RU2609469C1 - Quasicrystalline phase based concentrate for production of filled thermoplastic polymeric compositions and method for production thereof - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention refers to methods for production of concentrates based on thermoplastic matrices filled with quasicrystalline particles and intended for production of polymeric composition materials. A concentrate is described for production of thermoplastic polymeric compositions containing thermoplastic polymeric matrix and surface-modified quasicrystalline filler based on Al-Cu-Fe and Al-Cu-Cr systems with the following ingredient ratio (wt%): quasicrystalline filler - 10-60, thermoplastic polymeric matrix forming the rest, with particle size of quasicrystalline filler being less than 45 mkm. A method for production of the concentrate is also described.

EFFECT: concentrate based on quasicrystalline fillers and thermoplastic polymers is produced for ensuring homogeneous filler distribution.

2 cl, 6 dwg, 2 tbl

Description

The invention relates to methods for producing concentrates based on thermoplastic matrices filled with quasicrystalline particles, designed to obtain dispersion-strengthened polymer composite materials.

Studies of the properties of quasicrystals have been conducted for more than 20 years. The attractive features inherent in quasicrystals, which may be of interest from the point of view of practical applications, are usually considered a combination of their high hardness, wear resistance, low surface energy, low friction coefficient, significant radiation and corrosion resistance, low values of electrical and thermal conductivity and unusual optical properties

1. Shaitura S. and Enaleeva A.A. Fabrication of Quasicrystalline Coatings: A Review. Crystallography Reports, 2007, Vol. 52, No. 6, pp. 945-952.

2. Samavat F., Tavakoli M.H., Habibi S., et all Quasicrystals // Open Journal of Physical Chemistry, 2012, 2, 7-14.

3. Jean-Marie Dubois, Song Seng Kang and Alain Perrot. Towards applications of quasicrystals // Materials Science and Engineering, A 179 / A 180 (1994) 122-126.

4. Vekilov Yu. Kh., Chernikov M.A. Quasicrystals // Physics-Uspekhi, 53 (2010), p. 537-560.

5. Koester U., Liu W., Hertzberg H. and M. Michel, Mechanical properties of quasicrystalline and crystalline phases in Al-Cu-Fe alloys. // J. Non-Cryst. Solids 153/154 (1993) p. 446-452.

6. Jenks C.J., Thiel P.A. Surface Properties of Quasicrystals // MRS Bulletin. - 1997. - V. 22. - No. 11. - P. 55-58.

7. E. Huttunen-Saarivirta Microstructure, fabrication and properties of quasicrystalline Al-Cu-Fe alloys: a review // Journal of Alloys and Compounds 363 (2004) 150-174.

[5 Koester U., Liu W., Hertzberg H. and M. Michel, Mechanical properties of quasicrystalline and crystalline phases in Al-Cu-Fe alloys. // J. Non-Cryst. Solids 153/154 (1993) p. 446-452 7 E. Huttunen-Saarivirta Microstructure, fabrication and properties of quasicrystalline Al-Cu-Fe alloys: a review // Journal of Alloys and Compounds 363 (2004) 150-174. As the main disadvantage of quasicrystals, limiting their practical use, one can consider low fracture toughness of about 0.5-3.5 MPa,5m

[5 Koester U., Liu W., Hertzberg H. and M. Michel, Mechanical properties of quasicrystalline and crystalline phases in Al-Cu-Fe alloys. // J. Non-Cryst. Solids 153/154 (1993) p. 446-452 7 E. Huttunen-Saarivirta Microstructure, fabrication and properties of quasicrystalline Al-Cu-Fe alloys: a review // Journal of Alloys and Compounds 363 (2004) 150-174.

8. Thiel, J.-M. Dubois Quasicrystals. Reaching maturity for technological applications // Materials Today Volume 2, Issue 3, 1999, p. 3-7,

. Небольшое сопротивление распространению трещин при температурах ниже 450°С, ограничивает использование квазикристаллов в виде монолитных деталей и пленочных покрытий большой толщины.while metallic materials are characterized by values exceeding 40 MPa⋅m

. Small resistance to crack propagation at temperatures below 450 ° C limits the use of quasicrystals in the form of monolithic parts and large-thickness film coatings.

It is of interest to use quasicrystals of the Al-Cu-Fe and Al-Cu-Cr systems as dispersion hardening of aluminum alloys due to the high particle hardness and good combination with the matrix material [7 E. Huttunen-Saarivirta Microstructure, fabrication and properties of quasicrystalline Al-Cu- Fe alloys: a review // Journal of Alloys and Compounds 363 (2004) 150-174.

9. Roy M. Formation and magnetic properties of mechanically alloyed Al65 Cu20 Fe15 Quasicrystal // Journal of Magnetism and Magnetic Materials 302 (2006) 52-55.

Optimizing the thermoelectric efficiency of icosahedral quasicrystals and related complex alloys // PHYSICAL REVIEW B80, 205103 (2009).10. Enrique

Optimizing the thermoelectric efficiency of icosahedral quasicrystals and related complex alloys // PHYSICAL REVIEW B80, 205103 (2009).

11. Y. Takagiwa, T. Kamimura, S. Hosoi, J.T. Okada and K. Kimura Thermoelectric properties of polygrained icosahedral Al71-xGaxPd20Mn9 (x = 0, 2, 3, 4) quasicrystals // J of Applied Physics 104, 073721 (2008)].

Al-Cu-Fe quasicrystals are considered as promising fillers in the creation of composite materials with polymer matrices, providing an improvement in physical, mechanical, tribological, and thermal characteristics.

12. Laplanche G., Joulain A., Bonneville J., et all Microstructures and mechanical properties of Al-base composite materials reinforced by Al-Cu-Fe particles // Journal of Alloys and Compounds, Volume 493, Issues 1-2, March 18, 2010, Pages 453-460.

13. YH Qi, ZP Zhang, ZK Hei, Dong The microstructure analysis of Al-Cu-Cr phases in Al65Cu20Cr15 quasicrystalline particles / Al base composites // Journal of Alloys and Compounds, Volume 285, Issues 1-2, 30 June 1999 , Pages 221-228.

14. Tsai A.P., Aoki K., Inoue A., Masumoto T. Synthesis of Stable Quasicrystalline Particle-Dispersed Al Base Composite Alloys. // J. Mater. Res. 1993. V. 8. P. 5-7.

15. Kaloshkin S.D., Tcherdyntsev V.V., Laptev A.I., et all "Structure and Mechanical Properties of Mechanically Alloyed Al / Al-Cu-Fe Composites" // Journal of Materials Science, 2004, V. 39. P. 5399-5402.

16. Kaloshkin S.D., Tcherdyntsev V.V., Stepashkin A.A., et all "Mechanical Alloying of Metal Matrix Composites Reinforced by Quasicrystals" // Journal of Metastable and Nanocrystalline Materials, 2005, V. 24-25, P. 113-116. Epoxy binders can serve as matrix materials [12. Laplanche G., Joulain A., Bonneville J., et all Microstructures and mechanical properties of Al-base composite materials reinforced by Al-Cu-Fe particles // Journal of Alloys and Compounds, Volume 493, Issues 1-2, March 18 2010, Pages 453-460 13. YH Qi, ZP Zhang, ZK Hei, C. Dong The microstructure analysis of Al-Cu-Cr phases in Al65Cu20Cr15 quasicrystalline particles / Al base composites // Journal of Alloys and Compounds, Volume 285, Issues 1-2, 30 June 1999, Pages 221-228], polyphenylene sulfide PPS [13. YH Qi, ZP Zhang, ZK Hei, With Dong The microstructure analysis of Al-Cu-Cr phases in Al65Cu20Cr15 quasicrystalline particles / Al base composites // Journal of Alloys and Compounds, Volume 285, Issues 1-2, 30 June 1999, Pages 221-228], ultra-high molecular weight polyethylene UHMWPE [14. Tsai A.P., Aoki K., Inoue A., Masumoto T. Synthesis of Stable Quasicrystalline Particle-Dispersed Al Base Composite Alloys. // J. Mater. Res. 1993. V. 8. P. 5-7. 16. Kaloshkin SD, Tcherdyntsev VV, Stepashkin AA, et all "Mechanical Alloying of Metal Matrix Composites Reinforced by Quasicrystals" // Journal of Metastable and Nanocrystalline Materials, 2005, V. 24-25, P. 113-116.], Polyamide PA [15. Kaloshkin S.D., Tcherdyntsev V.V., Laptev A.I., et all "Structure and Mechanical Properties of Mechanically Alloyed Al / Al-Cu-Fe Composites" // Journal of Materials Science, 2004, V. 39. P. 5399-5402].

The use of quasicrystals for filling epoxy binders and thermoplastic polymers Al-Cu-Fe allows to increase the elastic modulus by 2 times and increase the heat resistance in comparison with the initial unfilled materials. The wear resistance of compositions with quasicrystals is higher than that of those filled with silicon carbide and alumina [12. Laplanche G., Joulain A., Bonneville J., et all Microstructures and mechanical properties of Al-base composite materials reinforced by Al-Cu-Fe particles // Journal of Alloys and Compounds, Volume 493, Issues 1-2, March 18 2010, Pages 453-460], which, combined with a low coefficient of friction, allows the manufacture of parts for dry friction bearings [13. YH Qi, ZP Zhang, ZK Hei, C. Dong The microstructure analysis of Al-Cu-Cr phases in Al65Cu20Cr15 quasicrystalline particles / Al base composites // Journal of Alloys and Compounds, Volume 285, Issues 1-2, 30 June 1999, Pages 221-228].

The low coefficient of friction is due to the fact that quasicrystals have a low surface energy (28 mJ / m ² ) [7. E. Huttunen-Saarivirta Microstructure, fabrication and properties of quasicrystalline Al-Cu-Fe alloys: a review // Journal of Alloys and Compounds 363 (2004) 150-174]. For comparison, the most slippery fluoroplastic has a surface energy of 18 mJ / m ² , a single crystal of Al ₂ O ₃ - 47 mJ / m ² , water - 72 mJ / m ² , pure metals - one to two orders of magnitude higher. This indicates that the interatomic bonds are substantially saturated even in the surface layer.

At the moment, depending on the oil field, the complicated well stock is from 25 to 70% of the total number of operating wells. Among the complicating factors are typical: free gas at the pump inlet, abnormally high ambient temperature at the depth of the pump suspension, the presence of mechanical impurities, scaling, asphaltene-resin-paraffin deposits (ASA), the borehole curvature, and the technological connectivity of all these problems. ASPO may account for up to 80% of the total number of wells of a complicated stock.

The use of low surface energy of quasicrystals, comparable with the surface energy of polymers, in the development of wear-resistant polymer coatings and massive products intended for use in oil pumping equipment, allows to obtain materials with a low deposition rate on their surface of asphaltene-resin-paraffin deposits and salt particles, which are the same of the main factors complicating oil production.

Protective coatings for the energy complex on the market are represented mainly by products based on polymers of the polyolefin group and polyurea. The main technology for producing composite materials for such protective coatings is the method of extrusion displacement of components with subsequent granulation.

The use of quasicrystals to create polymer matrix composite materials has a number of features. It is necessary to ensure the adhesive interaction between the matrix material - a polymer of the polyolefin group and quasicrystals with low surface energy, to ensure the dispersion of the filler particles less than 3 μm, the absence of phase impurities with high surface energy, to ensure uniform distribution of the filler in the matrix.

Taking these requirements into account, obtaining particles of a quasicrystalline filler of a given morphology is possible using the method of mechanochemical synthesis of precursors from pure components followed by annealing in an inert atmosphere or vacuum, since grinding of high-hard quasicrystalline particles obtained by other technologies in the form of bulk samples, ribbons, films, leads to their contamination by particles with high surface energy.

The objective of the invention is to simplify the technology of introducing quasicrystalline fillers into thermoplastic polymers of the polyolefin group.

The technical result consists in using to ensure uniform distribution of a quasicrystalline filler in a composite material with predetermined concentrations of quasicrystalline filler concentrates containing a polymer matrix based on thermoplastic polymers with high melt flow (not less than 15, according to ISO 1133-2011 (MFR), 190 ° С / 3 , 8 kg), and surface-modified quasicrystalline fillers based on Al-Cu-Fe and Al-Cu-Cr systems with a polycrystalline particle size of less than 45 microns, a quasicryst content -hydraulic phases in the vehicle more than 90 wt. % and mass fraction of filler in a concentrate of 10-60 mass. % and how to obtain it.

The technical result is achieved as follows.

The concentrate for the production of thermoplastic polymer compositions contains a thermoplastic polymer matrix and a surface-modified quasicrystalline filler based on Al-Cu-Fe and Al-Cu-Cr systems in the following ratio of components (wt.%):

quasicrystalline filler - 10-60

thermoplastic polymer matrix - the rest.

The particle size of the quasicrystalline filler is less than 45 microns.

The technical result is achieved as follows.

A method for producing a concentrate for producing thermoplastic polymer compositions includes surface modification of particles of a quasicrystalline filler in an alcohol solution of silanes, in the ultrasonic cavitation treatment mode, drying of the filler, extrusion mixing of a quasicrystalline filler with a thermoplastic polymer matrix having a high melt flow rate (not less than 15, according to ISO 11, at least 11, according to ISO 11 2011 (MFR), 190 ° C / 3.8 kg), at a temperature 10-20 ° C higher than the melting temperature of the polymer, and granulation.

The invention is illustrated by drawings, where figure 1 shows the microstructure of sintered quasicrystalline powders after annealing in argon, the Al-Cu-Fe system (Al ₆₅ Cu ₂₃ Fe ₁₂ ), figure 2 shows the microstructure of sintered quasicrystalline powders after annealing in argon, the Al-Cu system -Cr (Al ₇₃ Cu ₁₁ Cr ₁₆ ), FIG. 3 shows the structure of the Al-Cu-Fe quasicrystalline filler (Al ₆₅ Cu ₂₃ Fe ₁₂ ) after modification with triethoxivinylsilane, FIG. 4 shows the structure of the Al-Cu-Cr quasicrystalline filler (Al ₇₃ Cu ₁₁ Cr ₁₆₎ after the modification trietoksivinilsilanom, and Figure 5 shows the microstructure of quasi-crystal filler concentrates - thermoplastic polymer.

As starting materials for concentrates should be used:

Quasicrystals of the Al-Cu-Fe system, for example, Al65Cu23Fe12 in the form of aggregates with sizes less than 45 microns, consisting of individual polycrystalline particles with sizes less than 3 microns, with a quasicrystalline phase in the filler of at least 90 masses. %

Al-Cu-Cr quasicrystals, for example, Al73Cu11Cr16 in the form of aggregates with sizes less than 45 microns, consisting of individual polycrystalline particles with sizes less than 3 microns, the content of the quasicrystalline phase in the filler powder is at least 90 mass. %

For surface treatment of quasicrystalline fillers, alcohol solutions of silanes should be used, for example: Triethoxy (vinyl) silane, Polydimethylsiloxane, in ethyl alcohol of technical grade A according to GOST 10749. 1-80.

Thermoplastic polymers are used as a polymer matrix, for example, Evatane 28-40 brand ethylene vinyl acetate (vinyl acetate content 27-29 wt.%, Melting point 70 ° C), Evatane 28-05 brand ethylene vinyl acetate (vinyl acetate content 27-29 wt.%, Melting point 72 ° С), Lotader 3210 brand ethylene acrylate (content of butyl acrylate 6 wt.%, Maleic anhydride 3.1 6 wt.%), Melting point 107 ° С) and others.

The main stages of the process of obtaining granular concentrate

Preparation of quasicrystalline powders.

The microstructure of the starting quasicrystalline fillers is shown in FIG. 1 and 2.

For grinding quasicrystalline powders, the Fritsch Pulverisette 2 mortar mill is used; for this, a sample of 50 ± 1 g of powder is poured into the mortar.

Grinding time 10 min with a gradual increase in pressure.

After grinding, the quasicrystal powder is placed in a weighing cup.

Control weighing is carried out on a laboratory balance.

Next, the powder in the cup is placed in a thermostat at a temperature of about 105 ± 1 ° C, until the mass of the powder with the cup is leveled.

Then carry out the silanization of quasicrystalline powders. For silanization, solutions of silanes in ethyl alcohol are used. Using a volumetric beaker, 10 ± 1 ml of ethyl alcohol is measured. Using a mechanical single-channel dispenser, 2 ± 0.5 ml of silane is collected to prepare a 20% solution.

Dissolution is carried out in a flask with constant stirring using a magnetic stirrer. The rotation speed of the magnetic stirrer is 330 rpm. Quasicrystal powder is gradually added to a solution of silane in alcohol. Stirring is carried out for 10 min at room temperature in the ultrasonic cavitation treatment mode.

The prepared suspension is placed in a thermostat equipped with a hood, at a temperature of 60 ± 0.5 ° C for 6 hours. During drying, control weighing is carried out, drying is carried out until the mass is leveled. The structure of silane-treated quasicrystalline fillers is shown in FIG. 3 and 4.

Next, extrusion mixing of the planned quasicrystalline powders with a thermoplastic binder is carried out. After complete drying of the quasicrystal powder, the polymer is extruded with quasicrystals.

Ethylene vinyl acetate or ethylene acrylester are used as the matrix polymer. Extrusion mixing is carried out on a twin screw extruder LTE-16. The heating mode is set from room temperature to the optimum melting temperature of the polymer used plus 10 ± 20 ° C with an error of not more than ± 1 ° C.

Polymer granules and quasicrystal powder are gradually fed into the extruder volume. The speed of rotation of the screws of the extruder 20 rpm The prepared mixture passes through a die of the required size and cross section.

Then carry out granulation of the mixture.

The strand extruded from the extruder enters the bathtub with cold water, the temperature of which is 25 ± 1 ° С. By means of the rolls with which the bathtub is equipped, the strand moves at an optimum speed through the bathtub. After passing the bath and cooling, the strand enters the granulator, the rotational speed of the granulator rotor is set to 1000 rpm.

The obtained granular concentrate is placed in a thermostat at 80 ± 0.5 ° C until a stable mass. The dried granular concentrate is packed in bags, which are marked with the date of receipt and brand of raw materials. The microstructure of the obtained granular concentrates is presented in FIGS. 5 and 6.

To describe the properties of the obtained concentrates, melt flow indices were determined in accordance with ISO 1133-2011 (MFR), for a temperature of 190 ° C and standardized loads of 1.2-5 kg using a Ceast MF50 extrusion plastometer. The flow rates of the concentrate melts obtained for various quasicrystalline systems are presented in tables 1 and 2.

The obtained concentrates have high melt flow and are suitable for extrusion filling with quasicrystals of polymers of the polyolefin group with predetermined concentrations, ensuring uniform distribution of particles.

Claims (5)

1. A concentrate for the production of thermoplastic polymer compositions containing a thermoplastic polymer matrix and a surface modified quasicrystalline filler based on Al-Cu-Fe and Al-Cu-Cr systems in the following ratio of components, mass. %: quasicrystalline filler - 10-60 thermoplastic polymer matrix - the rest, while the particle size of the quasicrystalline filler is less than 45 microns. 2. A method of obtaining a concentrate for the production of thermoplastic polymer compositions, including surface modification of particles of a quasicrystalline filler in an alcohol solution of silanes under ultrasonic cavitation treatment, drying of the filler, extrusion mixing of a quasicrystalline filler with a thermoplastic polymer matrix at a temperature of 10-20 ° C above the melting temperature polymer, and granulation.

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