CC BY
56
ISSN 2522-1841 (Online) ISSN 0005-2531 (Print)
UDC 691.175.2
ABOUT THE DEVELOPMENT, APPLICATION AND INNOVATIONS OF POLYMER
COMPOSITES
1 2 11 G.Sh.Gasimova, L.Kh.Gasimzade, R.N.Lalayeva, L.Kh.Khamedova,
1F.A.Aqayeva,1R.V.Asadov,1A.L.Tagiyeva
institute of Polymer Materials, Ministry of Science and Education of the Republic of Azerbaijan
2Azerbaijan State Oil and Industry University
Received 21.10.2022 Accepted 15.03.2023
The physical-mechanical, thermophysical, and other important properties of polymer composites primarily depend on the polymer fillers used as modifiers. Examples of fillers include substances that act as structural modifiers, additives, mineral additives, and so on. As studies conducted in this area show, modifiers for various purposes are used to improve chemical and physical-mechanical parameters. The article provides information about the development and production of polymer composite materials. The possibility of obtaining and using composite materials in various fields of technology is shown. In addition, a review of studies that provide a broad understanding of polymer composite materials is also collected. It has been shown that the use of polymer composite materials can lead to significant advances in modern manufacturing. The article also provides information on organic and inorganic fillers with different properties. Based on this, the results of studies carried out in the direction of obtaining polymeric materials using carbon, carbon graphite, fiberglass, etc. are summed up. The nanocomposites of the new generation demonstrate innovative results. This paper shows innovative applications of polymer composite materials for various purposes. All this makes it possible to use the rich mineral resources of Azerbaijan in the production and operation of polymer composite materials.
Keywords: polymer, composite materials, filler, modification.
doi.org/10.32737/0005-2531-2023-2-186-200
Introduction
With the development of modern engineering and technology, there is always a need to develop new types of materials characterized by high strength properties, corrosion resistance, thermal stability and heat resistance, resistance to harsh climatic conditions, oil and gasoline resistance, etc. [1]. In addition, high technological properties are required from polymeric materials, which make it possible to improve their processing by main methods, such as injection molding, extrusion, pressing, vacuum pneumatic forming, etc. [2]. This is due to several factors, the main ones of which are formed within the framework of strict operational requirements. To change the properties of industrial polymers, various methods of their modification are used: plasticization, the loading of fillers, stabilizers, additives, structure forming agents, dressing of mineral fillers, the preparation of polymer mixtures, etc.
In this regard, in recent decades polymer matrix composite materials have attracted increasing interest in various potential applications [3].
Of course, despite the satisfactory quality characteristics of industrially produced polymers, it is not always possible to use them in their pure form, especially in machine-building, shipbuilding, aviation and radio-electronic industry, military, space, military space technology and industry [4]. This is due to several factors, the main ones of which are formed within the framework of strict operational requirements. To change the properties of industrial polymers, various methods of their modification are used: plasticization, the loading of fillers, stabilizers, additives, structure forming agents, dressing of mineral fillers, the preparation of polymer mixtures, etc.
This work presents an overview of the problems of obtaining and processing polymer
composite materials based on various types of mineral and polymer composites. The use of a number of modifiers allows you to regulate the structure and properties of polymer composites within sufficiently wide limits. Similar practice is widely used by specialists today, which opens up promising opportunities for wide application in various areas of industry. The purpose of the research is to consider the influence of the composition, structure, quantity and size of various fillers on the properties of polymer composite materials. In addition, find innovative opportunities for their application.
The concept of polymer-filler
The filled polymer was first produced by Dr. Backeland (Leo H. Backeland, USA) [51]. At the beginning of the 20th century, he discovered the synthesis method of phenolformaldehyde resin (bakelite). This resin itself is a brittle material with high strength. Backeland detected that an addition of fibers, including wood flour, to the resin (until it hardens) increases its strength. The material (bakelite) created by him quickly became popular [51].
Filled polymers are continuous heterophase composite materials. In them, the fillers are in the form of solid [14-17] , liquid [51]or gas [3] in a certain order with chaotic movement. These substances fill part of the matrix volume. At this time, the use of rare and expensive raw materials is reduced or the compositions are modified, giving them a new quality, and creating new properties. In most cases, filled polymers can be obtained from plastic masses, rubber, varnish coloring materials, glue and other composite materials. Depending on the type of polymer matrix, they are divided into filled reactoplasts, thermoplastics and rubbers [8]. Depending on the type of filler, filled plastics (dispersed parts of various shapes, including crushed fibers) are divided into reinforced plastics, gas-filled plastics, oil-filled plastics [9-12].
Depending on the nature of the filler, filled polymers are divided into asboplastics (filled asbestos), graphitoplastics (filled graphite), wood layered plastics (wood veneer), glass
plastics (glass fibers), boroplastics and nano-composites (nanoparticles can be 5-100 nm), etc.
The properties of filled polymers are determined by the structural features, the compatibility of the polymer matrix and filler, the dispersion and distribution of the filler in the polymer volume, and mutual movement at the polymer-filler interface. The filler polymer can improve or worsen the properties of the matrix. This will largely depend on the correct selection of the components of the mixture, their compatibility and a balanced approach to predicting the expected properties [13].
Usually, to obtain filled composites, solid fillers are used: finely dispersed granular (soot, sawdust, quartz, chalk, kaolin) or lamellar (talc, mica, graphite, kaolin, etc.), as well as various fibrous materials in the form of yarn, rope, fibers, paper, mats [14-17]. [14-17]. Gas-impregnated materials are obtained by foaming in the presence of special agent porophores or by mechanical foaming of volatile components [3]. The technology of obtaining gas-filled polymers using poro-phore has been studied. At that time, the basic possibilities of obtaining gas-filled polymers based on mixtures were widely investigated and completely incompatible polymers were used. To improve the compatibility of two- or three-component polymers, graft copolymers or finely dispersed organic compounds (structure builders) were used as basic compatibilizers [18, 19].
To increase the viscosity of the solution and prevent the gas filler from leaving the polymer mass, dicumyl peroxide is added as a binding agent. The development of the technology for the production of foam polymer materials made it possible to carry out the mechanical-chemical synthesis of the compositions with the given macrostructure and properties [20].
The term "reinforced filler" is included to describe discontinuous additives. To improve the mechanical properties of the polymer, its shape, geometry or chemical composition has been changed. The inorganic reinforcing filler is harder than the matrix and deforms less. This leads to an overall shrinkage of the matrix, especially near the matrix particle boundary
where the fibers touch the polymer, reducing the deformation and increasing the stiffness.
The main reasons that consider the application of modified additives as important are as follows:
• improvement and modification of properties
• lowering the total cost
• Improvement and control of processing conditions.
Types of modified polymer systems are: polymer composites, polymer-polymer blends, and foam polymers. Polymer composites are mixtures of polymers with inorganic or organic modifiers. Thus, they consist of two or more components and two or more phases.
Additives can be continuous, for example, in the form of long fibers or ribbons. Such additives are added to the polymer due to their regular geometric arrangement and are a common example of fiber-based thermoset laminates widely distributed throughout the product dimensions. These are classified as high quality polymer composites. On the other hand, the modified additives may be non-continuous (short), such that, for example, short fibers (say, less than 3 cm long), plates, spheres, or some amorphous particles are dispersed in a continuous matrix. Such systems are usually based on a thermoplastic matrix and act as low-quality polymer composites. Unlike their continuous additive counterparts, modified additives for polymer composites are classified differently:
• reinforcing elements
• fillers or reinforcing additives.
In composites with continuous reinforcing elements, mainly in the thermoactive matrix, long fibers or ribbons, in a certain geometrical order, can be the main components of the composite. Reinforcing elements are located in different orientations, as well as in different geometrical orders, in selected continuous composites (in orientation composites, they can make up 70% of the volume) [1-5].
It is usually produced by extrusion or injection molding. The content of additives usually does not exceed 30-40%. It should be noted that there are methods for the industrial produc-
tion of thermoplastic composites from continuous oriented fibers, which make it possible to obtain fibers for use in polyfunctional plastics.
In general, parameters affecting the properties of both continuous and discontinuous polymer composites include:
• properties of modifier additions (special properties, size, shape);
• composition;
• interaction of components at phase boundaries. This is due to the presence of a thick dividing layer. This is called "interphase boundary"
• production method.
In terms of production methods, all processes used to process unfilled, unmodified thermoplastics can be used to process non-continuous systems (with the exception of expanded granular polymers).In addition to ther-moforming, hot stamping of reinforced thermoplastic fibers is used for the production of large-structured products
Some fiber fillers
Glass fiber reinforced polymer composite materials are made from molten inorganic glass. Both thermoreactive synthetic resin (with phenol, epoxy, ether, etc.) and thermoplastic polymers (polyamide, polyethylene, polystyrene, etc.) are often used as a matrix. These materials have the necessary high strength, low electrical conductivity, and high electrical insulating properties [21]. The first reinforced glass plastics did not have many fibers. The fibers were mainly used to neutralize the rough defects of the fine matrix. However, over time, the purpose of the matrix has changed. It served to glue strong fibers. The content of fibers in glass-reinforced plastics is 80 wt%. As a filler, a fabric woven from glass fibers, called fiberglass, is used. Fiberglass is a very cheap material.
They are widely used in construction, shipbuilding, radio electronics, household goods, sports equipment, in the preparation of glass unit for modern window frames [21].
Carbon fibers serve as filler in some polymer composites. Carbon fibers are obtained on the basis of synthetic and natural acrylonitrile, synthetic and natural fibers obtained from oil
and coal tar. Thermal processing of fibers usually takes place in three stages: oxidation -220°C, carbonization - 1000-1500°C and graphitization - 1800-3000°C.
Fibers with high carbon content (99.5% by weight) are high fibers. Depending on the method of processing and the raw material, the obtained carbon fibers have different structures. The same matrices are used to produce carbon fiber and fiberglass. These are often thermoset and thermoplastic polymers.
The main advantage of carbon fibers over fiberglass is their low density and very high modulus of elasticity. Carbon plastics are very light and at the same time strong materials. Carbon fibers and carbon plastics have almost zero coefficient of linear expansion. All carbon plastics are good conductors of electricity, which limits their scope of application. Carbon plastics are used in aviation, rocketry, machine building, aerospace engineering, medical equipment, prostheses, lightweight bicycles and other sports equipment [22].
Carbon composite materials based on carbon fibers and carbon matrix produce the most heat-resistant composite materials. They can withstand temperatures of 3000°C for long periods in an inert or reducing environment. There are several methods of producing such materials. One of them is carbon fibers impregnated with phenol-formaldehyde resin and subjected to high temperature (20000C) [22]. At this time, pyrolysis of organic matter occurs and carbon is formed. The operation is repeated several times so that the material is less porous and denser.
Another method of obtaining carbon material is to burn ordinary graphite at atmospheric temperature with high methane content. Small size carbon, formed during the pyrolysis of methane, closes all holes in the graphite structure. The density of such material is one and a half times greater than the density of graphite (Scanning Microscope image of filler distribution within the composites. Figures 1 and 2) [51].
Fig.2. Analysis (SEM) of clinoptillolite - filled composite (ethylene-propylene copolymer and clinoptillolite) [51].
Carbon plastics are used for high-temperature rocket technology, high-speed aircraft belts, aircraft brake pads, and spacecraft electrothermal equipment [11-14, 22].
In composite materials containing boron fibers as a filler (applied on a thermosetting polymer matrix), the fibers can be monofilaments and strands (boron fibers are mixed with other fibers). Due to the high strength of the threads, the resulting material has high mechanical properties and is also resistant to aggressive environments (boron fibers have high compres-sive strength compared to other fibers). However, the brittleness of the material complicates their processing and limits the shape of boro-plastic products. In addition, the cost of boron fibers is very high (about $400/kg) [6-9].
This is also due to the peculiarities of the technology of their production (boron is obtained from chloride in the presence of tungsten by precipitation). Its price is equal to 30% of the price of fiber[6-9].The thermal properties of boron plastics are determined by the thermosta-bility of the matrix. Therefore, operating temperatures are usually not high.
The application of boron-containing plastics is limited by the high cost of producing boron-containing fibers. Therefore, they are mainly used in aviation and space engineering details. These details withstand long-term use. In thermoactive organic plastics, which sometimes contain natural and artificial fibers (in the form of jute, thread, paper) as filler, as a rule, epoxy, polyester and phenolic oils, as well as polyimides act as a matrix. The material contains 40-70% filler. In organic plastics based on thermoplastic polymer - polyethylene, the filler content varies widely from 2% to 70% [6-9].
Bioplastics have a low density; they are lighter than glass- and carbon fiber, due to their high tensile strength. They have high resistance to impact and dynamic loading, but at the same time, they have low strength during compression and bending [12].
After the industrial production of polypropylene, the first generation of fillers included talc sheets and asbestos fiber [11]. These
also have a good effect on hardness and heat resistance.
The search for a substitute for asbestos, harmful to humans, led to particles of calcium carbonate and mica flakes - second-generation fillers. Compared to talc, mica was more effective in hardness and heat resistance. Although calcium carbonate was less effective in increasing hardness, it increased the impact resistance of polypropylene homopolymers [10-12].
Organic and inorganic fillers
The degree of orientation of filler mac-romolecules plays an important role in improving the mechanical properties of organic plastics. Polyparaphenylene-terephthalamide - Kev-lar, as a macromolecule of rigid-chain polymers, is mainly oriented around the axis of the fibers and therefore has a high tensile strength along the fibers. Bulletproof vests are made from Kevlar reinforced materials [22-25].
Organoplastics are widely used in the automotive industry, shipbuilding, mechanical engineering, aviation and space technology, radio electronics, chemical engineering, and the production of sports equipment. More than 10,000 grades of filled polymers are known. Fillers are used both to reduce the value of the material and to give it special properties[7-9,12].
Today, thermosetting polymers are widely used. Silane coupling agents are used to improve the strong influence of fillers on the properties of polymer composites. Silane coupling agents create adhesion between the individual phases of the composite material. These phases are organic polymers, inorganic additives or reinforcing fibers. Silanes form bridges between previously weak surfaces that are molecular, i.e. strongly stable aqueous and chemically stable [6-9].
Hydrolysis and condensation of silanes occurs at the top of the mineral filler. As a result, oligomers with silane structures are formed. Oligosilanes are produced industrially. They are low viscosity liquids [22]. In standard extruders, plasticizers and adhesives, processing simplicity and safety are ensured by low emission of volatile products. Organosilanes react with the hydroxyl groups of the top layer and
form a covalent bond with the top layer of the filler.
Thus, they are effective at high concentrations of reactive hydroxyls. Silica, silicates, oxides and hydroxides are highly reactive compared to silanes. Any modification of the topcoat with silane must be confirmed by practical experiments. The production of silane parameters leads to the optimal shape of polymer composites.
Currently, various fillers are applied to thermoplastic and thermoset polymers. Calcium carbonate and kaolin (white clay) are inexpensive, their resources are practically unlimited, and their white color allows for various modifications.
Solid and flexible polyvinyl chloride materials are used in the production of pipes, electrical insulation, facing stones, polyester glass plastics, polyethylene and polypropylene fillers. The loading of talc (a soft white powder) to polypropylene increases the flexibility and heat-resistant modulus of that polymer. Soot is often used as a rubber filler, but it is also included in polyethylene, polypropylene, and polystyrene [15-24].
As usual, wood bran, ground walnut shells, plant and synthetic fibers are used as organic fillers. Starch is used as a filler in the production of biodegradable composites [26, 27].
The technology of obtaining textolites was developed in the 1920s on the basis of phenol-formaldehyde resin. The fabric is soaked in resin, then pressed at high temperatures. As a result, textalite plates are obtained.
As the first application of textolite, it is hard to underestimate its use for covering kitchen tables. The basic principles for the manufacture of textile products are preserved, but now not only plates are formed from them, but also figured products. Of course, the range of applications of these materials has expanded.
Thermoset and thermoplastic polymers are widely used as binders in textolites. Sometimes even inorganic binders based on silicate and phosphate are applied. Various materials (cotton, synthetic, glass, carbon, asbestos, basalt, etc. fibers) are used as fillers. The properties and application of textolites are diverse [28-30].
Modification of organic polymers with additives leads to the production of multiphase systems consisting of a continuous polymer phase (with some exceptions). The resulting mixtures are characterized by a unique microstructure that determines their properties.
Unlike polymer, which is stronger and stiffer, reinforcing elements usually have a higher modulus and strength. Thus, the modification of mechanical properties can be considered as their first function, although their presence cannot seriously affect thermal expansion, transparency, thermal stability.
The filler can often be used in thermoset-ting processes. The concentration and properties of additives, as well as their interaction with the matrix, are important control parameters in composite processing [20-24].
Traditionally, fillers have been viewed as modified additives due to their unpleasant shape and chemical composition. They can slightly increase the modulus of elasticity of the polymer, while the strength remains unchanged or decreases. The advantage of fillers is that the cost of the material is reduced due to the inclusion of a very valuable polymer.
Another potential economic benefit lies in its high electrical conductivity and reduced spoilage due to deformation.
Depending on the type of filler, other properties of the polymers may also be affected, for example the melt hardness may be increased by the loading of fibrous materials. On the other hand, when a large amount of inorganic filler is used, the injection molding expansion and thermal expansion are reduced [22-24].
A useful parameter for evaluating the effectiveness of filler is the ratio of its surface area to its volume. To get the necessary power, this ratio should be maximally high [25-28]. When creating reinforcing fillers, the goal of this process or material modification is to increase the particle size ratio and improve their compatibility. Such modifications can not only enhance and optimize the function of the filler, but also enhance and provide additional functions.
The wide range of functions obtained by mixing or modification of existing fillers expands their application range [29-32].
Some composites with different purposes
Some wear resistant composites
Modification of the mica surface (with binders) to improve adhesion, and modification of calcium carbonate with stearates to improve dispersion enhance these functions and provide additional benefits. This improvement in processing reduces the effectiveness and aging of the paint under prolonged heat exposure. When using different filler, completely new functions appear. For example, barium sulfate increases sound insulation, wollostanite scratches increase wear resistance, hard glass beads reduce density, and particulate-filled glass fiber aggregates create unique properties. These properties cannot be obtained from fillers of the same type [29-33].
In recent years, the method of increasing the friction properties of polymeric materials by including liquid phase lubricants and lubricating oils has become widespread. When liquid components are introduced in quantities that exceed their compatibility with the polymer binder, there is a possibility that the excess amount of liquid will separate from the matrix. The presence of a temperature gradient in the friction zone allows the migration of the high-temperature lubricant. Thus, it continuously generates a lubricant film on the friction surfaces. When lowering the temperature in the friction zone, the migration speed of the lubricant slows down, which allows to provide a self-lubricating effect for a long time [34].
The objects of the research are polymer composite materials modified with activated natural zeolite and polytetrafluoroethylene (PTFE - GOST 10007-80). Additionally, the research includes Motul SAE 5W30 eco-energy 8100 engine oil as an additive. For comparison, M-8B and Ravenol VMO SAE 5W-40 brand motor oils were used to obtain composites with high corrosion resistance and strength. At this time, the advantages of using M-8B mineral motor oil, which is characterized by low viscos-
ity as a liquid phase, became known. In this regard, it is interesting to study other types of motor oils in order to fully understand the mechanism of increase in corrosion resistance with such filling method PTFE. The technology of obtaining polymer composite materials consists of first impregnating the formed porous polymer with liquid motor oils of various origins and then solidifying the liquid phase during the processing of the composite. The impregnation of porous materials with liquid lubricant is carried out by immersion wetting and spontaneous impregnation processes, where pressure is generated by capillary effects as a result of bending on the surface of the liquid without applying additional force. This work presents a comparison of the results of tribotechnical research on composites based on PTFE and Motul sae 5w30 eco-energy 8100 engine oils [51]. Modification with M-8B motor oil outperforms composites obtained as a result of modification with Ravenol VSI 5W40 motor oil. This is probably due to the fact that complex esters included in the composition of oils ensure good adhesion of the polymer composite. It brings the materials to the surface of the counter wire, resulting in a rapid strong transition during the rubbing process [35, 51].
The paper [35] presents the results of a study of the influence of the type and concentration of mineral fillers and engine oil on the wear resistance and friction coefficient of composites based on polyolefins. Clinoptilolite, clay, molybdenum disulfide, and graphite were used as minerals. For a comprehensive interpretation of the structure, properties, and tribologi-cal characteristics of nanocomposites based on polyolefins, low density polyethylene (LDPE), ethylene-propylene block copolymer (BEP), PP, and high density polyethylene (HDPE) were used as the polymer base. It has been established that the introduction of nanoclay and motor oil into the composition of composites based on polyolefins leads to rather serious changes in their physical and mechanical properties and friction coefficient. As expected, the samples of oil-filled nanocomposites are relatively better in terms of the coefficient of fric-
tion. In the process of friction in the contact zone, the constant separation of oil from the content of filler particles naturally affects the significant reduction of friction and wear of materials [35].
Disadvantages of antifriction materials containing liquid lubricants are the limitation of the working reserve of the friction parts. This is due to the loading of a relatively small amount of liquid lubricant in the composition of the polymer material without complicating the production and processing technology, as well as without lowering the initial physical and mechanical properties of the polymer binder. These disadvantages are partially overcome by the use of special absorbers of liquid lubricants capable of adsorbing significant amounts of liquid in not too large volumes. In this regard, tribotechnical tests of polymer composite materials containing activated natural zeolites impregnated with SAE 5W30 oil were per-formed[35].Based on the conducted studies, the prospect of using Motul SAE 5W30 brand motor oil as a non-traditional PTFE modifier to obtain corrosion-resistant composites has been shown. The effectiveness of the modifying effect of this oil is probably due to its chemical composition, which differs in nature from the other two types of oil. Motul SAE 5W30 brand oil is based on complex esters, and M-8B and Ravenol VSI 5W40 brand oils are made from a mixture of mineral and synthetic unsaturated hydrocarbons. One of the main reasons for the increase in wear resistance is the presence of oxygen-retaining compounds in the volume and surface of the composite. Therefore, when the polymer composite material rubs against the surface of the opposite wire, it leads to the formation of a polymer layer that firmly adheres to the opposite wire, which prevents direct contact of the friction surfaces and thus protects the material from corrosion. The use of this type of materials will allow increasing friction resistance many times. It will also solve the problem of replacing fasteners, bearings and other parts. Significant studies on tribochemical processes during friction of heat-resistant structural polymers and dry friction parts based on them
have allowed to form ideas about self-lubrication of solid bodies. We are talking about the low coefficient of friction formed as a result of physical and chemical processes during the frictional interaction of the polymer composite with the opposite wire [35].
In recent years, intensive research has been carried out on new polymer dental restorative composites . The most common base binder for such compositions is a mixture of 4.4-bis-(methacryloxy-2-hydroxypropoxydiphenyl)-2,2-propane (bis-HMA) and triethylene glycol dimethacrylate (TGM-3)[38]. For improving the physical and mechanical properties of compositions on the base of mentioned binder is used various modifying additives, in most cases functional organosilicon oligomers. Therefore, it seemed promising to use methacrylate-containing bis-HMA + TGM-3 oligophos-phazenes, which were previously synthesized by the interaction of hydroxyaryloxycyclotri-phosphazenes (HARH) with methacryloylchlo-ride. However, the latter is unavailable, expensive and inconvenient to work with due to hy-drolytic instability.[38].
At filling of compositions with finely dispersed glass filler also smooth growth of mechanical characteristics up to the 10% content of phosphazene modifier is observed. At the same time, a positive factor is the reduction of water absorption by more than 2 times and water solubility by 80-100%. One of the most important indicators of dental restorative materials is their adhesion to dental tissues and metals. Application of considered modifiers significantly increases this indicator (when 5% phosphazene modifier is taken). That is, it begins to meet the requirements of GOST R 51202-98 in the adhesion of metals to dental tissues [36-38].
Ultra-high molecular weight polyethylene (UHMPE) is a unique polymer characterized by high impact and abrasion resistance, increased cracking resistance and low water absorption. The UHMPE has a higher wear resistance due to its structural features, its chains can be folded together into the shape of lamellar crystals. Amorphous segments cross
the intercrystalline zone to connect with adjacent crystals, which may be «bonding chains». The degree of connection between adjacent crystallites plays an important role in determining the physical properties of the specimen, these results in the UHMPE wear resistance being higher than PTFE. Its corrosion resistance makes it effective in resisting wear even at temperatures below zero. However, its widespread use is currently limited due to the lack of effective technologies for its processing into products. When heated above the melting point, the UHMPE heated above the melting temperature it does not melt into a viscous-fluid state, which is typical of thermoplastics, but only into a highly elastic state. In view of this peculiarity, UHMPE is very difficult to mold [40,41].
Scientists decided that one of the ways to solve this problem is to create polymer composites (PCM) based on a mixture of UHMPE with others polymers, in particular high-density poly-ethylene[39]. The ability of polyethylene to be processed by all available methods makes it possible to produce, on the basis of its mixtures with UHMPE, process materials with an improved performance complex. UHMPE with a molecular weight of 4.2 million and HDPE 273-83 markal are used for research objects and methods.
As the main object of research, the work was carried out using a composite polymer composite UHMPE and HDPE with a content of ultra-high molecular polyethylene in a mixture of 30 masses. % (based on previous studies in this field). To improve the technological and operational properties of this material, carbon nanostructures (CNSs) were used in this work, with carbon nanotubes (CNTs) and carbon na-noplates (CNPs) in concentrations ranging from 0.0025 to 0.05 mass.% Polymer mixtures based on HDPE and UHMPE have improved technological performance compared to UHMPE. However relatively low fluidity on the condition that such materials retain a valuable set of properties inherent to complex of properties inherent to UHMPE, does not allow for their effective processing by modern methods of extrusion and injection molding. The use of traditional methods of increasing polymer fluidity,
such as plasticization or introduction of lubricants, inevitably leads to deterioration of the deformation strength and operational characteristics of polymer composites based on UHMPE [39].
In this paper, a structural modification method with nanoscale systems was chosen to adjust the properties of composite materials based on high density polyethylene (HDPE) and ultra-high molecular weight polyethylene (UHMPE). Carbon nanotubes (NTPs) are a recent development that will help create a new generation of filled materials. Carbon nanotubes have high strength, excellent heat- and electrical conductivity . It is known that they can improve the mechanical characteristics and durability of UHMPE, promote connectivity and act as an antioxidant. Tensile strength, Jung module and material impact viscosity are increased by adding a certain number of carbon nanotubes [39]. In order to ensure the effective effect of nanomodifiers on the structure and properties of the polymer, it is necessary to achieve their uniform distribution in the polymer matrix. The high surface area and high surface energy of nanoparticles, leading to their aggregation, complicate the uniformity of their distribution. Therefore, scientists used a method specially developed for this purpose to introduce nano-modifiers into the polymer under conditions of ultrasonic exposure. The components were mixed in the melt on a twin-screw extruder with subsequent pelletizing of the resulting composition by strangulation.
Other composites for various purposes
Changes in the deformation-strength characteristics of the modified composite material can presumably be associated with changes in its structural organization at the supramo-lecular level: an increase in the density of the fluctuation network of intermolecular meshing, a decrease in the thickness of loosely packed inter crystalline layers and an increasing fraction of transitional interphase areas responsible for the integrity of the of the polymer composite framework.
Another example of a family of fillers that create new properties is pearlescent pigments. They are produced with the help of a
special shell (membrane) structure technology. They include plate-shaped bases made of mica, silica, alumina or glass. They are coated with metal oxide nanoparticles, for example, TiO2, fe2O3, Fe3O4, CrO3 and etc. [51]. By choosing suitable combinations other than traditional decorative applications, new substrate/coating areas are possible. These are solar heat reflection, laser marking of plastics and electrical conductivity [39, 40].
The vast majority of polymeric materials are dielectrics, and to increase the electrical conductivity, dispersed electrically conductive fillers, fibers, or antistatic surface-active additives are introduced into the polymer matrix. The electrical conductivity of particulate-filled polymer composite materials (PCM) is determined by the formation of a spatial structure formed from contacting filler particles. However, to obtain a manufacturable composite with a high current conductivity value, it is necessary to introduce a significant amount of filler into the polymer matrix, which can adversely affect the mechanical properties of finished products. To provide antistatic properties, they also introduce additives that have a plasticizing effect on the material and have a sufficiently low electrical resistance to ensure that the charge drains quickly while maintaining electrical insulating properties. It was studied in that the introduction of permanent polymer antistatic agents makes it possible to reduce the specific surface electrical resistance of HDPE to a maximum of 109-1010 Q [41].The effect of special grades of carbon black and single-walled carbon nanotubes on the electrophysical, physicomechanical, and rheological properties of a PE-based polymer composite material has also been studied.
The effect of nanofiller additives containing nanoparticles (NP) of copper oxide stabilized by a polymeric matrix of maleated polyethylene (MPE) on some properties of nanocomposites based on isotactic polypropylene (PP) and high-pressure polyethylene (PE) was studied by X-ray phase and thermogravimetric analysis methods. An improvement in the strength, deformation, and rheological parameters, as well as in the thermal-oxidative stability of the obtained nanocompo-
sites, was revealed, which, apparently, is associated with the synergistic effect of the interaction of copper-containing nanoparticles with anhydride groups of MPE. It has been shown that nanocom-posites based on PP/PE/NP can be processed both by pressing and by injection molding and extrusion [41-42].
These are usually solid materials; they do not mix with each other during melting in the matrix, both in the solid state and by creating certain dispersed structures, their distinctive feature is that they are applied in high concentrations (75 vol.%). Some surface modifiers and technological additives are used in low concentrations. Fillers can also be classified as inorganic substances. In addition, they can be divided according to their chemical properties, or their shape and size, or their aspect ratio. The most commonly used powdered fillers are mainly industrial minerals. These include talc, calcium carbonate, mica, kaolin, wol-lastonite [43, 44].
The most convenient response scheme of the modifiers is that they are suitable for a certain specific function. For example, mechanical, electrical or thermal properties, fire resistance, processability, liquid permeability, or the ability to change the cost of manufacturing composites.
Fillers are multifunctional and can be characterized as the first function and a number of additional functions [45, 46].
Next-generation composites
Polymer-matrix-based nanocomposites are newly classified as hybrid materials and had acquired the attention of the scientific community globally for the past 20 years. Such polymers are called nanocomposites when the amount of filler is nanosized. The functional and structural characteristics of polymers can be improved by effectual approaches represented by polymer composites. The development of the production and research of polymer nanocom-posites has been quite complex and has not always been amenable to scientifically based interpretation in assessing their structural features and properties. Studies of the influence of technological parameters processing of nanocompo-
sites for their final properties were extremely limited. These problems are very common in polymer materials science and in the production of special purpose structural products. The functional and mechanical characteristics of polymeric nanocomposites are based on the interaction among polymer matrix and nano-fillers [47, 48].
The results of studying the effect of the type and concentration of mineral filler on the basic physicochemical and physico-mechanical properties of filled nano-composites showed that the simultaneous loading of nano-particles and structure forming agents into the propylene-ethylene block copolymer contributes to a significant improvement in the main physical-mechanical characteristics of nanocomposites obtained on their basis [49].
Nanocomposites on the basis of clay and polypropylene have been prepared and their rheological properties have been studied. The results of investigation of influence of shift stress and temperature on flow rate, effective melt viscosity of nanocomposites and activation energy of viscous flow are presented. It has been shown that a use of natural mineral - clay as a filler favors essential improvement of fluidity of nanocomposites on the basis of polypropylene basis [50].
The influence of technological parameters of injection molding on the properties of a nano-composite based on a propylene-ethylene blockcopolymer, clinoptilolite, and molybdenum disulfide is considered. Mixing and pouring of products was carried out in a single technological circuit with a screw drive on a DE3132.250TS1 casting machine according to monotreme technology [51].The originality of the design of this equipment allowed the uniform dispersion of nanoparticles of fillers in the polymer matrix. It has been determined that increased temperature, shear stress, and process duration up to 10 seconds can have a certain degree of influence on the increase in the tensile stress of the nanocomposite, elongation at break, and reduction of abrasive wear [51].
In the paper [52] the results of the study of the influence of clinoptilolite concentration,
shear stress and temperature on the effective viscosity, shear rate and activation energy of the viscous flow of nanocomposites based on linear low-density polyethylene were presented. The natural mineral has been shown to contain kao-linite or nanoclay. During the diffusion of macro chains into the interlayer space of nanoclays, the latter decays and the surfactant, exchanged cations or anions, stearates present there, as a result migrate into the polymer matrix and then, as lubricants, improve the flowability of the melt of the nanocomposite. For the first time it was shown that natural minerals of Azerbaijan belong to the number of bifunctional fillers, which contribute to the enhancement of polymer composites and, at the same time, improve the flowability of their melt. Flow curves of nanocomposites based on linear low density polyethylene and clinoptilolite were determined. It was established that introduction of 5% wt. cli-noptilolite promotes an increase in shear rate 2.62 times [52].The results of the study of the influence of clinoptilolite concentration on the rheological and physico-mechanical characteristics of nanocomposites were presented. It was shown that when the concentration of clinoptilo-lite in the polymer matrix increases from 5 to 15wt% the shear rate is somewhat reduced, but remains higher than that of the initial polyolefin
[53].
The results of research of the effect of bentonite concentration on the regularity of crystallization and the nature of changes of ultimate tensile strength, tensile yield strength and elongation at break of nanocomposite materials basis of on the mixtures of high and low density polyethylene are presented [53].As a result of the conducted research it can be stated that in nanocomposite materials based on benton-ite+HDPE/LDPE with an increase in the concentration of bentonite over 1 mass %there is a slight decrease in tensile yield strength, with a simultaneous increase in ultimate tensile strength and heat resistance, a gradual decrease in elongation, an increase in the density of composites identified at room temperature and at 190°C, and a corresponding decrease in specific volume
[54]. The temperature of onset of crystallization
for composites with the composition of HDPE/LDPE, HDPE/LDPE+1% bentonite is 115°C, and for the rest of the studied sam-ples110-113°C. For the all examined samples were found the glass transition temperatures and the free volume was calculated [55-60].
The influence of additives of the nanofillers containing nanoparticles of copper oxide, stabilized by polymer matrix of high pressure polyethylene, prepared by mechano-chemical method on rheo-logical properties of mixed thermoplastic elastomers on the basis of isotactic polypropylene and ethylene-propylene-diene elastomer has been investigated. The viscosity, shift rate, shift tension and also activation energy of viscous flow of the compositions. It has been shown that in filling of the polymer mixture polypropylene/ethylene-propylene-diene elastomer with nanoparticles of the copper oxide at low temperatures it is observed a regime close to Newtonian regularity of melt flow, which is disturbed at temperature rise. A view of rheological curves evidences about pseudoplastic character of their flow with appearance of viscosity anomaly - by viscosity decrease in increase of shift rate characteristic for majority of polymers. Based on the developed research results, it can be determined that the activation energy of the viscous flow of the composite filled with nanoparticles of copper oxide is lower than the initial mixture of ethylene-propylene-diene elastomer. The obtained data show the possibility of reprocessing of nanocomposites by methods of high-speed molding under pressure. It has been shown by a method of scanning electron microscope that an introduction of the copper-containing nanofillers into polypropylene/ethy-lene-propylenediene elastomers leads to the formation of finely spherulitic layered structure of filled composition and thereby improvement of fluidity and rheological properties [61].
Conclusion
Based on the information provided above, it can be said that the use of various polymer and mineral fillers allows for a wide range of applications in the complex of important property. Using a new generation of nanoscale fillers has demonstrated the possibilities of cre-
ating materials that differ significantly from the original polymer matrix with high physical and mechanical properties. The preparation and obtaining of a complete complex of polymer composite materials allow designers and specialists involved in plastic compounding to extensively modify the technological capabilities of the extrusion process. It is evident from the research conducted above that the future development and operational processes of polymers will depend on the correct selection of optimal conditions for the exploitation of filled composite materials. The research conducted by renowned scientists has shown that polymer materials are obtained through the use of various modifiers and have the potential for wide application of composite additives. To achieve this goal, it is necessary to properly select, classify, and study the properties of fillers in order to gain an understanding of the structure of the filler-polymer system. The components of most of the above-mentioned polymer composites are found in rich deposits in Azerbaijan. This creates an opportunity to effectively use the material resources of the country's nature.
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POLiMER KOMPOZiTLORiN iNKl§AFI, TOTBiQi УЭ YENiLiKLORl HAQQINDA
G.§.Qasimova, L.X.Qasimzada, R.N.Labyeva, L.X.Xamadova, F.A.Agayeva, R.V.Osadov, A.L.Tagiyeva
Polimer kompozisiyalarinin möhkamliyi, istilik va digar mühüm xüsusiyyatlarinin böyük ölgüda asili oldugu mühüm göstaricilardan biri , istifada olunan polimerin doldurucularla uygunlugudur. Doldurucu kimi müxtalif qurulu§ этэ1э gatiranlardan, modifikatorlardan, mineral alavalar va s.istifada olunur. Bu tadqiqat i§inda polimer kompozitlarin kimyavi va fiziki-mexaniki parametrlarini yax§ila§dirmaq ügün müxtalif tayinatli modifikatorlardan istifada olunur. Maqalada polimer kompozit materiallarin inki§afi va emali haqqinda malumat verilir. Texnikanin müxtalif sahalarinda kompozit materiallarin alinmasi va istifadasinin mümkünlüyü göstarilir. Bundan alava, polimer kompozit materiallan haqqinda geni§ anlayi§i tamin edan tadqiqatlarin icmali da toplanmi§dir. Göstarilmi§dir ki, polimer kompozit materiallarin istifadasi müasir istehsalda ahamiyyatli iralilayi§lara sabab ola bilar. Maqalada müxtalif xüsusiyyatlara malik üzvi va qeyri-üzvi doldurucular haqqinda da malumat verilir. Yeni dövrün nanokompozitlari ila aparilan tadqiqatlar innovativ naticalar göstarir. Bütün bunlar polimer kompozit materiallarin istehsalinda va istismarinda Azarbaycanin zangin mineral ehtiyatlarindan istifada etmaya imkan verir.
Agar sözlzr: polimer, kompozisiya materiali, doldurucu, modifikasiya
О РАЗРАБОТКЕ, ПРИМЕНЕНИИ И ИННОВАЦИЯХ ПОЛИМЕРНЫХ КОМПОЗИТОВ
Г.Ш.Гасымова, Л.Х.Гасымзаде, Р.Н.Лалаева, Л.Х.Хамедова, Ф.А.Агаева,
Р.В.Асадов, А.Л.Тагиева
Одним из важных показателей, от которых в значительной степени зависят прочностные, термические и др. важные характеристики полимерных композиций, является совместимость используемого в качестве связующего полимера с наполнительям. В качестве наполнителей являються структурообразователи, модификаторы, минеральные добавки и др. Как показывают проведенные в этой области исследования, с целью улучшения химических и физико-механических показателей используют модификаторов различного назначения. В статье приведены сведения о развитии и разработке полимерных композиционных материалов. Показана возможность получения и применения композиционных материалов в различных областьях техники. Кроме того, также собран обзор исследований,о дающих широкое представление о полимерных композиционных материалах. Было показано, что использование полимерных композиционных материалов может привести к значительному прогрессу в современном производстве. В статье также представлена информация об органических и неорганических наполнителей с различными свойствами. Исследования нанокомпозитов нового поколения показывают инновационные результаты. Все это создает возможность использования богатых минеральных ресурсов Азербайджана в производстве и эксплуатации полимерных композиционных материалов.
Ключевые слова: полимер, композиционные материалы, наполнитель, модификация.
