CN102732037B - Graphene foam/polymer high-conductivity composite material preparation method and application thereof - Google Patents
Graphene foam/polymer high-conductivity composite material preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the graphene composite material field, and particularly to a graphene foam/polymer high-conductivity composite material, a preparation method and applications thereof. Steps of the method comprises as follows: providing a fully communicated three-dimension grapheme foam network and a precursor solution of a high-molecular polymer; mixing the graphene foam with the precursor solution of the high-molecular polymer to form a graphene foam/high-molecule polymer precursor mixture; and solidifying the precursor of the high-molecular polymer in the mixture to form a high-conductivity graphene foam composite material. The invention adopts the three-dimension graphene foam to form a fully- communicated graphite rapid transmission network by a seamless connection, which enables the graphene foam composite material to possess great conductivity and mechanical property and can be widely applied to the conductive composite materials and elasticity conductor field.
Description
Technical field:
The present invention relates to grapheme foam field of compound material, be specially a kind of grapheme foam/polymerization object height conducing composite material and its preparation method and application, adopt a kind of grapheme foam network of three-dimensional full-mesh as the conductive additive of matrix material, construct out a kind of matrix material with three-dimensional high conduction full-mesh network, can be widely used in the field such as conducing composite material and elastic conductor.
Background technology:
Graphene is the bi-dimensional cellular shape crystalline structure by the tightly packed one-tenth of monolayer carbon atom, is the basic structural unit that builds other dimension Carbon Materials (zero dimension soccerballene, one-dimensional nano carbon pipe, three-dimensional graphite).The crystalline structure of Graphene uniqueness makes it have excellent electricity, calorifics and mechanical property, if its electronic mobility under room temperature is up to 200,000cm
2/ Vs, thermal conductivity is up to 5300W/mk, and Young's modulus can reach 1TPa, is considered to the desirable additive of matrix material.The exterior appearance of its two-dimensional sheet and super large specific surface area can contact more closely with macromolecule polymer material generation is abundanter, have better and strengthen the property than the carbon nanotube of one dimension.
Because Graphene adds in polymer materials and needs larger consumption as strongthener, so the Graphene that matrix material is used at present can only be provided by chemical stripping method.But matrix material prepared by the Graphene being obtained by chemical stripping method has poor conductivity, because graphite raw material in chemical stripping process is peeled off by strong oxidation on the one hand, the Graphene obtaining has a large amount of textural defect and poor conductive capability, because the Graphene that chemical stripping method makes has less size on the other hand, be added to and between polymer materials rear panel and sheet, be aggregated thing molecule long-chain and intercept and open, the conductive path of formation certainly exists very large contact resistance.The method that Graphene mixes with high molecular polymer at present mainly contains situ aggregation method and solution mechanical blending method.But while adopting these ordinary methods to prepare matrix material; be difficult to two-dimentional graphene film to be dispersed in completely in liquid macroimolecule polymkeric substance or organic solvent; graphene film can again be reunited conventionally in high molecular polymer matrix; cause uneven distribution, make the performance of matrix material far below desired value.So how to obtain high-quality Graphene and graphene film be assembled into continuous conductive network and will be the key that obtains high conductive graphene based composites.At present, chemical Vapor deposition process is one of effective ways of preparing in a large number high-quality graphene, adopts three-dimensional porous foamed metal can also prepare the grapheme foam network of three-dimensional full-mesh as the template of chemical vapour deposition.If adopt the additive of this grapheme foam network as matrix material, a kind of general preparation method of high conductive graphene based composites will likely be developed.
Highly integrated and intelligentized developmental stage has been experienced in hyundai electronics industry, and next important developing direction will be flexible electronic device.The form to existing electronic product and application are produced great effect by the appearance of flexible electronic device, and electronic product will be no longer rigidity, but can be arbitrarily do not affect use properties when bending and stretching.The Application Areas of flexible electronic device will be very extensive, as thin-film display that can be curling, and soft electronics skin, the connection of joint of robot, and all wearable electronic products etc.Conventional rigid material is good electric property as metal and silicon etc. have, but do not possess snappiness and elasticity, can not directly be used for preparing flexible electronic device, will be vital so develop a kind of type material simultaneously with good mechanical stability and conductivity to the development of flexible electronic device.Graphene, as the thinnest in the world two-dimensional film material, not only has very high specific conductivity, and has good mechanical stability and snappiness, is the ideal material of preparing flexible electronic device.
Summary of the invention:
The object of the present invention is to provide a kind of grapheme foam/polymerization object height conducing composite material and its preparation method and application, it is grapheme foam network by the adopting a kind of three-dimensional full-mesh conductive additive as matrix material, construct out the method for the three-dimensional full-mesh conductive network of composite inner, there is high-performance, easy and simple to handle, cost is low and be easy to the feature regulating and controlling.
Technical scheme of the present invention is:
A kind of grapheme foam/polymerization object height conducing composite material, the shared ratio of grapheme foam is 0.01-10wt%, the shared ratio of high molecular polymer is 90-99.99wt%.
A preparation method for grapheme foam/polymerization object height conducing composite material, adopts a kind of grapheme foam network of three-dimensional full-mesh as the conductive additive of matrix material, constructs out the conductive network of the three-dimensional full-mesh of composite inner.The method, by filled high polymer polybenzazole precursor liquid solution in the grapheme foam of three-dimensional full-mesh, obtains having the matrix material of three-dimensional high conduction full-mesh network after curing cross-linked.
In the present invention, grapheme foam adopts Chinese patent application (application number 201110056973.3), denomination of invention: a kind of grapheme foam and preparation in macroscopic quantity method thereof with three-dimensional full-mesh network, the applying date: on March 10th, 2011.Wherein, the grapheme foam that adopts the method to prepare is Graphene forms three-dimensional full-mesh network structure in the mode of seamless link, and density is 0.1mg/cm
3-100mg/cm
3, porosity is 60%-99.9%, specific surface area is 130-2600m
2/ g, specific conductivity is 0.5S/cm-1000S/cm.
The preferable range of grapheme foam is as follows: grapheme foam density 3～5mg/cm
3, porosity 99.5～99.8%, specific surface area 300～850m
2/ g, specific conductivity 7～10S/cm.
The grapheme foam that the present invention adopts is except having the electricity and mechanical property of Graphene excellence, or a kind of network structure of three-dimensional full-mesh, has further strengthened snappiness, can bear more bending and tensile deformation.So the matrix material of being made up of the elastomeric polymer such as grapheme foam and silicon rubber will be a kind of high performance elastic conductor material, can be widely used in the fields such as flexible electronic device.
The high molecular polymer adopting in the present invention is that silicon rubber, rubber, Polyurethane, epoxy resin, paraffin, nylon, synthetic glass, polyimide, polyethylene, polystyrene or polypropylene etc. can liquid condition shapings or the macromolecule polymer material of cast molding.
In the present invention, the preparation of high molecular polymer precursor solution is divided into two kinds of situations and carries out.The liquid phase curing molding of high molecular polymer can to(for) silicon rubber, Polyurethane and epoxy resin etc., by polymkeric substance and solidifying agent by weight (3～10): 1 mixes and vigorous stirring 1～10 minute extremely full and uniform, vacuum de-soak 1～10 minute, obtains high molecular polymer precursor solution again; Dissolve in the high molecular polymer of organic solvent for synthetic glass, polyethylene, polystyrene and polypropylene etc., by polymkeric substance and acetone and other organic solvent by weight (0.05～1): 1 mixes afterwards vigorous stirring 10～20 hours to polymkeric substance dissolves completely and forms a thick solution, vacuum de-soak 1～10 minute, obtains polybenzazole precursor liquid solution again.
In the present invention, liquid high molecular polymer performed polymer or solution are injected to the mould that grapheme foam is housed, make it penetrate into grapheme foam network, and fully infiltrate.
In the present invention, high molecular polymer further carries out vacuum-treat after fully mixing with grapheme foam, to remove the bubble in polymkeric substance, and makes it to penetrate into more fully in the space of grapheme foam.Vacuum tightness 0.01-0.2atm used, vacuum processing time is at 10-100 minute.
In the present invention, grapheme foam/high molecular polymer mixture is added to the unnecessary solvent of heat abstraction, and further curing molding, 25～200 DEG C of solidification values, obtain the high grapheme foam matrix material conducting electricity.
The invention has the beneficial effects as follows:
1, the present invention has abandoned conventional composite materials dispersion-stirring-curing technological line, first the present invention adopt conductive additive--the three-dimensional porous foam of Graphene is the overall network of a connection, do not need the process of dispersing additive in traditional route, greatly simplify the preparation process of matrix material, also retained the intrinsic property of Graphene simultaneously.Secondly the present invention does not need to carry out the routine operations such as mechanical stirring in the time of admixed graphite alkene and high molecular polymer, only needs simple dipping to fill and processes, and but there will not be local problem of reuniting, and can reach higher homogeneity.
2, in the present invention, adopt the grapheme foam network of three-dimensional full-mesh as the conductive additive of matrix material, construct out the Quick conductive network of the three-dimensional full-mesh of composite inner, conductive capability is than high 3～6 orders of magnitude of conventional graphite thiazolinyl matrix material.
3, grapheme foam is except having the electricity and mechanical property of Graphene excellence, and still a kind of network structure of three-dimensional full-mesh, has further strengthened snappiness, can bear more bending and tensile deformation.So the matrix material of being made up of the elastomeric polymer such as grapheme foam and silicon rubber is a kind of high performance elastic conductor material.
4, the present invention has high-performance, easy and simple to handle, cost is low and be easy to the feature of structure regulating, is expected to become the universal method of the graphene-based matrix material of scale operation high-performance, can be widely used in the field such as conducing composite material and elastic conductor.
Brief description of the drawings:
Fig. 1 is the sign of grapheme foam (GF)/silicon rubber (PDMS) matrix material.Wherein, (a) be the optical photograph of matrix material, (b) be the stereoscan photograph of matrix material section, (c) be specific conductivity and the content of grapheme foam in matrix material of grapheme foam and matrix material thereof, (d) be the stress-strain curve of matrix material.
Fig. 2 be GF/PDMS matrix material under various deformation states optical photograph.Wherein, (a-b) being case of bending, is (c) stretched state, is (d) twisted state.
Fig. 3 is GF/PDMS matrix material before experience flexural deformation (a), the optical photograph of (c) after (b) and distortion when distortion.
Fig. 4 is GF/PDMS matrix material before experience tensile deformation (a), the optical photograph of (c) after (b) and distortion when distortion.
Fig. 5 is the resistance change of GF/PDMS matrix material under deformation state.Wherein, (a) for GF/PDMS matrix material is in the resistance change bending under 2.5mm radius-of-curvature state, (b) for GF/PDMS matrix material is in the resistance change bending under 0.8mm radius-of-curvature state, (c) for GF/PDMS matrix material is in the resistance change being stretched under 50% state of strain, (d) be stretched to the resistance change of fracture for GF/PDMS matrix material.
Embodiment:
Be described in further detail the present invention below by embodiment.
Embodiment 1
The present embodiment provides a kind of preparation method of grapheme foam/silicon rubber composite material, and concrete scheme comprises the following steps:
(1) provide a kind of grapheme foam and a kind of high molecular polymer precursor solution of three-dimensional full-mesh
The method of preparing this grapheme foam is chemical Vapor deposition process, the method grows the Graphene of three-dimensional communication at three-dimensional porous foamed metal surface catalysis cracking carbon-source gas, follow-uply moltenly obtains a kind of Graphene three-dimensional macro body of porous foam shape except metallic foam substrate.By the grapheme foam density 3～5mg/cm that regulates series of process parameter to obtain
3, porosity 99.5～99.8%, specific surface area 300～850m
2/ g, specific conductivity 7～10S/cm, the present embodiment is optimized for density 5mg/cm
3, porosity 99.7%, specific surface area 500m
2/ g, specific conductivity 10S/cm.
In the present invention, the foamed metal adopting is nickel foam, foam copper, foam iron or foam cobalt etc., and its pore size distribution is at 50-200PPI, and preferable range is 90-120PPI; Area density is 50-1000g/m
2, preferable range is 250-400g/m
2.In the present embodiment, foamed metal adopts nickel foam (70 millimeters × 300 millimeters × 1.2 millimeters), and its pore size distribution is about 110PPI, and area density is about 300g/m
2.
The high molecular polymer precursor solution adopting in matrix material is the solution of a kind of composition in silicon rubber, rubber, Polyurethane, epoxy resin, paraffin, nylon, synthetic glass, polyimide, polyethylene, polystyrene, polypropylene etc.Be appreciated that, the high molecular polymer relating in the technical program is not limited to above-mentioned several, any can liquid condition shaping or cast molding (can by the polymerization of low viscosity presoma curing mode maybe can be by dissolving, fusing forms low viscosity solution) macromolecule polymer material all can.
The macromolecule polymer solution that the present embodiment adopts is silicon rubber precursor solution, and model is DowCorning Sylgard 184 (containing solidifying agent).After the main body of silicon rubber and solidifying agent are mixed by the mass ratio of 10: 1, vigorous stirring approximately 5 minutes is to full and uniform, then vacuum de-soak 5 minutes, obtains silicon rubber precursor solution.
(2) grapheme foam and high molecular polymer precursor solution are mixed, form one grapheme foam/high molecular polymer mixture.Grapheme foam is placed in to a mould, and Implanted Silicon rubber precursor solution, make its infiltration and fully infiltrate grapheme foam.Grapheme foam fully mixes the rear vacuum-treat of further carrying out, vacuum tightness 0.05atm used, vacuum processing time 30 minutes with silicon rubber precursor solution.Vacuum-treat makes air bubble expansion in polymers soln emersion liquid level and removes, and polymers soln is penetrated in the space of grapheme foam more fully.
(3) solidify the high molecular polymer in mixture, thereby form the grapheme foam matrix material of high conduction.The homogeneous mixture of grapheme foam and silicon rubber precursor solution is heated to 80 DEG C, and heat preservation solidification 4 hours, obtains the grapheme foam/silicon rubber composite material of high conduction.
As can be seen from Figure 1, in the prepared grapheme foam/silicon rubber composite material of the present embodiment, Graphene content is about 0.5wt%, specific conductivity is about 10S/cm, basically identical with the specific conductivity of original grapheme foam, than high six orders of magnitude of the graphene-based matrix material of traditional chemical stripping method.And the tensile strength of matrix material is higher by 30% than silicon rubber.
From Fig. 2, Fig. 3 and Fig. 4 can find out, grapheme foam/silicon rubber composite material has good snappiness and elasticity, can bend arbitrarily, curling, stretching and distortion and do not destroy, and can return to original state completely after distortion.As can be seen from Figure 5, grapheme foam/silicon rubber composite material has very excellent electricity and mechanical property and very high mechanical stability as a kind of elastic conductor, in the time bending to 2.5mm radius-of-curvature, the resistance of matrix material only has slight rising, and after standing the alternating bending of 10,000 times, resistance does not also significantly change.Also only risen less than 30% as bent to resistance under the radius-of-curvature of 0.8mm and 50% tensile deformation when matrix material stands larger distortion, and can continue to bear the tensile deformation up to 95%.
Embodiment 2
The present embodiment provides a kind of preparation method of grapheme foam/epoxy resin composite material, and concrete scheme comprises the following steps:
(1) provide a kind of grapheme foam and a kind of high molecular polymer precursor solution of three-dimensional full-mesh
The method of preparing this grapheme foam is chemical Vapor deposition process, the method grows the Graphene of three-dimensional communication at three-dimensional porous foamed metal surface catalysis cracking carbon-source gas, follow-uply moltenly obtains a kind of Graphene three-dimensional macro body of porous foam shape except metallic foam substrate.By the grapheme foam density 3～5mg/cm that regulates series of process parameter to obtain
3, porosity 99.5～99.8%, specific surface area 300～850m
2/ g, specific conductivity 7～10S/cm, the present embodiment is optimized for density 5mg/cm
3, porosity 99.7%, specific surface area 500m
2/ g, specific conductivity 10S/cm.
In the present invention, the foamed metal adopting is nickel foam, foam copper, foam iron or foam cobalt etc., and its pore size distribution is at 50-200PPI, and preferable range is 90-120PPI; Area density is 50-1000g/m
2, preferable range is 250-400g/m
2.In the present embodiment, foamed metal is nickel foam (70 millimeters × 300 millimeters × 1.2 millimeters), and its pore size distribution is about 110PPI, and area density is about 300g/m
2.
The high molecular polymer precursor solution adopting in matrix material is the solution of a kind of composition in silicon rubber, rubber, Polyurethane, epoxy resin, paraffin, nylon, synthetic glass, polyimide, polyethylene, polystyrene, polypropylene etc.Be appreciated that, the high molecular polymer relating in the technical program is not limited to above-mentioned several, any can liquid condition shaping or cast molding (can by the polymerization of low viscosity presoma curing mode maybe can be by dissolving, fusing forms low viscosity solution) macromolecule polymer material all can.
The macromolecule polymer solution that the present embodiment adopts is epoxy resin precursor solution, and model is 6002 bisphenol A-type liquid-state epoxy resins, and solidifying agent is 5784 solidifying agent.After epoxy resin and solidifying agent are mixed by the mass ratio of 4: 1, vigorous stirring approximately 5 minutes is to full and uniform, then vacuum de-soak 5 minutes, obtains epoxy resin precursor solution.
(2) grapheme foam and high molecular polymer precursor solution are mixed, form one grapheme foam/high molecular polymer mixture.Grapheme foam is placed in to a mould, and injection ring epoxy resins precursor solution, make its infiltration and fully infiltrate grapheme foam.Grapheme foam fully mixes the rear vacuum-treat of further carrying out, vacuum tightness 0.1atm used, vacuum processing time 30 minutes with epoxy resin precursor solution.Vacuum-treat makes air bubble expansion in polymers soln emersion liquid level and removes, and polymers soln is penetrated in the space of grapheme foam more fully.
(3) solidify the high molecular polymer in mixture, thereby form the grapheme foam matrix material of high conduction.The homogeneous mixture of grapheme foam and epoxy resin precursor solution is heated to 100 DEG C, and heat preservation solidification 1 hour, obtains the grapheme foam/epoxy resin composite material of high conduction.
In the prepared grapheme foam/epoxy resin composite material of the present embodiment, Graphene content is about 0.5wt%, specific conductivity is about 10S/cm, basically identical with the specific conductivity of original grapheme foam, than high six orders of magnitude of the graphene-based matrix material of traditional chemical stripping method.
Embodiment 3
The present embodiment provides a kind of preparation method of grapheme foam/synthetic glass matrix material, and concrete scheme comprises the following steps:
(1) provide a kind of grapheme foam and a kind of high molecular polymer precursor solution of three-dimensional full-mesh
The method of preparing this grapheme foam is chemical Vapor deposition process, the method grows the Graphene of three-dimensional communication at three-dimensional porous foamed metal surface catalysis cracking carbon-source gas, follow-uply moltenly obtains a kind of Graphene three-dimensional macro body of porous foam shape except metallic foam substrate.By the grapheme foam density 3～5mg/cm that regulates series of process parameter to obtain
3, porosity 99.5～99.8%, specific surface area 300～850m
2/ g, specific conductivity 7～10S/cm, the present embodiment is optimized for density 5mg/cm
3, porosity 99.7%, specific surface area 500m
2/ g, specific conductivity 10S/cm.
In the present invention, the foamed metal adopting is nickel foam, foam copper, foam iron or foam cobalt etc., and its pore size distribution is at 50-200PPI, and preferable range is 90-120PPI; Area density is 50-1000g/m
2, preferable range is 250-400g/m
2.In the present embodiment, foamed metal is nickel foam (70 millimeters × 300 millimeters × 1.2 millimeters), and its pore size distribution is about 110PPI, and area density is about 300g/m
2.
The high molecular polymer precursor solution adopting in matrix material is the solution of a kind of composition in silicon rubber, rubber, Polyurethane, epoxy resin, paraffin, nylon, synthetic glass, polyimide, polyethylene, polystyrene, polypropylene etc.Be appreciated that, the high molecular polymer relating in the technical program is not limited to above-mentioned several, any can liquid condition shaping or cast molding (can by the polymerization of low viscosity presoma curing mode maybe can be by dissolving, fusing forms low viscosity solution) macromolecule polymer material all can.
The macromolecule polymer solution that the present embodiment adopts is synthetic glass precursor solution.Preparation method is dissolved synthetic glass and acetone completely and forms a thick solution by weight mixing afterwards vigorous stirring approximately 12 hours to synthetic glass at 0.1: 1, then vacuum de-soak 5 minutes, obtains synthetic glass precursor solution.
(2) grapheme foam and high molecular polymer precursor solution are mixed, form one grapheme foam/high molecular polymer mixture.Grapheme foam is placed in to a mould, and injects synthetic glass precursor solution, make its infiltration and fully infiltrate grapheme foam.Grapheme foam fully mixes the rear vacuum-treat of further carrying out, vacuum tightness 0.02atm used, vacuum processing time 30 minutes with synthetic glass precursor solution.Vacuum-treat makes air bubble expansion in polymers soln emersion liquid level and removes, and polymers soln is penetrated in the space of grapheme foam more fully.
(3) solidify the high molecular polymer in mixture, thereby form the grapheme foam matrix material of high conduction.The homogeneous mixture of grapheme foam and synthetic glass precursor solution is heated to 45 DEG C, acetone is fully volatilized, reheat to 150 DEG C and solidify 1 hour, obtain grapheme foam/synthetic glass matrix material of high conduction.
In the prepared grapheme foam/synthetic glass matrix material of the present embodiment, Graphene content is about 0.5wt%, specific conductivity is about 10S/cm, basically identical with the specific conductivity of original grapheme foam, than high six orders of magnitude of the graphene-based matrix material of traditional chemical stripping method.
The above results shows, the present invention adopts a kind of grapheme foam network of three-dimensional full-mesh as the conductive additive of matrix material, construct out a kind of matrix material with three-dimensional high conduction full-mesh network, there is high-performance, easy and simple to handle, cost is low and be easy to the feature of structure regulating, be expected to become the universal method of the graphene-based matrix material of scale operation high-performance, can be widely used in the field such as conducing composite material and elastic conductor.
Claims (6)
1. a preparation method for grapheme foam/polymerization object height conducing composite material, is characterized in that: in described matrix material, the shared ratio of grapheme foam is 0.01-10wt%, and the shared ratio of high molecular polymer is 90-99.99wt%; Grapheme foam is Graphene forms three-dimensional full-mesh network structure in the mode of seamless link, and density is 0.1mg/cm
3-100mg/cm
3, porosity is 60%-99.9%, specific surface area is 130-2600m
2/ g, specific conductivity is 0.5S/cm-1000S/cm;
Described grapheme foam/polymerization object height conducing composite material adopts the grapheme foam network of three-dimensional full-mesh as the conductive additive of matrix material, constructs out the conductive network of the three-dimensional full-mesh of composite inner; Grapheme foam and high molecular polymer precursor solution are mixed, form one grapheme foam/high molecular polymer presoma mixture; Solidify the high molecular polymer presoma in mixture, thereby form the grapheme foam matrix material of high conduction;
The preparation method of described grapheme foam network adopts chemical vapour deposition technique to split carbon-source gas and grow the Graphene of three-dimensional communication at the surface catalysis of three-dimensional porous foamed metal, follow-up molten except obtaining the Graphene three-dimensional macro body of porous foam shape after metallic foam substrate again.
2. according to the preparation method of grapheme foam/polymerization object height conducing composite material claimed in claim 1, it is characterized in that: described high molecular polymer is that silicon rubber, rubber, Polyurethane, epoxy resin, nylon, synthetic glass, polyimide, polyethylene, polystyrene or polypropylene can liquid condition shapings or the macromolecule polymer material of cast molding.
3. according to the preparation method of grapheme foam/polymerization object height conducing composite material claimed in claim 1, it is characterized in that: liquid high molecular polymer precursor solution is injected to the mould that grapheme foam is housed, make it penetrate into grapheme foam network, and fully infiltrate.
4. according to the preparation method of grapheme foam/polymerization object height conducing composite material claimed in claim 1, it is characterized in that: high molecular polymer presoma further carries out vacuum-treat after fully mixing with grapheme foam, to remove the bubble in polymkeric substance, and make it to penetrate into more fully in the space of grapheme foam.
5. according to the preparation method of grapheme foam/polymerization object height conducing composite material claimed in claim 1, it is characterized in that: grapheme foam/high molecular polymer presoma mixture is added to the unnecessary solvent of heat abstraction, and further curing molding, obtain the high grapheme foam matrix material conducting electricity.
6. according to the application of grapheme foam/polymerization object height conducing composite material claimed in claim 1, it is characterized in that: the Graphene that the three-dimensional grapheme foam of employing forms full-mesh in the mode of seamless link conducts network fast, make this grapheme foam matrix material be widely used in conducing composite material or elastic conductor field.
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