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Saule Abdrazakovna Sakibayeva, Dzhakipbekova Nagima Ormanbekovna, Ulbala Sultanovna Zhantasova, Gulnar Zhumadillaevna Mamytova, Madinur Rashytovna Sattarova, Aziza Bakytzhakizi Issa M. Auezov South Kazakhstan state university, Kazakhstan.
E-mail: isa.aziza@mail.ru
RESEARCH THE COMPLEX EFFECT OF NEW INGREDIENTS ON THERUBBER PROPERTIES
Abstract: The purpose of the this work was the research of complex influence of the new ingredients obtained on the basis of oil slimes on properties of rubbers. The results of the researches have shown a possibility of using in compounding of rubber mixes for production of wearproof onboard tape as ingredients — organic (softener) and mineral (filler) of a part of oil slime, polymeric sulfur of LLP "PKOP" (the vulcanizing agent). The rubber compounds are obtained with using of organic and mineral parts of oil slime of LLP "PKOP" and the polymeric sulfur which synthesized from gas technical sulfur of LLP "PKOP" is competitive both on the physical and mechanical properties, and at cost that, in turn, utilization of oily waste and rational use of sulfur in production of rubber products and buses allows to solve problems.
Keywords: oil slimes, organic and mineral parts of oil slime, sulfur polymer, rubber mixture, rubber, mixing, vulcanization, vulcanizing agent.
The oil industry in terms of negative impact on the In connection with the foregoing, the objective
environment is one of the leading positions among the of this work is to research the combined effect of new
industries, the development of which contributes to the ingredients, obtained on the basis of oil sludge on
increase in volumes generated oily wastes that have a properties of rubber compounds.
negative impact on the environment. In the Republic of In the previous analysis [2] we have found that
Kazakhstanoil industry is growing rapidly. In this regard, in the organic part of sludge LLP "PetroKazakhstan
certainly one of the priority tasks aimed at reducing OilProducts" (LLP "PKOP"), there are no light
the negative impact of waste on the environment fractions in composition and properties it is close to
and improving the resourcing of the economy, is the heavy oil residuals having a high content of gumsand
development and implementation of new perspective asphaltenes. The presence of large quantities of
directions of disposal of large waste oil refining with the aromatics and unsaturated hydrocarbons in the organic
creation of innovative industries. Therefore, the search part of sludge allowed us to use it as an emollient in
for rational use of sludge in various industries acquires the recipes of rubber compounds for the manufacture
a relevant importance for the economy of Kazakhstan. of rail pads. A study of the mineral part of sludge LLP
A wide range of compositions of oily waste requires the "PKOP" has allowed us to make a conclusion about
development ofeconomically viable and environmentally possibility of its use as filler in rubber compounds
efficient technologies contributing to the solution of the as it has high dispersity and well-developed specific
problem of comprehensive utilization of oil sludge. One surface. The analysis of granulometric composition
of the possible ways of disposing of sludge is its use as of mechanical impurities, isolated from sludge of LLP
ingredients in rubber compounds [1]. "PKOP" has shown that is 87.9% of the mineral part
of sludge is small (less than 0.5 mm). The value of the part of the fuel mass of oil sludge and containing atoms
specific surface of the sludge amounted to 31.2 m2/g. of iron, magnesium, aluminum, copper, etc. Mechanical
The mineral admixturesof oil sludge contains salts admixtures represent sand (quartz), clay (kaolinite), silt,
of alkali metals, organometallic compounds, which are corrosion products of metals (rust) [3].
Table 1. - Shows the chemical composition of mechanical impurities extracted from the oil sludge
Quality indicators, % Si02 FeA CaS0, CaO MgO ALO3 The loss of ignition
The values of quality indicators 35,6 11,5 5,3 3,3 2,6 1,2 40,5
X-ray diffraction analysis of sludge LLP "PKOP" on the device XDGP-3 (X-ray diffractometer general purpose) showed that the main components of the mineral part of sludge are quartz, calcite.
X-ray diffraction analysis of sludge LLP "PKOP" on the device XDGP-3 (X-ray diffractometer general purpose) showed that the main components of the mineral
part of sludge are quartz, calcite. In the sample (figure 1) diffraction peaks with the values of the interplanardis-tances d/n=4,24-4,08-3,24-2,45-2,28-1,81-1,53A0are crystalline arrays of ^-cvar (^SiO2) is the main phase. In small quantities by the values of the interplanardistances d/n=3,02-2,52-2,28-2,08A0observed calcium carbonate [4].
Figure 1. X-ray analysis of mineral component of sludge
It is known that fillers are introduced into the rubber mixture to improve the technological properties of increasing the physical-mechanical properties of rubbers, give them certain specific properties and reduce the cost ofproduction. The choice offiller is determined primarily by the size of its particles and their size distribution (polydispersity) and shape of the particles and the nature of their packaging. The dispersibility of the filler largely affects the final properties of the composite material. The
interaction of rubber with filler particles, a crucial role in the amplification of the rubbers played by the size and shape ofparticles and the structure ofthe filler surface [5].
To detect activity of organic parts and mineral parts of sludge LLP "PKOP" in rubber compounds were examined in standard rubber mixture based rubbersynt heticcaoutchoucisoprene SCI-3 for the manufacture side tape. Recipe rubber compound for the manufacture of wear-resistant side tape are shown in table 2.
Table 2. - Recipe rubber compound for abrasion-resistant side tape
The name of the ingredients 100 masses parts of rubber
Standard Research variation
1 2 3
SCI-3 40,0 40,0 40,0 40,0 40,0 40,0
Synthetic rubbers butadiene-methylstyrene SCMS-30 ARC 60,0 60,0 60,0 60,0 60,0 60,0
PolymericsulfurLLP «PKOP» 4,0 4,0 4,0 4,0 4,0 4,0
Sulfenamide «M» 1,2 1,2 1,2 1,2 1,2 1,2
Technicalstearicacid 2,0 2,0 2,0 2,0 2,0 2,0
WhiteZinc 5,0 5,0 5,0 5,0 5,0 5,0
Santogard PVI 0,4 0,4 0,4 0,4 0,4 0,4
Pine wood colophony EM 2,0 2,0 2,0 2,0 2,0 2,0
1 2 3
Softener AREG 4,0 — — — - —
Органическая часть нефтешлама - 4,0 4,5 5,0 5,5 6,0
Oil GO-6T 4,0 4,0 4,0 4,0 4,0 4,0
Wax protective WPP 2,0 2,0 2,0 2,0 2,0 2,0
Acetonanil RD 2,0 2,0 2,0 2,0 2,0 2,0
Deafen (IPPD) 2,0 2,0 2,0 2,0 2,0 2,0
Technicalcarbon F 514 40,0 40,0 40,0 40,0 40,0 40,0
Technicalcarbon F 234 40,0 35,0 30,0 25,0 20,0 15,0
The mineral part of sludge - 5,0 7,0 10,0 15,0 20,0
In the studied prescriptions were replaced: softener AREG (asphaltene-resinous emollient granular) on the organic part of sludge, and partially technical carbon F 234 on the mineral part of sludge, the quantity of the mineral part of sludge ranged from 5 to 20 m.p at 100 mass parts of rubber. As the curing agent used polymeric sulfur LLP "PKOP", synthesized from a gaseous technical sulphur LLP "PKOP" with the content of elemental sulfur is 90,4%, the stability of 85.6% (table 2).
The quality of sulphur curing agent of rubber compounds, to meet such requirements as a high degree of purity of the product (minimum content of harmful impurities — metals ofvariable valency) and high degree of dispersion [6]. The sulfur content in the gas technical sulfur LLP "PKOP" is 99,53%, indicating the high purity of the product.
Factors influencing the slow rate of diffusion of sulfur and accelerator in the elastomer, are — the increase in molar volume, polymerization of sulfur, the interaction of sulfur with other chemical compounds, adsorption on the surface of carbon black particles, replacement of the sulfur of sulfur-containing compounds, oligomers and polymers, as well as the binding of components of sulfur curing systems in solid solutions of intermolecular action, reduce or eliminate fading of sulfur on the surface of rubber compounds [7].
The polymer form is not soluble in the elastomers and has a low diffusion rate due to a sharp increase in molar volume. The molecular weight ofpolymeric sulfur, depending on the production method can vary from 10*10430*104' Polymeric sulfur at temperatures below
• S - S - S^ +R- COOH (acid) ■
II " II
OO
160 °C is a metastable modification and therefore it has a strong tendency to turn under normal conditions in the thermodynamically stable a-rhombicmodification that triggers the need for stabilization of polymeric sulfur. Therefore, at the present time the greatest attention is paid not so much to seek new methods of obtaining polymeric sulfur, as the most effective stabilizers [8].
For translation the gas technical sulfur LLP "PKOP" to the polymeric, as a modifier we have chosen a balance of fatty acids ", (bottoms residue of fatty acids) "BRFA", which is a waste oil and fat industry, in the manufacture of cottonseed oil, which is obtained by the process of selective treatment by furfurylated alcohol gossypol. The modifier "BRFA" is a mixture of saturated and unsaturated hydrocarbon compounds. It is highly soluble in water, alcohol, poorly soluble in organic solvents. As the surfactant chosen was a modified polyacrylamide (MPAA) is a gel— like viscous mass of light-brown color [9].
In the interaction of the molten sulfur with the modifier "BRFA" a dissolution modifier " BRFA" in the sulfur melt, and then chemical interaction with sulfur modifying agent. The process of chemical interaction of sulfur with a modifying additive proceeds in two stages. In the first stage, the transfer of sulfur in a reactive form as a result of decomposition at temperatures of 120-1500C by the disclosure ring cyclooctanone S8.In the second stage, the chemical interaction of sulfur with a modifying additive.
The proposed mechanism of formation a low molecular weight polymer chains of the modified sulfur has the form:
(R-C- O - S - S - S -O - C - R)
Further, surface-active substance modified Polyacrylamide "MPAA" structures of polymeric sulfur. In our view, the structuring process has the following mechanism. Polymers series "MPAA" as well as other amine-derivatives to form ions with a number of complex compounds of sulfur having a structure of the following type [8]:
The main task in the rubber manufacturing is the creation from the rubber and various ingredients in a sustainable multicomponentsystem with maximum mechanical strength and elasticity, and is able to keep the properties over a long period as in a static state and dynamic loads.
Surfactant in rubber compounds is widely used for activation of fillers of rubber mixtures. Treatment of surfactants improves the dispersion of fillers in rubber and increases the intensity of their wetting the rubber, lowering the surface tension between the rubber and powdered ingredients [10]. Modified polyacrylamide "MPAA", as a product of polyfunctional action, may be in the elastomer compositions of properties of the surfactants, plasticizer, antioxidant and modifier, and activate the curing process. "MPAA'raisesincreasing the level of interfacial interaction, increases efficiency particulate structures of technical carbon in the elastomeric compositions, this improves the dispersion in a mixture that promotes the formation of a more
The total duration of mixing in all cases was the same — 29 min. Difficulties during the process of mixing was observed.After the first stage of the rubber blend was twice passed through rollers, the mixture was cooled to room temperature, ripen rubber compounds was at least 2 hours, then proceeded to the second stage. The finished rubber mixture twice again passed through
responsible structure for the technical performance of rubbers.
It is known that "BRFA'rich in substituted polyphenols, fatty acids, triglycerides, hydrocarbons, azo-compounds and other compounds, is an effective modifier of complex action. The above listed compounds contained in the "BRFA", in combination with phosphorus-containing modifier has a plasticizer effect in rubber compounds [11]. It is also known that fatty acids and their derivatives, when they are introduced in the rubber compound affect the vulcanization characteristics. It is a valuable assistant for the dissolution of zinc oxide, used as accelerator activators, and thus accelerates the curing process, allowing you to adjust the duration of scorchingof rubber compounds [12].
The blend mode is usually determined by the following mandatory factors: order of introduction of ingredients and time of introduction of each ingredient or group of ingredients; mixing time of the mixture after the introduction of ingredients and order of mixing; mixing time; temperature of the rolls. Also, the blend mode is also the size of the gap, as this value has an impact on temperature and duration ofmixing (table 3).
The manufacture of rubber mixtures was carried out on a laboratory drum (roll) HT (heating) 32001600/1600.
The temperature of the rolls 50 rolls front-60 °C, backward 60-70°.
Rolls diameter 160 mm.
Length of rolls 320 mm.
The drive power is 4.6-7 kilowatt.
The optimum loading — 1 kg minimum.
rollers. Prior to testing, the raw rubber compound was kept for days at room temperature. When performing the mixing and milling of rubber compounds violations and deviations were observed. The rubber compounds were characterized by uniform distribution of ingredients in the rubber, which ensured the homogeneity of the rubber compound properties.
Table 3. - Characteristics of laboratory rolls
Rubbercompound Technical characteristics of rolls and keeping the mixing process
Friction Mixing The temperature of the mixture when removed from roll, °C.
Wear-resistantsidetape 1:1,2 1 stage - 25 2 stage - 4 1stage - 45 2 stage -30
Plastoelastic properties of rubber compounds are very important technological parameters that significantly affect the processing of rubber compounds. From plastoelastic properties depend on such processing properties as the processing speed, the ability to keep
the given form, the smoothness of the surface, tendency to scorching [4,12]. Data analysis of table 4 shows that the indicators plastoelastic properties of raw rubber compounds meet the standards of control in the dosage of the mineral part of sludge -10 m.p.
Table 4. - Plastoelastic properties of rubber compounds for abrasion-resistant side tape
Indicators Rate of control Master blend 100 masses. parts rubber
5,0 7,0 10,0 15,0 20,0
Plasticity, conventional units 0,20+5 0,22 0,29 0,28 0,20 0,21 0,19
Viscosity according to Mooney, conventional units 70+5 70 70 69 72 68 72
For definition of parameters of technological processes in the production of rubber needs to be known indicators of curing ability rubber compounds, their tendency to premature vulcanization is the beginning of curing and velocity (for processing), for the process of curing, in addition to the above indicators, the optimum vulcanisation plateau, the area of reversion. The ability
of rubber mixtures to premature vulcanization gives vulcanization characteristics taken on a Monsanto rheometer [13].
Table 5 shows the estimates of the parameters of vulcanization characteristics of rubber mixtures for the manufacture of wear-resistant side tape.
Table 5. - Results of calculation of vulcanization characteristics of rubber compounds for abrasion-resistant side tape on the Monsanto rheometer, mode: 155Cx20 minutes
Indicators Standard 6 m.p. Oil FO-6T The organic part of sludge 100 m.p in rubber
5,0 7,0 10,0 15,0 20,0
Minimum torque, M H^m 8,0 9,0 8,6 8,2 8,0 8,0
Saving the viscous-flow state, min 1/22// 1/35// 1/25// 1/27// 1/22// 1/28//
The beginning of vulcanization, M2 H^m 10,0 11,0 10,6 10,2 10,0 10,0
The start time of vulcanization, M min 2/05// 2/10 2/10// 2/10// 2/05// 2/10
Point in the optimum vulcanization M3, H^m 34,1 34,2 34,16 34,12 34,1 35
The time to reach the optimum vulcanization, min 18/00// 18/10// 18/00// 17/30// 18/00// 17/40//
The maximum torque M4, H^m 37 37 37 37 37 37
The maximum degree of vulcanization t4 min 19/15// 19/20// 19/15// 19/20// 19/15// 19/27//
Data analysis of table 6 shows that the optimal ratio of components, leading to the reduction of the minimum viscosity and increasing the start time of vulcanization, has the best technological properties of rubber compounds that are observed when 10 mass parts of the mineral part of sludge for rubber mixtures, intended for the manufacture of wear-resistant side tape.
As mentioned above on technological and operational properties of rubber mixtures and vulcanizates is strongly influenced by the molecular weight (M), molecular weight distribution (MWD) of rubber, as well as the type and dosage used fillers. The distribution of curing agents in the rubber compound, and the nature of the processes of change-linkage in the presence of insoluble
components (mainly the fillers). Activity fillers when used with uncrystallizable rubbers is significantly higher than when applied with crystallizing rubbers. As a result, there is a need of analysis of the combined effect of filler and curing agent on the crystallization process [14].
The obtained results can be explained with the changes occurring in the rubber matrix in the presence of the filler. Between the filler and the elastomer arise when one of three types: physical adsorption and chemisorption, formed in the process of preparation of a rubber mixture and in the curing process. Chemisorption of when determine the amount associated with the filler rubber and carbon rubber gel samples [15].
Increasing content of sulphur chemically bound to the surface of the filler, the proportion of rubber that is associated with the filler. When sulfuric vulcanization in the presence of the filler there is a migration of sulfur and mainly of the sulfenamide to the solid surface and their adsorption and chemisorption on the surface of the filler. The amount of adsorbed substance is proportional to its content in the mixture and speed of migration. The difference in the rate ofmigration ofsulfur and accelerator to the surface of the filler leads to an increase of sulfides break up ties in the matrix of the rubber remote from the surface of the filler [16].
Thus, in the presence of the mineral part of sludge take place several processes simultaneously: the migration of curing agents to a solid surface and decrease of their content in the rubber matrix remote from the solid surface (this should take into account the different speed of migration of each ingredient); the increase in the number of connected rubber. The intensity of
these processes mainly at the stage of vulcanization, will determine the type and dosage of curing agent used. The decrease in the content of curing agent in the rubber matrix increases the rate of crystallization. The increasing sulfides break up the relationships due to the greater speed of migration of the accelerator to hard surface dramatically slows down the process of crystallization and this effect is mainly at small dosages filler.
Research the physical and mechanical properties of rubbers, synthesized using organic and mineral parts of the sludge confirmed the feasibility of their use in the manufacture of rubber products. As mentioned above, the organic portion of the sludge has good compatibility with synthetic rubbers and is easily inserted in the rubber compound and improves the dispersion of powdered ingredients. Data analysis of table 6 shows that the best results are observed at a dose of 10 mass parts of the mineral part of sludge for rubber mixtures, intended for the manufacture of wear-resistant side tape.
Table 6. - Physical-mechanical properties of rubber compounds for abrasion-resistant side tape
Name of indicators 100 masses parts of rubber
Standard 5,0 7,0 10,0 15,0 20,0
Conditional tensile strength, kg s/sm2, not less than 190 185 187 192 190 185
Conditional stress at elongation 300%, kg s/sm2 120 110 115 122 122 118
Elongation at break,% 410 400 390 405 415 420
Shore hardness A, conditional unit 77 78 79 80 79 77
In the diagram (figure 2) clearly shows that the General level of physical and mechanical properties of the investigated rubber close to the reference.
500 400 300 200 100 -0
□ conditional tensile strength, Krc2/cM
□ conditional stress at elongation 300%
□ elongation at break,%
□ Shore hardness A, ycn.eg.
Standard 5
10
15
20
Figure 2. Diagramdependenceon physical-mechanical properties of rubber compounds for abrasion-resistant side strips from the content of the mineral part of sludge LLP "PKOP".
Conducted enlarged-laboratory tests on the basis of obtaining the rubber mixtures for the manufacture of
of LLP "EkoTire" with the results of the optimum wear-resistant side tape.
technological parameters of obtaining rubber mixtures Thus, the research results showed the possibility
with organic and mineral parts of sludge, the technology of use in the formulation of rubber compounds
7
for the manufacture of wear-resistant side tape as synthesized from the gas technical sulfur LLP "PKOP",
ingredients — organic (emollient) and mineral (filler) is competitive both in its physical and mechanical
part of the sludge, polymeric sulfur(curing agent), LLP properties, and cost, which in turn, allows to solve
"PKOP". The conducted research allows to claim that the problems of disposal of oily waste and the rational use of
rubber compound produced using organic and mineral sulphur in the manufacture of rubber products and tires. parts of sludge LLP "PKOP" and polymeric sulfur, are
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