CN111186823A - Polymer-assisted preparation method of two-dimensional material and composite material thereof - Google Patents
Polymer-assisted preparation method of two-dimensional material and composite material thereof Download PDFInfo
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Abstract
The invention discloses a method for preparing a two-dimensional material and a composite material thereof with the assistance of a polymer, which comprises the following steps: s1, mixing a polymer solution and a layered material, and grinding to obtain a two-dimensional material/polymer composite material, wherein the viscosity of the polymer solution is 500-500000 mPa & S, and the polymer solution comprises a polymer and a solvent; s2, filtering the polymer in the two-dimensional material/polymer composite material to obtain the two-dimensional material. The method provided by the embodiment of the invention can realize large-scale controllable preparation of the high-quality two-dimensional material, is convenient to operate, has simple and rapid process flow, is suitable for industrial production, and ensures high yield while realizing high quality standard, and the prepared two-dimensional material has the advantages of large sheet diameter and thin thickness.
Description
Technical Field
The invention relates to the technical field of two-dimensional material preparation, in particular to a method for polymer-assisted preparation of a two-dimensional material and a composite material thereof.
Background
With the development of science and technology, a plurality of emerging technologies such as wearable electronic devices, convenient medical diagnosis and artificial intelligence emerge in recent years, and the generation and application of the emerging technologies also put higher requirements on the performance of related materials. Due to the advantages of excellent structure and electrical properties, flexibility, large specific surface area, high carrier mobility and the like, the graphene has wide application prospects in the fields of electronic devices, energy storage, biomedicine, catalysis and the like, and opens a new era of two-dimensional material research. In addition to graphene, two-dimensional materials include transition metal chalcogenides, boron nitride (also known as "white graphene"), alkenes, and the like, encompassing metals, semiconductors, insulators. Various two-dimensional materials have various characteristics in the application field, and are expected to realize subversion and innovation development.
The premise of industrial application of the two-dimensional material is to realize large-scale controllable preparation of the two-dimensional material, and two major methods for preparing the two-dimensional material on a large scale at present comprise: a bottom-up chemical vapor deposition growth method and a top-down stripping method. The chemical vapor deposition method can be used for preparing two-dimensional materials with large size, high quality and adjustable thickness, but the method has low efficiency, low yield and high requirement on equipment. The stripping method has high yield, low cost, simplicity and convenience, and the prepared two-dimensional material is easy to process and assemble, so that the method is concerned. In recent years, researchers have developed a series of liquid phase stripping methods, such as an ultrasonic method, an electrochemical stripping method, and the like, which can achieve the preparation of two-dimensional materials such as graphene, transition metal sulfides, boron nitride, and the like, but each of these methods has some problems that are difficult to solve. For example, the ultrasonic method has the defects of low yield, small diameter of the prepared two-dimensional material sheet, low controllability of the layer number, difficulty in large-scale production, noise pollution generated in the ultrasonic process and the like. The electrochemical stripping method has the problems of high cost and difficulty in removing additives for assisting stripping.
Patent CN201710355473.7 discloses a method for preparing high-quality large-size two-dimensional material, which comprises: mixing the layered material with the grinding particles, extruding, grinding and stripping the layered material, then dispersing the stripped layered material in a solvent, and taking supernatant after the grinding particles and the thicker layered material are settled to obtain the high-quality large-size two-dimensional material dispersion liquid. The method has the disadvantages that the grinding particles are hard inorganic particles, and the acting force of the grinding particles on the laminated material not only leads the laminated material to be stripped, but also leads the two-dimensional material sheet obtained by stripping to be broken, thereby limiting the size of the sheet diameter.
Therefore, aiming at the problems, a method for preparing high-quality two-dimensional materials on a large scale is developed, and the method has important significance for realizing large-scale application of the materials.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a method for polymer-assisted preparation of a two-dimensional material and a composite material thereof, the two-dimensional material prepared by the method has large sheet diameter and thin thickness, high quality is realized, high yield is ensured, and the method can be used for large-scale production.
The technical scheme adopted by the invention is as follows:
in a first aspect of the present invention, there is provided a method for polymer-assisted preparation of a two-dimensional material, comprising the steps of:
s1, mixing a polymer solution and a layered material, and grinding to obtain a two-dimensional material/polymer composite material, wherein the viscosity of the polymer solution is 500-500000 mPa & S, and the polymer solution comprises a polymer and a solvent;
s2, filtering the polymer in the two-dimensional material/polymer composite material to obtain the two-dimensional material.
The polymer solution is prepared by dissolving a polymer in a solvent, wherein the polymer may be a water-soluble polymer or a water-insoluble polymer.
The polymer assisted method of preparing a two-dimensional material according to some embodiments of the present invention is a water-soluble polymer and a water-insoluble polymer, the water-soluble polymer including at least one of a natural water-soluble polymer, a chemically modified natural polymer, a synthetic water-soluble polymer.
A polymer-assisted method of making a two-dimensional material according to some embodiments of the present invention, the natural water-soluble polymer comprising at least one of starch, cellulose, animal gum, vegetable gum; the chemically modified natural polymer comprises at least one of modified starch and modified cellulose; the synthetic water-soluble polymer comprises at least one of polyethyleneimine, polyacrylamide, polyvinylpyrrolidone, polyacrylic acid, polyethylene oxide, melamine formaldehyde resin and urea formaldehyde resin. The vegetable gum includes but is not limited to sodium alginate and the modified cellulose includes but is not limited to carboxymethyl cellulose.
According to some embodiments of the present invention, the polymer solution in step S1: the mass ratio of the layered material is (5-5000): 1.
according to some embodiments of the invention, the polymer-assisted method of preparing a two-dimensional material, the solvent comprises at least one of water, ethanol, isopropanol, acetone, benzene, N-dimethylformamide.
Polymers according to some embodiments of the invention assist in the preparation of two-dimensional materials including at least one of graphite, layered sulfides, layered selenides, layered tellurides, layered boron nitrides, layered micas, layered clays, layered vermiculites, layered silicates, black phosphorus, black arsenic phosphorus, titanium oxides.
The layered sulfide includes layered molybdenum disulfide, layered tungsten disulfide, and the like.
According to the polymer-assisted method for preparing the two-dimensional material, the grinding force in the step S1 is 50-500N/cm2The grinding time is 0.5-100 h.
According to the method for preparing the two-dimensional material by the aid of the polymer, a mortar type grinding instrument is used in the grinding process in the step S1, and the grinding pestle and the scraper force are adjustable. In some embodiments the rotation speed of the mortar mill is 100 r/min.
According to the method for polymer-assisted preparation of a two-dimensional material according to some embodiments of the present invention, the filtering in step S2 includes any one of centrifugal washing and dialysis.
A method for polymer-assisted preparation of a two-dimensional material according to some embodiments of the invention is characterized in that the step of centrifugal washing is: dispersing the two-dimensional material/polymer composite material into a solvent, centrifuging and removing supernatant, wherein the centrifugation speed is more than or equal to 1000r/min, the centrifugation time is more than or equal to 30min, and the centrifugation times are more than or equal to 5; the molecular weight cut-off of the dialysis bag used for dialysis is 1-35 ten thousand.
In a second aspect of the present invention, there is provided a method for polymer-assisted preparation of a composite material, the composite material being a two-dimensional material/polymer composite material, comprising the steps of: mixing raw materials including a polymer solution and a layered material, and grinding to obtain the two-dimensional material/polymer composite material, wherein the viscosity of the polymer solution is 500-500000 mPa & s, and the polymer solution comprises a polymer and a solvent.
The polymer-assisted method of making a composite according to some embodiments of the present invention is a water-soluble polymer including at least one of a natural water-soluble polymer, a chemically modified natural polymer, a synthetic water-soluble polymer.
The polymer assisted method of preparing a composite according to some embodiments of the present invention, the natural water soluble polymer comprises at least one of starch, cellulose, animal gum, vegetable gum; the chemically modified natural polymer comprises a modified cellulose; the synthetic water-soluble polymer comprises at least one of polyethyleneimine, polyacrylamide, polyvinylpyrrolidone, polyacrylic acid, polyethylene oxide, polyvinyl alcohol, melamine formaldehyde resin and urea formaldehyde resin. The vegetable gum includes but is not limited to sodium alginate and the modified cellulose includes but is not limited to carboxymethyl cellulose.
According to some embodiments of the invention, the polymer solution: the mixing mass ratio of the layered materials is (5-5000): 1.
the polymer assisted method of making a composite according to some embodiments of the present invention, the solvent comprises at least one of water, ethanol, isopropanol, acetone, benzene, N-dimethylformamide.
Polymers according to some embodiments of the invention assist in the preparation of composites comprising at least one of graphite, layered sulfides, layered selenides, layered tellurides, layered boron nitrides, layered micas, layered clays, layered vermiculites, layered silicates, black phosphorus, black arsenic phosphorus, titanium oxides.
The two-dimensional material/polymer composite material provided by the embodiment of the invention can be directly used for assembly and application, for example, the two-dimensional material/polymer composite film or block is assembled by using methods such as spin coating, electrostatic spraying, screen printing, ink-jet printing, freeze drying and the like, and has wide application prospects in the fields of flexible electronic devices, energy storage, catalysis, conductive ink, intelligent hydrogel, sensors and the like.
In a third aspect of the invention, a sensor is provided comprising a composite material obtained according to the above-described polymer-assisted method of making a composite material.
The embodiment of the invention has the beneficial effects that:
the embodiment of the invention provides a method for preparing a two-dimensional material with the assistance of a polymer, wherein the interaction between the polymer and a layered material and a shearing friction force generated in a grinding process are utilized to strip the layered material, and the polymer in a composite material can be removed by centrifugal washing, dialysis and other methods to obtain a pure two-dimensional material.
In addition, the embodiment of the invention can realize large-scale controllable preparation of the two-dimensional material by using the polymer as an auxiliary material, and can prepare the two-dimensional material/polymer composite material by a one-step method.
Drawings
FIG. 1 is a pictorial view of a two-dimensional boron nitride dispersion liquid prepared in example 1 under laser irradiation;
FIG. 2 is an atomic force microscopic image and thickness information curve of two-dimensional boron nitride prepared in example 1;
FIG. 3 is a plot of the plate diameter distribution of the two-dimensional boron nitride dispersion prepared in example 2;
FIG. 4 is a scanning electron micrograph of six layered boron nitrides used in example 3;
FIG. 5 is a pictorial view of six two-dimensional boron nitride dispersions prepared in example 3;
FIG. 6 is a graph showing the sizes of the flakes of six two-dimensional boron nitride dispersions prepared in example 3;
FIG. 7 is a pictorial representation of a two-dimensional boron nitride dispersion made with the aid of six polymers in example 4;
FIG. 8 is an atomic force micrograph of two-dimensional boron nitride prepared using polyacrylamide-assisted milling in example 4;
FIG. 9 is a scanning electron micrograph of three layered materials used in example 5;
fig. 10 is a diagram of two-dimensional graphene dispersion, two-dimensional molybdenum disulfide dispersion, and two-dimensional tungsten disulfide dispersion obtained by polyethyleneimine solution-assisted preparation in example 5;
FIG. 11 is a plot of the plate size distribution of the two-dimensional molybdenum disulfide dispersion prepared in example 5;
figure 12 is an atomic force microscope image of two-dimensional tungsten disulfide prepared in example 5;
fig. 13 is a physical diagram and a schematic diagram of the assembled graphene/thermoplastic polyurethane composite pressure sensor in example 6;
FIG. 14 is a graph of the change in resistance under pressure for a conventional pressure sensor and a graphene/thermoplastic polyurethane composite pressure sensor as determined in example 6;
FIG. 15 is a graph comparing the resistance change of the conventional pressure sensor of example 6 and the graphene/thermoplastic polyurethane composite pressure sensor of this example under mechanical scraping;
FIG. 16 is a comparison graph of the light mirror before and after mechanical scraping of the graphene/thermoplastic polyurethane composite film and the conventional carbon film in example 6 for 200 times.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The embodiment provides a method for preparing a two-dimensional material with the assistance of a polymer, wherein the two-dimensional material is two-dimensional boron nitride, and the method comprises the following specific steps:
s1, adding 1.0g of layered boron nitride powder (boron nitride powder of Tianyuan New materials company, H-BN-F) and 20.0g of polyethyleneimine solution (Sigma-Aldrich company, average Mn-60,000 by GPC, average Mw-750,000 by LS, water as a solvent, the mass ratio is 50%) into a mortar of a mortar grinder, and manually stirring uniformly in advance. Starting the mortar type grinding instrument, and adjusting the grinding pestle force (-150N/cm)2) And grinding for 8 hours. And after grinding, adding 100mL of deionized water into a mortar, and uniformly stirring to obtain the two-dimensional boron nitride/polyethyleneimine mixed dispersion liquid.
S2, standing, taking supernatant, centrifuging for 1h at 10000r/min, centrifuging for 5 times, and removing residual polyethyleneimine to obtain the two-dimensional boron nitride dispersion.
The two-dimensional boron nitride dispersion prepared as described above was irradiated with laser light, and as a result, as shown in fig. 1, the boron nitride dispersion produced a tyndall phenomenon under laser irradiation, and it was confirmed from this figure that this example successfully exfoliated layered boron nitride into two-dimensional boron nitride.
The atomic force microscopic image and the thickness information curve of the boron nitride prepared in the above manner are shown in fig. 2, wherein (a) in fig. 2 represents the atomic force microscopic image, and (b) in fig. 2 represents the thickness information curve of the boron nitride, and it can be seen from fig. 2 that the two-dimensional boron nitride prepared in this example has a size of about 1 μm in sheet diameter and a thickness of about 10 nm.
Example 2
This example provides a two-dimensional boron nitride, which was prepared in the same manner as in example 1, except that the centrifugation in step S2 was carried out at a centrifugation rate of 3000r/min for a period of 15 min.
The two-dimensional boron nitride dispersion liquid prepared in this example was measured for its plate diameter distribution curve by a dynamic light scattering instrument, and as shown in FIG. 3, the average plate diameter of the two-dimensional boron nitride in the supernatant after centrifugation was 653.5 nm.
Example 3
This example provides six two-dimensional boron nitride dispersions, which are prepared in the same manner as in example 1, except that the layered boron nitrides used are boron nitride powder from qinhuangyuno high-new materials development ltd (BNH30, qinhuangyuno), boron nitride powder from mei-chart ltd (PT110, mei-chart for short), cosmetic grade boron nitride from united micropowder company (UNI-BN 2831, united micropowder for short), boron nitride powder from fosman technology (beijing) ltd (325 mesh, fosman for short), boron nitride powder from new celestial resources ltd (H-BN-F, new celestial resources for short), and boron nitride powder from dandong institute of responsibility limited (HSL, dandong chemical).
Taking the six kinds of layered boron nitride used in this example, as shown in fig. 4, a scanning electron microscope image of the six kinds of layered boron nitride is shown, and it can be seen from the figure that the sizes of the six kinds of layered boron nitride are all large, and within the range of 10 to 50 μm, the physical diagrams of the six kinds of two-dimensional boron nitride dispersions prepared by using the six kinds of layered boron nitride as raw materials respectively correspond to those shown in fig. 5, the six kinds of two-dimensional boron nitride dispersions prepared are stable and uniform, and effective peeling can be realized on the six kinds of layered boron nitride raw materials by adopting a polymer auxiliary grinding peeling mode. The six kinds of two-dimensional boron nitride prepared in this example were tested by a dynamic light scattering instrument, and the sizes of the plate diameters are shown in fig. 6, and the results show that the average plate diameter of the two-dimensional boron nitride dispersion obtained by the method for preparing a two-dimensional material with the aid of the polymer provided in the examples of the present invention is 400 to 700 nm.
Example 4
This example provides a method for preparing a two-dimensional boron nitride dispersion with the aid of six different polymers, which comprises the following steps:
polyethyleneimine solution: it was purchased directly (Sigma-Aldrich reagent company, average Mn: 60,000by GPC, average Mw: 750,000by LS, water as solvent, 50% by mass), and its viscometer test result was 28120 mPas;
sodium carboxymethyl cellulose solution: weighing 1.0g of sodium carboxymethylcellulose powder (Aladdin reagent company, viscosity 800-;
polyacrylamide solution: weighing 1.0g of polyacrylamide powder (Michelin reagent company, nonionic type, molecular weight of 700 ten thousand), dissolving in 50.0g of water, stirring to be uniform, and measuring the result by a viscometer to be 8000mPa & s;
sodium alginate solution: weighing 1.0g sodium alginate powder (Sigma-Aldrich reagent company, medium viscosity, from brown algae), dissolving in 50.0g water, stirring to uniform, and measuring with viscometer to obtain 2850 mPas;
polyvinylpyrrolidone solution: weighing 5.0g polyvinylpyrrolidone powder (Allantin reagent company, average molecular weight 58000, K29-32), dissolving in 16.0g water, and stirring to obtain a uniform solution;
soluble starch solution: 1.0g of soluble starch powder (Sigma-Aldrich reagent Co., ACS reagent) was weighed out, dissolved in 30.0g of water and stirred until homogeneous, with a viscometer test result of 5500 mPas.
The two-dimensional boron nitride dispersion liquids prepared by the aid of the six polymers are respectively marked as a-f, and the real object diagrams of the dispersion liquids are shown in fig. 7.
Wherein, the atomic force microscopic image of the two-dimensional boron nitride prepared by the polyacrylamide auxiliary grinding stripping is shown in figure 8, and under the preparation condition, the sheet diameter of the two-dimensional boron nitride is 1-2 μm.
Example 5
This example provides a method for preparing a two-dimensional material by using a polymer to assist a layered material, the preparation process is the same as that of example 1, except that the layered material is: expandable graphite, layered molybdenum disulfide, layered disulfide.
The three layered materials used above were characterized by scanning electron microscopy as shown in figure 9, from which it can be seen that the expandable graphite has a size of about 500 μm, the layered molybdenum disulphide has a size of about 2 μm and the layered disulphide has a size of about 6 μm. In this embodiment, physical diagrams of the two-dimensional graphene dispersion liquid, the two-dimensional molybdenum disulfide dispersion liquid, and the two-dimensional tungsten disulfide dispersion liquid, which are obtained by performing auxiliary preparation on the three layered materials by using a polyethyleneimine solution, are respectively shown in fig. 10 a-c.
The distribution curve of the sheet diameter of the two-dimensional molybdenum disulfide dispersion prepared as described above was measured by a dynamic light scattering instrument, and as shown in FIG. 11, the average sheet diameter of molybdenum disulfide in the molybdenum disulfide dispersion was 242.7 nm.
Fig. 12 is an atomic force microscope image of two-dimensional tungsten disulfide obtained by using polyethyleneimine to assist grinding and stripping in this example, and it can be seen from the image that under this preparation condition, the size of the two-dimensional tungsten disulfide sheet diameter is about 400 nm.
Example 6
The embodiment provides a two-dimensional material/polymer composite material, specifically graphene/thermoplastic polyurethane, which is prepared by the following steps:
weighing 5g of thermoplastic polyurethane, dissolving in 100mL of N, N-dimethylformamide, and stirring to be uniform to obtain a thermoplastic polyurethane solution.
0.5g of expandable graphite and 20.0g of the thermoplastic polyurethane solution were added to a mortar of a mortar grinder and stirred uniformly by hand. Starting the mortar type grinding instrument, and adjusting the grinding pestle force (-150N/cm)2) And grinding for 8 hours to obtain the graphene/thermoplastic polyurethane composite dispersion liquid.
And standing the graphene/thermoplastic polyurethane composite dispersion liquid for 8 hours, taking supernatant liquid, pouring the supernatant liquid into a polytetrafluoroethylene mold, and heating at 50 ℃ for 8 hours to dry the supernatant liquid to obtain the graphene/thermoplastic polyurethane composite film.
The conventional pressure sensor and the graphene/thermoplastic polyurethane composite pressure sensor are prepared by using the carbon film and the graphene/thermoplastic polyurethane composite film prepared in the embodiment, and the related properties of the sensors are measured. Conventional pressure sensors: the top electrode is a carbon film, the bottom electrode is a silver loop, the middle of the top electrode is separated from the two end electrodes by a rubber ring gasket, and when pressure is applied, the top electrode is in contact with the bottom electrode to generate resistance change. The real-world diagram and the schematic diagram of the graphene/thermoplastic polyurethane composite pressure sensor assembled by using the graphene/thermoplastic polyurethane composite film instead of the carbon film are respectively shown as a and b in fig. 13. The resistance changes of the conventional pressure sensor and the graphene/thermoplastic polyurethane composite pressure sensor of the embodiment under pressure are measured, and the results are shown in fig. 14, which shows that the resistance change linearity of the graphene/thermoplastic polyurethane composite pressure sensor is better. Fig. 15 is a graph comparing the resistance change under mechanical scraping of the conventional pressure sensor and the graphene/thermoplastic polyurethane composite pressure sensor of the present embodiment, and it can be seen from the graph that the graphene/thermoplastic polyurethane composite pressure sensor has better stability under mechanical scraping. The experimental result shows that the pressure sensor obtained by using the two-dimensional material/polymer composite material provided by the embodiment of the invention has more excellent resistance change linearity and mechanical stability.
Fig. 16 is a comparison image of the optical mirror before and after 200 mechanical scratches on the graphene/thermoplastic polyurethane composite film and the conventional carbon film on the substrate, and it can be seen from the comparison image that the surface appearance of the graphene/thermoplastic polyurethane composite film is not significantly changed after 200 mechanical scratches, while the surface of the conventional carbon film has significant scratches and the appearance is damaged.
Claims (10)
1. A method for polymer-assisted preparation of a two-dimensional material, comprising the steps of:
s1, mixing a polymer solution and a layered material, and grinding to obtain a two-dimensional material/polymer composite material, wherein the viscosity of the polymer solution is 500-500000 mPa & S, and the polymer solution comprises a polymer and a solvent;
s2, filtering the polymer in the two-dimensional material/polymer composite material to obtain the two-dimensional material.
2. The method for polymer-assisted preparation of two-dimensional materials according to claim 1, wherein the polymer is a water-soluble polymer and a water-insoluble polymer, and the water-soluble polymer comprises at least one of natural water-soluble polymers, chemically modified natural polymers, and synthetic water-soluble polymers.
3. The method for polymer-assisted preparation of two-dimensional materials according to claim 2, wherein the natural water-soluble polymer comprises at least one of starch, cellulose, animal glue, vegetable glue; the chemically modified natural polymer comprises at least one of modified starch and modified cellulose; the synthetic water-soluble polymer comprises at least one of polyethyleneimine, polyacrylamide, polyvinylpyrrolidone, polyacrylic acid, polyethylene oxide, melamine formaldehyde resin and urea formaldehyde resin.
4. The method for polymer-assisted preparation of a two-dimensional material according to any one of claims 1 to 3, wherein the polymer solution in step S1: the mass ratio of the layered material is (5-5000): 1.
5. the polymer-assisted method for preparing a two-dimensional material according to any one of claims 1 to 3, wherein the solvent comprises at least one of water, ethanol, isopropanol, acetone, benzene, N-dimethylformamide.
6. A method for polymer-assisted preparation of a two-dimensional material according to any one of claims 1 to 3, characterized in that the layered material comprises at least one of graphite, layered sulfides, layered selenides, layered tellurides, layered boron nitrides, layered micas, layered clays, layered vermiculite, layered silicates, black phosphorus, black arsenic phosphorus, titanium oxide.
7. The method for polymer-assisted preparation of a two-dimensional material according to any one of claims 1 to 3, wherein the filtering means in step S2 comprises any one of centrifugal washing and dialysis.
8. The method for polymer-assisted preparation of two-dimensional materials according to claim 7, wherein the step of centrifugal washing is: dispersing the two-dimensional material/polymer composite material into a solvent, centrifuging and removing supernatant, wherein the centrifugation speed is more than or equal to 1000r/min, the centrifugation time is more than or equal to 30min, and the centrifugation times are more than or equal to 5; the molecular weight cut-off of the dialysis bag used for dialysis is 1-35 ten thousand.
9. A method for polymer-assisted preparation of a composite material, wherein the composite material is a two-dimensional material/polymer composite material, comprising the steps of: mixing raw materials including a polymer solution and a layered material, and grinding to obtain the two-dimensional material/polymer composite material, wherein the viscosity of the polymer solution is 500-500000 mPa & s, and the polymer solution comprises a polymer and a solvent.
10. A sensor comprising a composite material obtained by the polymer-assisted method of making a composite material according to claim 9.
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