CN110713711A - Nylon 11/graphene/hollow glass bead composite material and preparation method and application thereof - Google Patents
Nylon 11/graphene/hollow glass bead composite material and preparation method and application thereof Download PDFInfo
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- CN110713711A CN110713711A CN201911085932.XA CN201911085932A CN110713711A CN 110713711 A CN110713711 A CN 110713711A CN 201911085932 A CN201911085932 A CN 201911085932A CN 110713711 A CN110713711 A CN 110713711A
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/28—Glass
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K9/00—Use of pretreated ingredients
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- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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Abstract
The invention relates to the technical field of composite materials, in particular to a nylon 11/graphene/hollow glass bead composite material and a preparation method and application thereof. The nylon 11/graphene/hollow glass bead composite material provided by the invention comprises nylon 11, graphene and modified hollow glass beads; the modified hollow glass beads are silane coupling agent modified hollow glass beads. The graphene and the modified hollow glass beads in the nylon 11/graphene/hollow glass bead composite material provided by the invention can improve the impact strength, the bending strength and the bending modulus of nylon 11, and meanwhile, the addition of the graphene and the modified hollow glass beads plays a role in heterogeneous nucleation, so that the crystallization rate of nylon 11 is improved. Meanwhile, the hollow glass beads modified by the silane coupling agent can greatly increase the probability of reaction with the chemical bonds of the nylon 11 base material.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a nylon 11/graphene/hollow glass bead composite material and a preparation method and application thereof.
Background
It is well known that crystalline particle size, crystallinity, crystallization rate, etc. have a significant effect on the properties of polymers. Nylon 11 is a kind of polyamide, and although its crystallinity is not so high, the presence of the crystalline region makes pure nylon 11 a crystalline polymer in which an ordered phase and a disordered phase coexist. The existence of crystal regions in the nylon 11 aggregation state influences the mechanical property, the dielectric property and the like of the nylon 11. Therefore, it is becoming important to improve the crystallization property of nylon 11, and further improve the mechanical property and dielectric property of nylon 11.
Disclosure of Invention
The invention aims to provide a nylon 11/graphene/hollow glass bead composite material and a preparation method thereof, wherein the nylon 11/graphene/hollow glass bead composite material has a high crystallization rate and is convenient to process and manufacture, and the nylon 11/graphene/hollow glass bead composite material has good mechanical property and dielectric property.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a nylon 11/graphene/hollow glass bead composite material, which comprises nylon 11, graphene and modified hollow glass beads;
the modified hollow glass beads are silane coupling agent modified hollow glass beads.
Preferably, the mass ratio of the nylon 11 to the graphene to the hollow glass beads is 300: (0.15-3): (9-33).
The invention also provides a preparation method of the nylon 11/graphene/hollow glass bead composite material, which comprises the following steps:
sequentially purifying the hollow glass beads in acid liquor and alkali liquor, mixing with a silane coupling agent, and modifying to obtain modified hollow glass beads;
mixing nylon 11, graphene and the modified hollow glass beads, and sequentially performing extrusion granulation and injection molding to obtain the nylon 11/graphene/hollow glass bead composite material.
Preferably, the silane coupling agent is one or more of a silane coupling agent KH-550, a silane coupling agent KH560, a silane coupling agent KH570, a silane coupling agent KH590 and a silane coupling agent KH 620.
Preferably, the mass ratio of the silane coupling agent to the hollow glass beads is (10-50): 100.
preferably, the extrusion granulation is performed in a twin-screw extruder;
the rotating speed of a main machine of the double-screw extruder is 10-100 Hz, and the rotating speed of a feeding machine of the double-screw extruder is 1-10 Hz.
Preferably, the temperature of the extrusion granulation is divided into six zones; the temperatures of the six zones are respectively as follows: 215-225 ℃, 225-235 ℃, 235-245 ℃, 245-255 ℃ and 240-250 ℃.
Preferably, the injection molding pressure of the injection molding is 30-60 MPa, and the temperature is 240-250 ℃;
and the pressure maintaining pressure of the injection molding is 35-45 MPa, and the pressure maintaining time is 2-6 s.
Preferably, the injection molding temperature is divided into five zones; the temperatures of the five zones are respectively as follows: 250-260 ℃, 240-250 ℃ and 240-250 ℃.
The invention also provides the application of the nylon 11/graphene/hollow glass bead composite material or the nylon 11/graphene/hollow glass bead composite material prepared by the preparation method in the technical scheme in the fields of high-temperature resistant materials, stealth materials and aerospace materials.
The invention provides a nylon 11/graphene/hollow glass bead composite material, which comprises nylon 11, graphene and modified hollow glass beads; the modified hollow glass beads are silane coupling agent modified hollow glass beads. The graphene addition plays a role in heterogeneous nucleation, the crystal form of nylon 11 is changed, and the addition of the modified hollow glass beads hinders the growth of crystals in a (010,110) plane normal phase; the two synergistically act to increase the crystallization rate of nylon 11. Meanwhile, the probability of reaction with the chemical bond of the nylon 11 matrix material can be greatly increased. According to the description of the embodiment, the nylon 11/graphene/hollow glass bead composite material has a crystallization rate constant Zt of 0.4-2.0;
meanwhile, graphene and modified hollow glass beads in the nylon 11/graphene/hollow glass bead composite material provided by the invention can improve the mechanical property and dielectric property of nylon 11, and according to the records of the embodiment, the impact strength of the nylon 11/graphene/hollow glass bead composite material provided by the invention can maximally reach 19.89KJ/m22.1 times of pure nylon 11, and the bending strength and the bending modulus of the material are both improved compared with those of the pure nylon 11; the magnetic conductivity and the return loss of the material are also greatly improved compared with those of pure nylon 11.
Drawings
FIG. 1 is an infrared spectrum of pure nylon 11, a nylon 11/graphene composite material as described in comparative example 1, and a nylon 11/graphene/hollow glass bead composite material as described in example 1;
FIG. 2 is an XRD pattern of pure nylon 11, the nylon 11/graphene composite material described in comparative example 1, and the nylon 11/graphene/hollow glass bead composite material described in example 1;
fig. 3 is a diagram of non-isothermal crystallization performance of pure nylon 11 and the nylon 11/graphene composite material described in comparative example 1 at different cooling rates (a is pure nylon 11, b is the nylon 11/graphene composite material described in comparative example 1);
FIG. 4 is a diagram of non-isothermal crystallization performance of the nylon 11/graphene/hollow glass bead composite material of examples 1-5 at different cooling rates (a is example 1, b is example 2, c is example 3, d is example 4 and e is example 5);
fig. 5 is a graph of crystallinity versus temperature for the nylon 11/graphene composite described in comparative example 1 at different cooling rates;
FIG. 6 is a graph showing the crystallinity and temperature of the nylon 11/graphene/hollow glass bead composite material according to examples 1-5 at different cooling rates (a is example 1, b is example 2, c is example 3, d is example 4, and e is example 5);
fig. 7 is a graph of the crystallinity of the nylon 11/graphene composite material of comparative example 1 at different cooling rates versus time;
FIG. 8 is a graph of the crystallinity of the nylon 11/graphene/hollow glass bead composite material according to examples 1-5 at different cooling rates versus time (a is example 1, b is example 2, c is example 3, d is example 4, and e is example 5);
FIG. 9 is a graph of lg { -ln [1-X (t) ] } to lgt of the nylon 11/graphene composite material of comparative example 1 at different cooling rates;
FIG. 10 is a graph of lg { -ln [1-X (t) } lgt of the nylon 11/graphene/hollow glass bead composite material of examples 1-5 at different cooling rates (a is example 1, b is example 2, c is example 3, d is example 4 and e is example 5);
FIG. 11 is a scanning electron microscope image of the impact cross section of pure nylon 11, the nylon 11/graphene composite material described in comparative example 1, and the nylon 11/graphene/hollow glass bead composite materials described in examples 1-2 (a is pure nylon 11, b is comparative example 1, c is example 1, and d is example 2);
FIG. 12 is a graph showing the change in impact strength between the nylon 11/graphene/hollow glass bead composite described in examples 1 to 5 and the nylon 11/graphene composite described in comparative example 1 (3% in example 1, 5% in example 2, 7% in example 3, 9% in example 4, 11% in example 5, and 0% in comparative example);
FIG. 13 is a graph showing the change in tensile strength and elongation at break of the nylon 11/graphene/hollow glass bead composite described in examples 1 to 5 and the nylon 11/graphene composite described in comparative example 1 (3% for example 1, 5% for example 2, 7% for example 3, 9% for example 4, 11% for example 5, and 0% for comparative example);
FIG. 14 is a graph showing the change in flexural strength and flexural modulus of the nylon 11/graphene/hollow glass bead composite described in examples 1 to 5 and the nylon 11/graphene composite described in comparative example 1 (3% in example 1, 5% in example 2, 7% in example 3, 9% in example 4, 11% in example 5, and 0% in comparative example);
FIG. 15 is a graph showing the dielectric constant comparison between nylon 11/graphene/hollow glass bead composites of examples 1 to 5 under different frequency conditions (3% in example 1, 5% in example 2, 7% in example 3, 9% in example 4, and 11% in example 5);
fig. 16 is a graph showing the dielectric loss comparison of the nylon 11/graphene/hollow glass bead composite material according to examples 1 to 5 under different frequency conditions (3% in example 1, 5% in example 2, 7% in example 3, 9% in example 4, and 11% in example 5);
fig. 17 is a comparison graph of magnetic storage coefficients of the nylon 11/graphene/hollow glass bead composite material according to examples 1 to 5 under different frequency conditions (3% in example 1, 5% in example 2, 7% in example 3, 9% in example 4, and 11% in example 5);
fig. 18 is a graph showing the comparison of the magnetic loss coefficients of the nylon 11/graphene/hollow glass bead composite material according to examples 1 to 5 under different frequency conditions (3% in example 1, 5% in example 2, 7% in example 3, 9% in example 4, and 11% in example 5);
FIG. 19 shows the return loss R of the nylon 11/graphene/hollow glass bead composite material of examples 1 to 5 under different frequency conditionsLComparative graph (3% for example 1, 5% for example 2, true)7% for example 3, 9% for example 4 and 11% for example 5).
Detailed Description
The invention provides a nylon 11/graphene/hollow glass bead composite material, which comprises nylon 11, graphene and modified hollow glass beads;
preferably, suction filtration is carried out; the drying is not particularly limited in the present invention and may be carried out by a process known to those skilled in the art.
In the invention, the silane coupling agent is preferably one or more of a silane coupling agent KH-550, a silane coupling agent KH560, a silane coupling agent KH570, a silane coupling agent KH590 and a silane coupling agent KH 620. When the silane coupling agents are more than two of the above specific choices, the specific ratio of the specific substances is not limited in any way, and the specific substances can be mixed according to any ratio.
In the present invention, the modification is preferably carried out in a system in which absolute ethanol is used as a medium; the modified atmosphere is preferably an inert atmosphere; the gas of the inert atmosphere is preferably carbon dioxide, nitrogen or a rare gas, and more preferably nitrogen. The modification is preferably carried out under stirring conditions, and the stirring is not particularly limited in the present invention, and a process well known to those skilled in the art may be employed.
After the modified hollow glass microspheres are obtained, nylon 11, graphene and the modified hollow glass microspheres are mixed, and extrusion granulation and injection molding are sequentially carried out to obtain the nylon 11/graphene/hollow glass microsphere composite material.
The graphene and nylon 11 are preferably pretreated in the present invention before mixing. In the present invention, the pretreatment of the graphene is preferably: adding graphene into an ethanol water solution, and sequentially performing ultrasonic dispersion, freeze drying and drying; the ultrasonic dispersion, freeze drying and drying are not limited in any way, and can be carried out by adopting the processes well known to the skilled person. In the present invention, the pretreatment of the nylon 11 is preferably drying; the drying temperature is preferably 60-100 ℃, more preferably 80 ℃, and the drying time is preferably 10-15 h, more preferably 12 h. The drying is preferably carried out in a vacuum drying oven.
The present invention does not limit the mixing in any particular way, and the mixing may be carried out by a process known to those skilled in the art. In the invention, before extrusion granulation, the mixed materials are preferably subjected to melt extrusion; the melt extrusion is not particularly limited in the present invention, and may be carried out by a process known to those skilled in the art.
In the present invention, the extrusion granulation is performed in a twin-screw extruder; the main machine rotating speed of the double-screw extruder is preferably 10-100 Hz, and more preferably 30 Hz; the rotating speed of a feeding machine of the double-screw extruder is preferably 1-10 Hz, and more preferably 3.5 Hz.
In the present invention, the temperature of the extrusion granulation is preferably divided into six zones; the temperatures of the six zones are preferably: 215-225 ℃, 225-235 ℃, 235-245 ℃, 245-255 ℃ and 240-250 ℃, more preferably 220 ℃, 230 ℃, 240 ℃, 250 ℃, 250 ℃ and 245 ℃.
In the invention, the injection pressure of the injection molding is preferably 30-60 MPa, and more preferably 55 MPa; the injection molding temperature is preferably 240-250 ℃, and the injection molding temperature is preferably divided into five zones; the temperatures of the five zones are preferably: 250-260 ℃, 240-250 ℃ and 240-250 ℃, more preferably 255 ℃, 245 ℃, 245 ℃ and 245 ℃. The pressure of the injection molding is preferably 50-60 MPa, and more preferably 55 MPa.
The pressure maintaining pressure of the injection molding is preferably 35-45 MPa, and more preferably 40 MPa; the dwell time is preferably 2 to 6s, more preferably 4 s.
After the injection molding is finished, the injection molded material is preferably dried, and the drying time is preferably 24 hours.
The invention also provides the application of the nylon 11/graphene/hollow glass bead composite material or the nylon 11/graphene/hollow glass bead composite material prepared by the preparation method in the technical scheme in the application fields of high-temperature resistant materials, stealth materials and aerospace materials. The method of the present invention is not particularly limited, and a method known to those skilled in the art may be selected.
The nylon 11/graphene/hollow glass bead composite material, the preparation method and the application thereof provided by the present invention are described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Under the condition of stirring, sequentially purifying hollow glass microspheres in hydrochloric acid and sodium hydroxide solution, cleaning with absolute ethanol solution, modifying with a silane coupling agent KH-550, performing suction filtration, and drying for 24h to obtain modified hollow glass beads;
mixing 300g of nylon 11, 0.6g of graphene and 9g of modified hollow glass microspheres, sequentially carrying out melt extrusion, extrusion granulation (220 ℃, 230 ℃, 240 ℃, 250 ℃, 250 ℃ and 245 ℃, the main machine rotating speed of a double-screw extruder is 30Hz, the feeding machine rotating speed is 3.5Hz) and injection molding (255 ℃, 245 ℃, 245 ℃ and 245 ℃, the injection molding pressure is 55MPa, the pressure maintaining pressure is 40MPa, and the pressure maintaining time is 4s), and drying for 24h to obtain the nylon 11/graphene/hollow glass microsphere composite material.
Example 2
Under the condition of stirring, sequentially purifying hollow glass microspheres in concentrated hydrochloric acid and sodium hydroxide solution, cleaning with absolute ethanol solution, modifying with a silane coupling agent KH-550, performing suction filtration, and drying for 24h to obtain modified hollow glass beads;
mixing 300g of nylon 11, 0.6g of graphene and 15g of modified hollow glass microspheres, sequentially carrying out melt extrusion, extrusion granulation (220 ℃, 230 ℃, 240 ℃, 250 ℃, 250 ℃ and 245 ℃, the main machine rotating speed of a double-screw extruder is 30Hz, the feeding machine rotating speed is 3.5Hz) and injection molding (255 ℃, 245 ℃, 245 ℃ and 245 ℃, the injection molding pressure is 55MPa, the pressure maintaining pressure is 40MPa, and the pressure maintaining time is 4s), and drying for 24h to obtain the nylon 11/graphene/hollow glass microsphere composite material.
Example 3
Under the condition of stirring, sequentially purifying hollow glass microspheres in concentrated hydrochloric acid and sodium hydroxide solution, cleaning with absolute ethanol solution, modifying with a silane coupling agent KH-550, performing suction filtration, and drying for 24h to obtain modified hollow glass beads;
mixing 300g of nylon 11, 0.6g of graphene and 21g of modified hollow glass microspheres, sequentially carrying out melt extrusion, extrusion granulation (220 ℃, 230 ℃, 240 ℃, 250 ℃, 250 ℃ and 245 ℃, the main machine rotating speed of a double-screw extruder is 30Hz, the feeding machine rotating speed is 3.5Hz) and injection molding (255 ℃, 245 ℃, 245 ℃ and 245 ℃, the injection molding pressure is 55MPa, the pressure maintaining pressure is 40MPa, and the pressure maintaining time is 4s), and drying for 24h to obtain the nylon 11/graphene/hollow glass microsphere composite material.
Example 4
Under the condition of stirring, sequentially purifying hollow glass microspheres in concentrated hydrochloric acid and sodium hydroxide solution, cleaning with absolute ethanol solution, modifying with a silane coupling agent KH-550, performing suction filtration, and drying for 24h to obtain modified hollow glass beads;
mixing 300g of nylon 11, 0.6g of graphene and 27g of modified hollow glass microspheres, sequentially carrying out melt extrusion, extrusion granulation (220 ℃, 230 ℃, 240 ℃, 250 ℃, 250 ℃ and 245 ℃, the main machine rotating speed of a double-screw extruder is 30Hz, the feeding machine rotating speed is 3.5Hz) and injection molding (255 ℃, 245 ℃, 245 ℃ and 245 ℃, the injection molding pressure is 55MPa, the pressure maintaining pressure is 40MPa, and the pressure maintaining time is 4s), and drying for 24h to obtain the nylon 11/graphene/hollow glass microsphere composite material.
Example 5
Under the condition of stirring, sequentially purifying hollow glass microspheres in concentrated hydrochloric acid and sodium hydroxide solution, cleaning with absolute ethanol solution, modifying with a silane coupling agent KH-550, performing suction filtration, and drying for 24h to obtain modified hollow glass beads;
mixing 300g of nylon 11, 0.6g of graphene and 33g of modified hollow glass microspheres, sequentially carrying out melt extrusion, extrusion granulation (220 ℃, 230 ℃, 240 ℃, 250 ℃, 250 ℃ and 245 ℃, the main machine rotating speed of a double-screw extruder is 30Hz, the feeding machine rotating speed is 3.5Hz) and injection molding (255 ℃, 245 ℃, 245 ℃ and 245 ℃, the injection molding pressure is 55MPa, the pressure maintaining pressure is 40MPa, and the pressure maintaining time is 4s), and drying for 24h to obtain the nylon 11/graphene/hollow glass microsphere composite material.
Example 6
Under the condition of stirring, sequentially purifying hollow glass microspheres in concentrated hydrochloric acid and sodium hydroxide solution, cleaning with absolute ethanol solution, modifying with a silane coupling agent KH-550, performing suction filtration, and drying for 24h to obtain modified hollow glass beads;
mixing 300g of nylon 11, 1.2g of graphene and 33g of modified hollow glass microspheres, sequentially carrying out melt extrusion, extrusion granulation (220 ℃, 230 ℃, 240 ℃, 250 ℃, 250 ℃ and 245 ℃, the main machine rotating speed of a double-screw extruder is 30Hz, the feeding machine rotating speed is 3.5Hz) and injection molding (255 ℃, 245 ℃, 245 ℃ and 245 ℃, the injection molding pressure is 55MPa, the pressure maintaining pressure is 40MPa, and the pressure maintaining time is 4s), and drying for 24h to obtain the nylon 11/graphene/hollow glass microsphere composite material.
Example 7
Under the condition of stirring, sequentially purifying hollow glass microspheres in concentrated hydrochloric acid and sodium hydroxide solution, cleaning with absolute ethanol solution, modifying with a silane coupling agent KH-550, performing suction filtration, and drying for 24h to obtain modified hollow glass beads;
mixing 300g of nylon 11, 1.8g of graphene and 33g of modified hollow glass microspheres, sequentially carrying out melt extrusion, extrusion granulation (220 ℃, 230 ℃, 240 ℃, 250 ℃, 250 ℃ and 245 ℃, the main machine rotating speed of a double-screw extruder is 30Hz, the feeding machine rotating speed is 3.5Hz) and injection molding (255 ℃, 245 ℃, 245 ℃ and 245 ℃, the injection molding pressure is 55MPa, the pressure maintaining pressure is 40MPa, and the pressure maintaining time is 4s), and drying for 24h to obtain the nylon 11/graphene/hollow glass microsphere composite material.
Example 8
Under the condition of stirring, sequentially purifying hollow glass microspheres in concentrated hydrochloric acid and sodium hydroxide solution, cleaning with absolute ethanol solution, modifying with a silane coupling agent KH-550, performing suction filtration, and drying for 24h to obtain modified hollow glass beads;
mixing 300g of nylon 11, 2.4g of graphene and 33g of modified hollow glass microspheres, sequentially carrying out melt extrusion, extrusion granulation (220 ℃, 230 ℃, 240 ℃, 250 ℃, 250 ℃ and 245 ℃, the main machine rotating speed of a double-screw extruder is 30Hz, the feeding machine rotating speed is 3.5Hz) and injection molding (255 ℃, 245 ℃, 245 ℃ and 245 ℃, the injection molding pressure is 55MPa, the pressure maintaining pressure is 40MPa, and the pressure maintaining time is 4s), and drying for 24h to obtain the nylon 11/graphene/hollow glass microsphere composite material.
Example 9
Under the condition of stirring, sequentially purifying hollow glass microspheres in concentrated hydrochloric acid and sodium hydroxide solution, cleaning with absolute ethanol solution, modifying with a silane coupling agent KH-550, performing suction filtration, and drying for 24h to obtain modified hollow glass beads;
mixing 300g of nylon 11, 3.0g of graphene and 33g of modified hollow glass microspheres, sequentially carrying out melt extrusion, extrusion granulation (220 ℃, 230 ℃, 240 ℃, 250 ℃, 250 ℃ and 245 ℃, the main machine rotating speed of a double-screw extruder is 30Hz, the feeding machine rotating speed is 3.5Hz) and injection molding (255 ℃, 245 ℃, 245 ℃ and 245 ℃, the injection molding pressure is 55MPa, the pressure maintaining pressure is 40MPa, and the pressure maintaining time is 4s), and drying for 24h to obtain the nylon 11/graphene/hollow glass microsphere composite material.
Comparative example 1
Respectively drying 190g of nylon 11 and 0.38g of graphene, mixing, performing compression molding (the pressure is 12MPa, the temperature is 220 ℃, and the heat preservation time is 6min), and cooling to room temperature to obtain the nylon 11/graphene composite material.
Comparative example 2
Referring to comparative example 1, the only difference is that the amount of graphene is 0.76 g.
Comparative example 3
Referring to comparative example 1, the only difference is that the amount of graphene is 1.14 g.
Comparative example 4
Referring to comparative example 1, the only difference is that the amount of graphene is 1.52 g.
Comparative example 5
Referring to comparative example 1, the only difference is that the amount of graphene is 1.9 g.
Test example
Infrared spectrum test:
according to the GB/T6040-2002 standard, infrared spectrum tests (the test range is 4000-650 cm) are carried out on pure nylon 11, the nylon 11/graphene composite material in the comparative example 1 and the nylon 11/graphene/hollow glass bead composite material in the example 1-1Resolution of 4cm-1) The test results are shown in FIG. 1, and it can be seen from FIG. 1 that 3298cm-1Is the stretching vibration peak of N-H in the main chain; 1050cm-1Is Si-O stretching vibration absorption peak; 1553cm-1Absorption peak 1322cm for the combination of N-H in-plane bending and C-N bending vibration-1Is a combined absorption peak of C-N stretching vibration and C-H in-plane bending; 1558cm-1Is represented by CH2Is a rocking vibration. The nylon 11/graphene/hollow glass bead composite material described in example 1 includes nylon 11, graphene and hollow glass beads, wherein Si — O bonds have been successfully introduced into the molecular chains of the hollow glass beads, which indicates that the silane coupling agent is successful in modifying the surfaces of the hollow glass beads.
XRD test:
XRD (X-ray diffraction) tests (test by an X-ray diffractometer of a D/max-rB model manufactured by Japan, with a voltage of 40KV, a current of 100mA and a Cu target (K) were carried out on pure nylon 11, the nylon 11/graphene composite material described in comparative example 1 and the nylon 11/graphene/hollow glass bead composite material described in example 1αWavelength 0.15408nm), scanning speed: 4 °/min, scan angle 5 ° -60 °), the test result is shown in fig. 2, and as can be seen from fig. 2, pure nylon 11 has two diffraction peaks at 2 θ ═ 10 ° and 20.5 °, and the crystal structure at this time corresponds to the α crystal form of nylon 11. When graphene is added into nylon 11, the diffraction peak is split, and two diffraction peaks appear at 20.1 degrees and 22.37 degrees respectively, which indicates that the crystal form of PA11 is changed, wherein the diffraction peak at 22.37 degrees corresponds to the crystal face of the gamma crystal form of nylon 11; compared with nylon 11/graphene/hollow glass bead composite material, the nylon 11/graphene/hollow glass bead composite materialThe 22.37 DEG diffraction peak of the composite material which is split disappears, and the improvement of the crystallization performance is proved, and the increase of the crystallization rate is promoted by adding the micro-beads.
And (4) SEM test:
carrying out SEM test on pure nylon 11, the nylon 11/graphene composite material described in the comparative example 1 and the nylon 11/graphene/hollow glass bead composite material described in the examples 1-2, wherein the test process comprises the following steps: the gold plating treatment was carried out by using a scanning electron microscope SU-5000, manufactured by Hitachi high and New technology, and using a gold plating apparatus. Under the nitrogen atmosphere, an accelerating voltage of 20KV is used, an electron scanning microscope is used for observing, scanning and processing, and then photographing is carried out;
the test results are shown in fig. 11, where a is pure nylon 11, b is the nylon 11/graphene composite material prepared in comparative example 1, c is the nylon 11/graphene/hollow glass bead composite material prepared in example 1, and d is the nylon 11/graphene/hollow glass bead composite material prepared in example 2, as can be seen from fig. 11, the impact section of pure nylon 11 is relatively smooth, which indicates that nylon 11 is brittle fracture; the impact section of the nylon 11/graphene composite material is uneven, and mainly due to the fact that the added graphene enables a sample to generate silver stripes under the impact action of external force, and the impact strength of the material is improved; the notch impact section of the nylon 11/graphene/hollow glass bead composite material becomes more complex, a 'sea island' distribution structure is presented, and certain energy is required for the modified hollow glass beads to be pulled out of the nylon 11 matrix, so that the impact strength of the material is improved, and the impact strength is consistent with the subsequent impact strength test result of the nylon 11/graphene/hollow glass bead composite material.
And (3) testing the crystallization property:
6mg of pure nylon 11, the nylon 11/graphene composite material described in the comparative example 1 and the nylon 11/graphene/hollow glass bead composite material described in the examples 1 to 5 were dried, and then added into an aluminum crucible of a differential scanning calorimeter, and the mixture was sealed and compacted for non-isothermal crystallization and melting behavior determination. High-purity nitrogen is introduced in the whole testing process to stabilize the testing environment, and the nitrogen flow is 50 mL/min. An empty aluminum crucible was placed for comparison. The sample was first raised to 250 ℃ at a rate of 20 ℃/min. Then, the temperature was maintained for 5min to eliminate the heat history. Then cooling to 30 deg.C at cooling rate of 2.5 deg.C/min, 5 deg.C/min, 10 deg.C/min, 20 deg.C/min and 40 deg.C/min, and keeping the temperature for 10 min. Recording DSC curves recorded in the whole process, and analyzing the non-isothermal crystallization and melting behaviors of the material;
the test results are shown in fig. 3-8, wherein fig. 3 is a graph of non-isothermal crystallization performances of the nylon 11/graphene composite material described in the pure nylon 11 and the comparative example 1 at different cooling rates (a is the pure nylon 11, and b is the nylon 11/graphene composite material described in the comparative example 1), and as can be seen from fig. 3, the non-isothermal crystallization peaks of the nylon 11 and the nylon 11/graphene composite material are both larger in the cooling rate, the wider in the peak shape, the wider in the coverage temperature range, and the peak value of the crystallization peak moves towards the low temperature direction;
FIG. 4 is a diagram of non-isothermal crystallization performance of the nylon 11/graphene/hollow glass bead composite materials of examples 1-5 at different cooling rates (a is example 1, b is example 2, c is example 3, d is example 4 and e is example 5), and it can be seen from FIG. 4 that the non-isothermal crystallization peaks of the nylon 11/graphene/hollow glass bead composite materials of examples 1-5 are also single peaks, and compared with b in FIG. 3, it can be seen that the nylon 11/graphene/hollow glass bead composite materials of examples 1-5 have a higher degree of crystal perfection and a wider crystallization temperature zone compared with the nylon 11/graphene composite material of comparative example 1, resulting in a higher overall temperature of the crystallization peak than that of comparative example 1;
fig. 5 is a graph of crystallinity versus temperature for the nylon 11/graphene composite described in comparative example 1 at different cooling rates; as can be seen from fig. 5, with the increase of the cooling rate, the molecular chain of the nylon 11/graphene composite material moves violently under the high temperature condition, and no time is available for forming crystal nuclei, so the crystallization starting temperature gradually moves to the low temperature;
FIG. 6 is a graph of the crystallinity and the temperature of the nylon 11/graphene/hollow glass bead composite materials of examples 1-5 at different cooling rates (a is example 1, b is example 2, c is example 3, d is example 4 and e is example 5), and it can be seen from FIG. 6 that the initial temperature of crystallization of the nylon 11/graphene/hollow glass bead composite materials of examples 1-5 also gradually shifts to a low temperature along with the increase of the cooling rate, but the initial temperature of crystallization of the nylon 11/graphene/hollow glass bead composite materials is higher than that of comparative example 1 as a whole;
fig. 7 is a graph of the crystallinity of the nylon 11/graphene composite material of comparative example 1 at different cooling rates versus time; as can be seen from fig. 7, the smaller the cooling rate of the nylon 11/graphene composite material is, the longer the crystallization time is, which indicates that the nucleation speed of the nylon 11/graphene composite material is reduced and the crystallization time is increased along with the reduction of the cooling rate;
fig. 8 is a graph of the crystallinity of the nylon 11/graphene/hollow glass bead composite material according to examples 1 to 5 at different cooling rates versus time (a is example 1, b is example 2, c is example 3, d is example 4, and e is example 5), and it can be seen from fig. 8 that the nylon 11/graphene/hollow glass bead composite material according to examples 1 to 5 also has a longer crystallization time with a smaller cooling rate, but the crystallization time of the nylon 11/graphene/hollow glass bead composite material is lower than that of comparative example 1 as a whole.
Non-isothermal crystallization kinetic performance analysis was performed on the nylon 11/graphene composite material described in comparative example 1 and the nylon 11/graphene/hollow glass bead composite material described in examples 1 to 5 by using a equi-isothermal crystallization kinetics Avrami equation modified Jeziorrny method, and the analysis results are shown in FIGS. 9 to 10:
wherein, FIG. 9 shows lg { -ln [1-X (t) { (t) } of the nylon 11/graphene composite material in comparative example 1 at different cooling rates]The curves of (i) and (ii) are from (i) to (lgt), and the n and logZ of the nylon 11/graphene composite material at different cooling rates can be obtained according to the curvest1And Zc1Values, as shown in table 1:
FIG. 10 shows lg { -ln [1-X (t) { [1-X ] } of the nylon 11/graphene/hollow glass bead composite material of examples 1 to 5 at different cooling rates]The curve of (9) } -lgt, according to which the nylon 11/graphene/hollow glass bead composite material can be obtained at different cooling ratesN and logZ of lower nylon 11/graphene composite materialt1And ZcValues, as shown in table 1:
table 1 shows that the nylon 11/graphene composite material described in comparative example 1 and the n and logZ of the nylon 11/graphene/hollow glass bead composite material described in examples 1 to 5 under different cooling ratest1And Zc1Value of
As can be seen from table 1, the Avrami index value (i.e., n value) of the nylon 11/graphene composite material is reduced within a range of 1.10 to 2.60 (compared with 2.73 to 3.69 of pure nylon 11), which indicates that the graphene promotes nucleation and crystal growth of non-isothermal crystallization of nylon 11, and the Avrami index value of the nylon 11/graphene/hollow glass bead composite material described in examples 1 to 5 is within a range of 1.30 to 2.30; for the crystallization rate Zt, the range of the crystallization rate constant of the nylon 11/graphene composite material is 0.2-1.9, and the range of the crystallization rate constant of the nylon 11/graphene/hollow glass bead composite material described in example 1 is 0.4-2.0.
And (3) testing impact strength:
according to the test standard of GB/T1843-2008, the nylon 11/graphene/hollow glass bead composite material described in the embodiment 1-5 and the nylon 11/graphene composite material described in the comparative example 1 are subjected to an impact performance test, and the impact strength is calculated;
as shown in FIG. 12, it can be seen that the impact strength of the composite material is improved by adding the modified hollow glass beads, the impact strength of the material shows a trend of increasing and decreasing with the increase of the content of the modified hollow glass beads, and when the content of the modified hollow glass beads is 5%, the impact strength of the material reaches a maximum value of 19.89KJ/m22.1 times that of pure PA 11. Low content of modified hollow glass microspheresThe material is uniformly dispersed in a resin matrix, and when the resin matrix is stressed, cavities and a large number of microcracks are generated around particles, so that a large amount of energy is absorbed, the toughness of the material is increased, and the impact strength of the material is improved; when the content of the modified hollow glass beads is too high, agglomeration occurs to reduce the impact strength of the composite material.
And (3) testing tensile strength:
the nylon 11/graphene/hollow glass bead composite material described in the embodiment 1-5 and the nylon 11/graphene composite material described in the comparative example 1 were tested for tensile strength and elongation at break, and the test procedures were as follows: the bent sample strips were tested in an environment at room temperature (25 ℃) using a universal testing machine according to the GB/T9341-2008 standard, wherein the test speed was 2 mm/min.
As shown in fig. 13, it can be seen that the tensile strength of the PA 11/graphene composite material is decreased as a whole by adding the modified hollow glass beads, the tensile strength of the composite material shows a tendency of decreasing first and then increasing, and when the content of the modified hollow glass beads is 5%, the tensile strength of the material is the lowest, 37.6MPa, which is 0.76 times that of pure PA 11; after that, the tensile strength of the added modified hollow glass microspheres is gradually increased. Pure PA11 breaks at tensile break after each orientation unit is fully oriented, and has a relatively large number of chemical bonds to be broken at break, resulting in high tensile strength and elongation at break. After the modified hollow glass beads are added, the load transfer area of the matrix is reduced, and the stress transfer is hindered, so that the tensile strength of the composite material is reduced. The modified hollow glass beads can be used as a stress concentrator to generate crazing to absorb energy, when the content of the beads is increased, the initiated crazing is increased, and when the content of the hollow glass beads is increased, the tensile strength of the material is improved to some extent. The addition of the modified hollow glass beads can reduce the elongation at break of the material, because the modified hollow glass beads limit the movement of PA11 macromolecules, and the modified hollow glass beads cannot be fully oriented along the stress direction during stretching, so that the elongation at break is reduced.
Flexural strength and flexural modulus test:
the bending strength and the bending modulus of the nylon 11/graphene/hollow glass bead composite material described in the embodiment 1-5 and the nylon 11/graphene composite material described in the comparative example 1 are tested, and the test process is as follows: the bent specimens were tested at room temperature (25 ℃) in accordance with the GB/T9341-2008 standard using a universal tester, with a test speed of 2 mm/min.
The test results are shown in fig. 14, and it can be seen that the addition of the modified hollow glass beads enhances both the flexural strength and the flexural modulus of the composite material, and the trend is increasing. The reason is that the addition of the modified hollow glass beads limits the movement of the nylon 11 when the nylon is subjected to bending stress, so that the material is more difficult to deform, the rigidity is improved, and the bending strength and the bending modulus are increased.
And (3) dielectric property test:
the nylon 11/graphene/hollow glass bead composite material described in the embodiment 1-5 is subjected to a dielectric property test, and the test result is shown in fig. 15-19:
fig. 15 is a comparison graph of dielectric constants of the nylon 11/graphene/hollow glass bead composite materials of examples 1 to 5 under different frequency conditions, and as can be seen from fig. 15, the dielectric constants of the nylon 11/graphene/hollow glass bead composite materials of examples 1 to 5 are increased and then decreased, wherein the dielectric constant of example 2 is the largest, and the dielectric constant is 6.61 under the condition of 30 MHz. Since the modified hollow glass beads show agglomeration problems in nylon 11 as their addition amount increases. Therefore, the dielectric constant of the nylon 11/graphene/hollow glass bead composite material is increased and then reduced;
fig. 16 is a graph showing the dielectric loss comparison of the nylon 11/graphene/hollow glass bead composite materials of examples 1 to 5 under different frequency conditions, and it can be seen from fig. 16 that the dielectric loss of the nylon 11/graphene/hollow glass bead composite materials of examples 1 to 5 tends to increase, and the dielectric loss of the composite materials has a peak value within the frequency range of 2000 to 2500 Mfz. The dielectric loss is obviously increased after the modified hollow glass beads are added. Because the spherical hollow structure of the modified hollow glass microspheres is beneficial to the loss of the electromagnetic waves in the matrix. Furthermore, the dielectric loss of the material is further increased by the agglomeration of the modified hollow glass microspheres.
Fig. 17 is a comparison graph of magnetic storage coefficients of the nylon 11/graphene/hollow glass bead composite materials of examples 1 to 5 under different frequency conditions, and as can be seen from fig. 17, the magnetic storage coefficients of the nylon 11/graphene/hollow glass bead composite materials of examples 1 to 5 are increased and then decreased, wherein the dielectric constant of example 4 is the largest, and the magnetic storage coefficient of the nylon 11/graphene/hollow glass bead composite material of example 4 is 8.24 at a frequency of 0 MHz. The spherical hollow structure of the modified hollow glass microsphere has a promoting effect on the magnetic property of the material;
fig. 18 is a comparison graph of magnetic loss coefficients of the nylon 11/graphene/hollow glass bead composite materials of examples 1 to 5 under different frequency conditions, and it can be seen from fig. 18 that the magnetic loss coefficients of the nylon 11/graphene/hollow glass bead composite materials of examples 1 to 5 are increased first and then decreased. The nylon 11/graphene/hollow glass bead composite shown in example 2 had the smallest magnetic loss coefficient. Because the modified hollow glass beads obviously enhance the loss of the composite material. The agglomeration phenomenon of the modified hollow glass beads is also a main reason for increasing the magnetic loss coefficient of the material;
FIG. 19 shows the return loss R of the nylon 11/graphene/hollow glass bead composite material of examples 1 to 5 under different frequency conditionsLIn comparison, FIG. 19 shows the return loss R of the nylon 11/graphene/hollow glass bead composite materials of examples 1 to 5LThe return loss R of the nylon 11/graphene/hollow glass bead composite material shown in example 2 is increased and then decreasedLAt the maximum, the nylon 11/graphene/hollow glass bead composite material in example 2 can better satisfy the electromagnetic matching property, so that more frequency bands of electromagnetic waves enter the composite material to be attenuated and lost.
According to the embodiment, the graphene and the modified hollow glass beads in the nylon 11/graphene/hollow glass bead composite material provided by the invention can improve the impact strength, the bending strength and the bending modulus of the nylon 11, and meanwhile, the graphene and the modified hollow glass beads are added to play a role in heterogeneous nucleation, so that the crystallization rate of the nylon 11 is improved. Meanwhile, the hollow glass beads modified by the silane coupling agent can greatly increase the probability of reaction with the chemical bonds of the nylon 11 base material.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The nylon 11/graphene/hollow glass bead composite material is characterized by comprising nylon 11, graphene and modified hollow glass beads;
the modified hollow glass beads are silane coupling agent modified hollow glass beads.
2. The nylon 11/graphene/hollow glass bead composite material according to claim 1, wherein the mass ratio of the nylon 11 to the graphene to the modified hollow glass beads is 300: (0.15-3): (9-33).
3. The preparation method of the nylon 11/graphene/hollow glass bead composite material according to claim 1 or 2, characterized by comprising the following steps:
sequentially purifying the hollow glass beads in acid liquor and alkali liquor, mixing with a silane coupling agent, and modifying to obtain modified hollow glass beads;
mixing nylon 11, graphene and the modified hollow glass beads, and sequentially performing extrusion granulation and injection molding to obtain the nylon 11/graphene/hollow glass bead composite material.
4. The method according to claim 3, wherein the silane coupling agent is one or more selected from the group consisting of a silane coupling agent KH-550, a silane coupling agent KH560, a silane coupling agent KH570, a silane coupling agent KH590, and a silane coupling agent KH 620.
5. The preparation method according to claim 3, wherein the mass ratio of the silane coupling agent to the hollow glass beads is (10-50): 100.
6. the method of claim 3, wherein the extrusion granulation is performed in a twin screw extruder;
the rotating speed of a main machine of the double-screw extruder is 10-100 Hz, and the rotating speed of a feeding machine of the double-screw extruder is 1-10 Hz.
7. The production method according to claim 3 or 6, wherein the temperature of the extrusion granulation is divided into six zones; the temperatures of the six zones are respectively as follows: 215-225 ℃, 225-235 ℃, 235-245 ℃, 245-255 ℃ and 240-250 ℃.
8. The preparation method of the ball 3, wherein the injection molding pressure is 30-60 MPa, and the temperature is 240-250 ℃;
and the pressure maintaining pressure of the injection molding is 35-45 MPa, and the pressure maintaining time is 2-6 s.
9. The production method according to claim 3 or 8, wherein the injection molding temperature is divided into five zones; the temperatures of the five zones are respectively as follows: 250-260 ℃, 240-250 ℃ and 240-250 ℃.
10. The nylon 11/graphene/hollow glass bead composite material according to claim 1 or 2 or the nylon 11/graphene/hollow glass bead composite material prepared by the preparation method according to any one of claims 3 to 9 is applied to the fields of high-temperature resistant materials, stealth materials and aerospace materials.
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