structure is stabilized by the second crosslinking. Thus, double network processing is a general means to lower the hysteresis of filled rubbers.


2013 ◽  
Vol 86 (4) ◽  
pp. 572-578 ◽  
Author(s):  
Julie Diani ◽  
Yannick Merckel ◽  
Mathias Brieu ◽  
Julien Caillard

ABSTRACT The authors compared the mechanical behavior and, more precisely, the Mullins and the cyclic (post-Mullins) softenings of two filled rubbers. A crystallizing natural rubber and a noncrystallizing styrene–butadiene rubber of similar compositions resulting in similar cross-link densities and filled with 40 phr of N347 carbon-black fillers were tested in cyclic uniaxial tension at room temperature and at 85 °C. Crystallization in filled rubbers is known to increase stress at high stretch, stretch at break, cycle hysteresis, and fatigue lifetime and to reduce crack propagation. In this study, it is shown that crystallization also seems to enhance the Mullins softening (softening at the first cycle) and to favor the apparent cyclic softening. Results reveal that natural rubber shows an amplitude dependence on the cyclic softening, whereas the styrene–butadiene rubber does not. Finally, results demonstrate that studying filled rubber softening cannot help predict lifetime.


2003 ◽  
Vol 76 (4) ◽  
pp. 832-845 ◽  
Author(s):  
William L. Hergenrother ◽  
Ashley S. Hilton

Abstract A technique is described allowing a relatively simple determination of χ as a function of vr from swelling in heptane. A good measure of the true νe of the cured elastomer at all values of vr was demonstrated by substituting this relationship for χ in the Flory-Rehner (F-R) equation. The relationship was established over a wide range of vr values by using samples that had the νe of the cured elastomer determined by tensile retraction (TR). Applying this function to samples treated using the thiol probe method of Campbell gave an improved measure of the types of crosslinks present in sulfur-cured stocks. An identical equation describing χ as a function of vr in heptane was obtained with NR, EPDM and SBR containing up to a 0.31 volume fraction of carbon black (CB) and other fillers. The presence of up to 10 % of clay, talc, silica, resins or metal oxides in the CB had no noticeable effect on the relationship measured. However, when the filler contained about 50% silica a distinctly different slope in the relationship was found. The percent S1, S2 and Sx distribution measured was contrasted between measurements made by 13C NMR, swelling with χ = constant or χ as a function of vr.


2011 ◽  
Vol 284-286 ◽  
pp. 1969-1973
Author(s):  
Xiao Ling Hu ◽  
Yong Ouyang ◽  
Xiong Zhou ◽  
Wen Bo Luo

The tensile stress-strain relationship of rubbers is fairly linear and can be used for obtaining tensile modulusE. In this work we analyzed the tensile stress-strain relationship of filled rubber experimentally and employed the extended 2D homogenization method to compute the modulus of the carbon black (CB) filled rubbers with various CB volume fractions ranging from 5% to 25%. The results reveal that the modulus of CB-filled rubbers increased with the increase in CB volume fraction and in CB aggregation.


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