CN110139896A - Multipurpose graphene composite material - Google Patents

Multipurpose graphene composite material Download PDF

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Publication number
CN110139896A
CN110139896A CN201780068881.2A CN201780068881A CN110139896A CN 110139896 A CN110139896 A CN 110139896A CN 201780068881 A CN201780068881 A CN 201780068881A CN 110139896 A CN110139896 A CN 110139896A
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graphene
composite material
substrate
kodalk
hydration
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CN201780068881.2A
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CN110139896B (en
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杜桑·洛西克
M·J·尼内
D·N·H·德兰
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University of Adelaide
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University of Adelaide
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation
    • C01B32/192—Preparation by exfoliation starting from graphitic oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/198—Graphene oxide
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/02—Inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides

Abstract

The present invention relates to the graphene composite materials for the graphene based material for including hydration kodalk intercalation.

Description

Multipurpose graphene composite material
Technical field
The present invention relates generally to graphene based materials.Particularly, the present invention relates to graphene composite material including this is multiple The purposes of the substrate of condensation material, the preparation method of the composite material and the composite material.
Background technique
Protection object resistance routine use such as building and industrial substrate and environmental condition exist in today's society to be shown The challenge of work.For example, many objects adversely can be worn away caused abrasion, germ contamination and Fire-damaged etc. by such as burn into Factor influences, and slightly gives a few examples.
The challenge is coped with, a large amount of research has been carried out to develop the means for protecting object.Such protection is provided Usual approach be to be coated with protectiveness material or handle the object.For example, object be usually coated with can protect object from The various coating products of corrosion, abrasivity abrasion or germ contamination.Object can also be handled with fire retardant, fire-retardant to improve its Property.
Although used many protection systems are present for protecting the prior art of object to have proved to be effectively All demonstrate the environmental problem of themselves.For example, tin system antibacterium Contamination Coatings and halogenated flame retardant, although applying In effectively, but they use cause significant environmental problem now.
Further, it is said in the sense that the multifunctionality that traditional protection system shortage uses in a variety of different applications, The protection system is that typical case is specific.
The multiple performance of graphene (Gr) has only just been realized now.Graphene is the allotrope of carbon, and the homoatomic is different Body, which has, densely fills the typical sp into D crystal ladder with honeycomb2One atomic thickness of the carbon atom of bonding Plane platelet structures.The carbon atom of covalent bonding is usually formed the repetitive unit comprising 6 member rings, but can also be formed 5 member rings and/ Or 7 member ring.The layer of the carbon atom of such covalent bonding is commonly referred to as graphene " piece (sheet) ".Graphene can be artificial synthesized Ground is advantageously prepared by the peeling of graphite.
The special performance of graphene is now to be applied in protection system, promotes for example, improved air impermeability, chemically-resistant Property, fire-retardant and antibacterial effect (antibacterial effects) and super lubricity.
However, although graphene within a protection system there are many prospect, many graphene systems for being developed so far are protected Protecting system is not able to satisfy the quality requirements of Conventional protection systems.Therefore many graphene system protection systems are converted to failing Viable commercial product.
Therefore, there are still the chances of exploitation new graphene based material with a variety of functions for example in protection application.
Summary of the invention
Present invention accordingly provides a kind of graphene composite materials comprising the graphene system material of hydration kodalk intercalation Material.
The present invention also provides a kind of preparation methods of graphene composite material, and providing the method includes (i) includes stone The liquid composition of black alkene based material and hydration kodalk, and (ii) remove liquid from the composition, to retain institute The graphene based material and the hydration kodalk in composition are stated, wherein the technique of the removing liquid in step (ii) Promote intercalation of the hydration kodalk in the graphene based material, to provide the graphene composite material.
Invention further provides a kind of substrates comprising graphene composite material, graphene system composite wood Material includes the graphene based material of hydration kodalk intercalation.
It has surprisingly been found that show can be by a variety of improved property for graphene composite material according to the present invention It can assign to the characteristic of substrate.Composite material display protects various substrates to be resistant to a series of the only of varying environment/use conditions Special ability.It assigns to such improved performance of substrate and is surprisingly better than every kind of constituent component by composite material in list It assigns when solely using to the performance of substrate.
E.g., including the substrate of graphene composite material can advantageously show improved anti-flammability, improvement it is wear-resisting Consumption and/or improved microbial resistance (antimicrobial properties).
Therefore the present invention further provides for the substrate with improved anti-flammability, which includes graphene system composite wood Material, wherein the graphene composite material includes the graphene based material for being hydrated kodalk intercalation.
The present invention also provides the substrates with improved abrasion performance, which includes graphene composite material, wherein The graphene composite material includes the graphene based material for being hydrated kodalk intercalation.
Invention further provides the substrates with improved microbial resistance, which includes graphene system composite wood Material, wherein the graphene composite material includes the graphene based material for being hydrated kodalk intercalation.
Although will focus on graphene composite material for provide improved anti-flammability, improvement abrasion performance and/ Or the purposes of improved microbial resistance describes the present invention, however, it is to be understood that the present invention is not limited to these applications.
Therefore, invention further provides the substrate of the improved performance with more than one, which includes graphite Alkene composite material, wherein the graphene composite material includes the graphene based material for being hydrated kodalk intercalation.
The present invention also provides a kind of methods of more than one performance for improving substrate, and the method includes providing to have stone The substrate of black alkene composite material, wherein the graphene composite material includes the graphene system material for being hydrated kodalk intercalation Material.
The substrate may include graphene composite material or that graphene system is provided with by any suitable means is multiple Condensation material.For example, substrate can be coated with, be impregnated with, being blended and/or compounded with graphene composite material.
Although by graphene composite material assign the various improved performances to substrate can be by different mechanism It acts on and does not expect to be bound by theory, it is believed that the common trait of most of (if not all) such improved performances Good combination can not only be formed with substrate derived from composite material, and composite material itself has strong internal combustion knot Structure.It is or undesirable to be bound by theory, it is believed that hydration kodalk plays an important role on promoting such binding characteristic.
Graphene composite material may include graphene based material, and the graphene based material is selected from graphene, oxidation Graphene, redox graphene, the graphene oxide of partial reduction and a combination thereof.
It is according to the present invention suitable for the substrate that uses include: comprising cellulosic material, polymer, metal, ceramics, glass and Those of a combination thereof.
In further aspect of the invention described in detail below and embodiment.
Detailed description of the invention
The present invention will be described with reference to following non-limiting figure herein, in which:
Fig. 1 shows the schematic diagram of graphene composite material used according to the invention；
Fig. 2 shows (a) substrates for being provided with graphene composite material according to the present invention and (b) by making according to the present invention The flame-retarding characteristic that graphene composite material provides；
Fig. 3 shows (a) paper, the paper that (b) is handled with redox graphene and (c) with reduction-oxidation according to the present invention The flammability test of graphene/hydration kodalk composite material processing paper；
Fig. 4 shows the pine lath for carrying out combustion test (being exposed to butane flame 12 seconds with the distance of 20mm), wherein (a) Using pine lath and (b) using coated with redox graphene according to the present invention/hydration kodalk composite material Pine lath；With
Fig. 5 shows the pellet formed by sawdust for carrying out testing vertical flammability (UL-94), wherein (a) is using by sawdust shape At pellet and (b) using by being provided with redox graphene according to the present invention/hydration kodalk composite material saw Consider the pellet formed to be worth doing；
Fig. 6, which is shown, to be not coated with substance (glass control), is being coated with graphene oxide (GO control), redox graphene (rGO, by N2H2) present on (and control) and the culture dish of graphene composite material according to the present invention (rGO/SMB) 0 and 24 hour bacterial clump；With
Fig. 7 show the graphene composite material (rGO/SMB) according to the present invention on Cu and glass baseplate relative to The bonding of graphene oxide (GO control) and redox graphene (rGO control) and the comparison characterization of wear characteristic.
Fig. 8 shows polymer (water solubility-PVA) sample for carrying out combustion test (UL-94), does not locate wherein (top) uses Sample, and (bottom) are managed using poly- with redox graphene according to the present invention/hydration kodalk composite material dipping Close object sample.
Fig. 9 shows polymer (oil-soluble-polystyrene) sample for carrying out combustion test (UL-94), wherein (top) is adopted It is soaked with untreated samples, and (bottom) using with redox graphene according to the present invention/hydration kodalk composite material The polymer samples of stain.
Some figures are submitted with colour and can be according to requiring to provide.
Specific embodiment
The present invention provides unique graphene composite materials.Graphene composite material includes that hydration kodalk is inserted The graphene based material of layer.
In the context of the present invention, it includes graphite that statement " graphene system " composite material, which is intended to refer to that the composite material has, Alkene, graphene oxide, the graphene oxide of partial reduction, redox graphene or its two or more combined composition. Statement " graphene system " material therefore can be used herein as graphene (material or piece), graphene oxide (material or Piece), the graphene oxide (material or piece) of partial reduction, redox graphene (material or piece) or its two or more combination Facilitate description.
The Brief Discussion of the property of graphene provided above.
Graphene oxide is the oxidised form of graphene, is usually prepared by the peeling of graphite oxide.Think to aoxidize stone Black alkene has the graphene replaced with the oxygen-containing group (oxygenated groups) such as hydroxyl and epoxy group (epoxide) Architecture.Many technologies such as so-called Brodie, Staudenmaier or Hummers method can be used in graphene oxide To prepare.
Graphene oxide can restore, to form the reduction form of graphene oxide.Redox graphene is due to damage Lose its oxygen-containing group and chemically and physically all different from graphene oxide.The reduction degree of graphene oxide can change, should Variation is reflected in the residual quantity of oxygen-containing group.It is frequent in the art in the case where graphene oxide does not restore completely Graphene oxide as partial reduction.Redox graphene and the graphene oxide of partial reduction are compared with graphene oxide It is less hydrophilic.Redox graphene is referred to as graphene in the art sometimes, as substantially all oxygen-containing group The instruction being removed.It is known in the art for making the technology of graphene oxide reduction or partial reduction.For example, graphene oxide can To be restored or partial reduction by chemistry or thermal reduction.
Graphene oxide, the graphene oxide of partial reduction and redox graphene are similar to graphene with covalently knot The carbon atom chip architecture of conjunction.
Graphene composite material includes the graphene based material for being hydrated kodalk intercalation.Therefore composite material itself will Multiple graphene based material pieces including being hydrated kodalk intercalation therebetween.The schematic diagram of graphene composite material is in Fig. 1 It shows, Fig. 1 emphasizes stratiform (layered) chip architecture of graphene based material and the hydration metaboric acid in stratiform chip architecture interpolation layer Sodium (NaBO2.xH2O)。
Graphene based material by being hydrated kodalk " intercalation " means that being hydrated kodalk as solid residue exists Between the layer of graphene based material chip architecture on.In other words, with metaborate monohydrate kodalk intercalated graphite alkene based material.
Without doubt, graphene composite material itself also exists as solid.
The stratiform chip architecture of graphene based material may include graphene, graphene oxide, partial reduction graphite oxide Alkene, redox graphene or its two or more combination.
In one embodiment, graphene composite material includes the graphene and oxygen reduction for being hydrated kodalk intercalation One or both of graphite alkene.
Kodalk used according to the invention is " hydration ".By making kodalk hydration mean kodalk packet Containing the water for physically and/or chemically absorbing and/or combining, such as the crystallization water.Hydrated compound is typically with label .xH2O comes It indicates.
If being hydrated kodalk then can use hydration kodalk with intercalation in graphene based material Physical form is not particularly limited.
In one embodiment, graphene based material intercalation has micron particles, nano particle, film, sheet material or combinations thereof Form hydration kodalk.
As used herein, refer to that " nano particle " be full-size is particle no more than 100nm.
As used herein, refer to that " micron particles " be full-size are particle no more than 1000nm.
When for particle form, the full-size for being hydrated kodalk will be usually in the range of about 50-500nm.
In general, graphene composite material will will include the graphene based material peace treaty of about 20 weight % to about 80 weight % The hydration kodalk of institute's intercalation of 20 weight % to about 80 weight %.
Graphene composite material may include more than one other components.In the case, it will therefore adjust stone The weight % of the inorganic metal hydrate of black alkene based material and/or intercalation.
Graphene based material used according to the invention and hydration kodalk can for commercial source or pass through ability Technology known to domain is made.
Graphene composite material is prepared in which can be convenient by the following method, and the method includes (i) offers to include The liquid composition of graphene based material and hydration kodalk, and (ii) remove liquid from the composition, to retain The graphene based material and the hydration kodalk in the composition, wherein in step (ii) removing liquid work Skill promotes intercalation of the hydration kodalk in the graphene based material, to provide the graphene composite material.
It include graphene based material and the liquid composition for being hydrated kodalk by providing, the composition certainly will be also Including liquid.The liquid can be organic system (solvent), water system or combinations thereof.
Those skilled in the art will understand, and graphene based material is substantially insoluble in most liquid, but It can be readily dispersed in liquid.
It can be solvable or insoluble in liquid composition for being hydrated kodalk.
In one embodiment, the preparation method of the composite material includes: that (i) is provided including graphene based material and water The water system liquid composition of kodalk is closed, and (ii) removes water from the composition.
Hydration kodalk is set to be included in the liquid dispersion of graphene based material and remove from resulting composition Liquid (thus retaining graphene based material and the hydration kodalk in composition) becomes hydration kodalk in graphite Intercalation in the layer structure of alkene based material.
If in composition retain graphene based material and hydration kodalk, then can by any suitable means from Liquid is removed in composition.
In one embodiment, liquid is removed from the composition by evaporation.As needed, heat can be applied to this Composition is to promote such evaporation.
In the case where hydration kodalk dissolves in the liquid for composition, removing liquid from composition will Promote the formation of hydration kodalk particle or crystal of the intercalation in the layer structure of graphene based material.
In the case where hydration kodalk is insoluble in the liquid for composition, removing liquid from composition will Intercalation of the pre-existing hydration kodalk particle in the layer structure of graphene based material can be merely facilitated.In this situation Under, used kodalk particle will have of course size appropriate such intercalation occurs.
The hydration kodalk itself for being used to form graphene composite material can be pre-formed and introduce for making In the liquid composition provided for graphene composite material.Selectively, hydration kodalk can be used as graphene system A part of the preparation method of composite material and be prepared in situ.
Therefore, including graphene based material and hydration kodalk liquid composition can by include graphene oxide and The water system liquid composition of sodium borohydride provides, and wherein graphene oxide is by sodium borohydride reduction, to provide reduction-oxidation graphite Alkene and hydration kodalk.
In one embodiment, graphene composite material is produced by following: it includes graphene oxide that (i), which is provided, With the water system liquid composition of sodium borohydride, wherein sodium borohydride reduction graphene oxide is to provide redox graphene and water Close kodalk；(ii) removes water from being formed by composition, to retain graphene based material and the water in composition Kodalk is closed, wherein the technique of the removing water in step (ii) promotes the hydration kodalk in the graphene based material In intercalation to provide the graphene composite material.
The present invention provides the substrate with more than one improved performance, and the substrate includes graphene system composite wood Material, wherein the graphene composite material includes the graphene based material for being hydrated kodalk intercalation.
The present invention also provides the methods for more than one the performance for improving substrate, and the method includes providing to have graphene The substrate of composite material, wherein the graphene composite material includes the graphene based material for being hydrated kodalk intercalation.
More than one improved performance include but not limited to improved anti-flammability, improvement abrasion performance, improve it is anti- Microbes.
" improve (improving) ", " improved (improved) " or " with improvement (to are referred in context of the invention Improve) " performance is intended to refer to performance of the substrate relative to the substrate for not including graphene composite material according to the present invention Improvement.
Graphene composite material can advantageously assign improved performance to various substrates.
The substrate being suitably used according to the present invention include: comprising cellulosic material, polymer, metal, ceramics, glass and Those of a combination thereof.
The example of cellulosic material includes but not limited to timber, paper, sawdust and natural fiber.
The example of polymer includes but not limited to thermosetting polymer and thermoplastic polymer.
The specific example of polymer includes but not limited to polyolefins, polyamide-based, polyesters, polyvinyl alcohol, polyphenyl Vinyl, polyacrylate, polyurethanes, polycarbonate-based, epoxy resin.
The example of metal includes but not limited to steel, copper and aluminium.
The physical form that can be used to substrate is not particularly limited.For example, substrate can be sheet material, film, plate, pencil (beam), the shape of particle, powder, slab (plank) or any formed product.
There is the substrate of the composite material by substrate " comprising " graphene composite material or " offer ", it is meant that this is multiple Condensation material is suitably physically associated with substrate, to assign improved performance.In other words, substrate includes that graphene system is compound Material is provided with graphene composite material, so that the composite material with substrate material physical is associated.
Graphene composite material can be located in surface and/or the base material substrate of substrate.By by composite coated , absorb or be impregnated in substrate material, and/or be compounded with substrate material, substrate may include or be provided with composite material.
For example, the composite material can be used as the film on the surface of substrate and exist and/or composite material can be distributed Throughout base material substrate material.
Substrate can be provided with graphene composite material by any suitable means.
When providing the substrate with graphene composite material, graphene composite material can be with preform state (that is, form of composite material itself) uses.For example, graphene composite material can form a part of liquid composition, The liquid composition is coated on substrate using coating technique well known by persons skilled in the art or is impregnated in substrate.Herein In the case of, liquid composition may include the stone of the dispersion in liquid (organic system (solvent), water system or combinations thereof) Black alkene composite material.
As preforming material, graphene composite material can also be with the use of the form of solid (such as powder) and and base Material combination of materials, wherein the gained blend of substrate material and graphene composite material is optionally processed, to provide by wrapping Include product made of the substrate material of graphene composite material.For example, substrate can be the form of thermoplastic polymer, thus Thermoplastic polymer and graphene based material melt-processed, so that providing includes the graphite for being distributed across thermoplastic polymer matrix The thermoplastic polymer product of alkene composite material.
As preforming material, graphene composite material can also be blended with cellulosic materials such as such as sawdust, and Compression gained blend includes the so-called reconstituted wood product for being distributed across the graphene composite material of product to be formed.
Selectively, graphene composite material can be used as a part being arranged to the process of substrate and use forerunner Body component and be prepared in situ.For example, it further includes being hydrated in the liquid of kodalk that graphene based material, which can be scattered in,.Gained liquid Then body composition can be used for being coated or impregnated with the substrate.Liquid is removed from the liquid composition for being coated with or being impregnated, Retain the graphene based material and hydration kodalk in composition simultaneously, being formed in situ for composite material can be promoted.
In one embodiment, substrate is provided with graphene system using the presoma component of graphene composite material Composite material.
" the presoma component " of graphene composite material mentioned in this article is intended to include graphene based material and hydration Kodalk.As " presoma component ", be hydrated kodalk will not intercalation have a graphene based material, but intercalation is as providing A part of the process of substrate with graphene composite material occurs.
Graphene composite material or its presoma component can be provided in the form of coating composition, the coatings combine Object is applied to substrate using the traditional technology such as injection, dip-coating, scraper and/or brushing.
Coating composition can be the form of coating composition.
In the case where substrate is suitably absorbent, the liquid including graphene composite material or its presoma component Composition can be used for impregnating the substrate.
Selectively, graphene composite material itself can be blended with substrate material, wherein gained blend is optionally Further processing is for example compressed or is squeezed out.
In one embodiment, by being coated with the composition for including graphene composite material or its presoma component Substrate makes substrate be provided with graphene composite material.Applying cloth base material with composition can be for example, by injection, dip-coating, scraper And/or it the technologies such as brushes and carries out.
In another embodiment, by the way that substrate to be used to the combination including graphene composite material or its presoma component Object dipping, makes substrate be provided with graphene composite material.It can be by the way that substrate be immersed in combination with composition immersed substrate It is carried out in object.
The composition including graphene composite material for being coated or impregnated with substrate can be liquid composition.Combination The liquid component of object can be organic system (solvent), water system or combinations thereof.The composition may include that other components for example polymerize Object.
In further embodiment, substrate is thermoplastic polymer, and by by the polymer and graphene system Composite material melt-processed makes substrate be provided with graphene composite material.
In further embodiment, substrate is thermosetting polymer, and by by graphene composite material with Persursor material for thermosetting polymer to be made is blended, and substrate is made to be provided with graphene composite material.For heat to be made The persursor material of solidity polymer includes polymerization and is crosslinked to form the monomer and prepolymer of thermosetting polymer substrate.
In one embodiment, by using the liquid composition including graphene composite material to be coated with or soak substrate Stain makes substrate be provided with graphene composite material.
In another embodiment, substrate is provided with graphene composite material in the following manner: (i) uses substrate Liquid composition including graphene based material and hydration kodalk is coated or impregnated with, and (ii) from being coated with or impregnated Remove liquid in liquid composition and retain graphene based material in composition and hydration kodalk simultaneously, thus formed and Graphene composite material is provided.
In further embodiment, substrate is provided with graphene composite material in the following manner: (i) is by substrate With including graphene based material and be hydrated the water system composition of kodalk and be coated or impregnated with, and (ii) from being coated with or impregnated Liquid composition in remove water, thus formed and graphene composite material is provided.
As described herein, the hydration kodalk for being used to form graphene composite material can be pre-formed and draw Enter to be used to prepare graphene composite material and in the liquid composition that provides.Selectively, hydration kodalk can be used as It prepares or is formed a part of the process of graphene composite material and be prepared in situ.
Therefore, " the presoma component " of graphene composite material can also include before being used to prepare hydration kodalk Drive body compound.The precursor compound of hydration kodalk may include oxidized sodium borohydride, the carbon that combines with borax Sour sodium and the sodium tetraborate combined with sodium hydroxide.
In one embodiment, substrate is provided with graphene composite material in the following manner: (i) offer includes The water system liquid composition of graphene oxide and sodium borohydride, wherein the graphene oxide is by sodium borohydride reduction to provide reduction Water system liquid composition provided in substrate step (i) is coated with or is soaked by graphene oxide and hydration kodalk, (ii) Stain, and (iii) remove water from the water system liquid composition for being coated with or being impregnated, compound to form and provide graphene system Material.
The present invention may further include the hydration for providing and having a part for not forming graphene composite material itself The substrate of kodalk.In the case, substrate will will include graphene composite material and further include not forming graphene The hydration kodalk of a part of composite material.
For example, in one embodiment, by used substrate hydration kodalk dipping.In the case, will Substrate is hydrated kodalk dipping and then can also be impregnated and/or be coated with graphene composite material.
There is provided has the substrate of the hydration kodalk of a part for not forming graphene composite material itself can be into The anti-flammability of one step raising substrate.
As coating on base material, graphene composite material can as expected purposes with the film of average thickness Form provides.For example, the thickness of graphene composite material film can be 500 microns or less.
The improved anti-flammability of substrate
Graphene composite material according to the present invention can assign improved anti-flammability to substrate.
Substrate can include or be provided with graphene composite material as described herein.
Relevant anti-flammability is those of known in the art and the inflammability including substrate and burning velocity, sudden and violent in substrate Release, self-extinguishment and the dilatancy of toxic/flammable volatile matter from substrate, charcoal when being exposed to the ignition source such as fiery or very hot Formation/yield and oxygen barrier performance.
For example, it has been found that the substrate for being provided with graphene composite material according to the present invention is shown relative to not set The identical substrate of with good grounds graphene composite material of the invention, it is reduced inflammability, lower burning velocity, significant Expansion effect and one of release of reduction of toxic/flammable volatile matter or a variety of when being exposed to ignition source.
Techniques known in the art can be used to determine in the anti-flammability of substrate.Such technology include TGA, STA, UL-94, Calorimeter, limit oxygen index (LOI) measurement.
The substrate of the improved anti-flammability of display according to the present invention will be certainly this as flammable substrate.Change speech It, the present invention can provide the flammable substrates with improved anti-flammability.
The example of such flammable substrates includes: comprising those of cellulosic material, polymer and a combination thereof.
The example of cellulosic material include it is described herein those.
The example of polymer include it is described herein those.
In one embodiment, flammable substrates include cellulosic material, polymer material or combinations thereof.
Think that the excellent anti-flammability assigned from graphene composite material to substrate is worked by a variety of mechanism.
It is undesirable to be bound by theory, it is believed that, hydration kodalk plays the function of radiator, because its experience heat absorption is de- Water and discharge water into ambient enviroment.Think that this promotes unique expansion effect in turn.
Think that graphene based material synergistically works including at least four combination function below to promote by providing Into fire resistance: (i) anti-block enters flammable substrates, and (ii) provides self-extinguishment, and (iii) prevents toxic and flammable from substrate Property volatile matter escape, and (iv) show carbon formed and expansion effect.
Think that graphene based material also functions to the effect of carbon donor, to establish physics between the substrate and flame of non-fuel Barrier, to protect substrate.
Further, it is believed that hydration kodalk promotes between the layer of graphene based material and substrate and compound graphite Height between alkene composite material combines, and thus provides strong flame retardant systems.In composite material with the coating shape on substrate In the case that formula provides, this is particularly useful.
The unique anti-flammability assigned by graphene composite material can be further illustrated with reference to Fig. 2.
Fig. 2 (a) indicates the substrate for being coated with graphene composite material according to the present invention.Graphene composite material applies Layer is considered as including the graphene based material for being hydrated kodalk intercalation.
Fig. 2 (b) shows the substrate for being exposed to the graphene composite material coating of Fig. 2 (a) of fire.Think according to the present invention The graphene composite material used provides several mechanism, and improved anti-flammability is assigned to substrate by this.Firstly, and still It is undesirable to be bound by theory, it is believed that the hydration kodalk of intercalation not only promotes good between the layer of graphene based material structure Good bonding (adhesion), also bonding of the promotion graphene composite material for substrate.Such bond properties provides strong Flame retardant systems.Think that the layer structure of the strong bonding of graphene composite material hinders transmitting of the oxygen to substrate, thus subtracts A possibility that few substrate kindling.Similarly, it is believed that the layer structure of the strong bonding of graphene composite material obstruction can be Toxic and also combustion-supporting volatile component (such as the CH from substrate4) release.Further, when being exposed to fire, hydration Kodalk can undergo heat absorption to be dehydrated, and thus play the function of radiator, also discharge water into ambient enviroment.Think that this is anti- Come over to promote unique expansion effect.It has been found that such comprehensive characteristics of graphene composite material play it is efficient, effectively and The function of strong flame retardant systems.
It is clearly shown in FIG. 3 by the excellent anti-flammability that graphene composite material assigns, which shows a series of The result of flame assay.In flame assay, outturn is made to be exposed to open fire and its flammable function as the time Assessment.Fig. 3 (a) tests body paper sample, and Fig. 3 (b) test is only coated with the body paper sample of redox graphene, and Fig. 3 (c) The body paper sample of the with good grounds graphene composite material of the invention of Test coverage, the composite material include that hydration kodalk is inserted The redox graphene of layer.Such as can be high-visible from Fig. 3, body paper sample and the paper coated with redox graphene It easily lights and the completely burned after about 10 seconds.However, being coated with graphene composite material according to the present invention Outturn cannot be lighted when being exposed to open fire at least 120 seconds.
Similarly, Fig. 4 shows the pine lath for carrying out combustion testing (being exposed to butane flame 12 seconds with the distance of 20mm), Wherein (a) is compound using redox graphene according to the present invention/hydration kodalk is coated with using pine lath and (b) The pine lath of material.It can be seen that untreated pine lath almost burns after the 30 seconds, and it can see coating The pine lath of with good grounds composite material of the invention only influenced at its contact point by flame, and fire is not propagated and lath Remainder does not damage largely.
In addition, Fig. 5 shows the pellet formed by sawdust for carrying out vertical burn test (UL-94), wherein (a) is using by sawing The pellet formed and (b) are considered to be worth doing using by being provided with redox graphene according to the present invention/hydration kodalk composite material Sawdust formed pellet.The pellet (b) of coating is displayed without the excellent anti-flammability of flame propagation behavior.For composite material Flame (flaming) or scorching hot burning is not observed in the sample of processing, and therefore, those sample classifications are V-0.Composite wood Expect that the burning of the sample of processing stops immediately without the vertical raising of flame, and untreated sawdust pellet shows higher degree Combustibility: end (reaching holding jig) is lasted up to about linear burning velocity 0.5mm/s.
Fig. 8 and 9 show flammable polymeric (PVA and polystyrene-top) how by with reduction according to the present invention Graphene oxide/hydration kodalk composite material is compounded and assigns anti-flammability (bottom).
The improved microbial resistance of substrate
Graphene composite material according to the present invention can assign improved microbial resistance, such as antibacterium to substrate Property and/or antifungal activity.
Substrate can be provided with graphene composite material as described herein.
Relevant antimicrobial property is known in the art those, and including prevent or reduce it is on base material for example The microorganisms such as bacterium or fungi colonize (colonisation).
For example, it has been found that include graphene composite material according to the present invention substrate relative to do not include according to this The identical substrate of the graphene composite material of invention, prevents or reduces colonizing for the microorganism such as bacterium or fungi.It changes Yan Zhi, it has been found that the substrate including graphene composite material according to the present invention shows Microbicidal or suppression microorganism Property, such as press down bacillary, bactericidal property, restraining epiphyte and/or fungicidal.
The microbial resistance of substrate can be determined by techniques known in the art.
The substrate of the improved microbial resistance of display according to the present invention will colonize shadow vulnerable to microorganism for itself certainly Loud substrate.In other words, the present invention can provide the substrate that influence is colonized vulnerable to microorganism with improved bacteria resistance.
The example for colonizing the substrate of influence vulnerable to microorganism includes: comprising cellulosic material, polymer, glass, metal, pottery Those of porcelain and a combination thereof.
The example of cellulosic material include it is described herein those.
The example of polymer include it is described herein those.
The example of glass include it is described herein those.
The example of metal include it is described herein those.
Ceramics example include it is described herein those.
In one embodiment, the microbial resistance of the substrate including graphene composite material according to the present invention is Bacteria resistance and/or antifungal activity.
Term " microorganism (microbe) " mentioned in this article or association term such as " (microbial) of microorganism " " microbial organisms (microbial organism) " is intended to refer to including in archeobacteria or Eukaryotic field As any organism existing for microscopic cells.Therefore, which is intended to cover the protokaryon or eukaryotic with microscopic size Or organism and bacterium, archeobacteria and eubacteria and, for example, the eukaryotic microorganisms such as yeast and fungi including all species.
Relevant microorganism also includes gram-positive bacteria and Gram-negative bacteria.
Think that the excellent microbial resistance assigned from graphene composite material to substrate passes through a variety of mechanism realities It is existing.It is undesirable to be bound by theory, it is believed that, microbial resistance is related to: by the destructive rouge of sharp edges graphene based material Matter extracts (the microorganism hole of its integrality for destroying microbial film and intertexture, to generate the disturbance of cell membrane) and graphite Electric charge transfer between alkene based material piece and the microbial cell for causing DNA to damage.Further, also think in the composite The presence of hydration kodalk itself assigns anti-microbial effect.In the case where substrate and water system environment contact, it is hydrated inclined boron Sour sodium can be slowly leached advantageously from composite material to assign such anti-microbial effect.It is therefore contemplated that composite material is whole Body assigns effective antimicrobial property to substrate.
The unique microbial resistance assigned by graphene composite material can be shown with further reference to Fig. 6.
Fig. 6, which is shown, to be not coated with substance (glass control), is being coated with graphene oxide (GO control), coated with oxygen reduction fossil Black alkene (rGO, by N2H2) and be coated with graphene composite material (rGO/SMB) according to the present invention culture dish on present 0 and 24 hour bacterial clump.The only rGO/SMB sample significant reduction that shows bacterial colonization after 24 hours.
The improved abrasion performance of substrate
Graphene composite material according to the present invention can assign improved abrasion performance to substrate.
Substrate can be provided with graphene composite material as described herein.
Relevant abrasion performance characteristic is known in the art those, and including measurement in experience abrasive force (abrasive Abrasion loss when force).
For example, it has been found that include graphene composite material according to the present invention substrate relative to do not include according to this The identical substrate of the graphene composite material of invention, shows improved abrasivity.
The abrasion performance of substrate can be determined by techniques known in the art.Such technology includes ASTM D4060.
The substrate of the improved abrasion performance of display according to the present invention will be certainly substrate vulnerable to abrasion influence itself. In other words, the present invention can provide the substrate influenced vulnerable to abrasion with improved abrasion performance.
The example of substrate vulnerable to abrasion performance influence includes: comprising cellulosic material, polymer, glass, metal, ceramics Those of with a combination thereof.
The example of cellulosic material include it is described herein those.
The example of polymer include it is described herein those.
The example of glass include it is described herein those.
The example of metal include it is described herein those.
Ceramics example include it is described herein those.
Think that the excellent abrasion performance assigned from graphene composite material to substrate is realized by a variety of mechanism. It is undesirable to be bound by theory, it is believed that, abrasion performance by the lubricity that is provided by graphene based material, by hydration kodalk Pair of the strong internal combustion of the composite structure of offer and the graphene composite material also provided by hydration kodalk The combination of the strong combination of substrate is worked.It is therefore contemplated that composite material integrally assigns strong abrasion performance system to substrate.
The unique abrasion performance assigned by graphene composite material can be shown with further reference to Fig. 7.
Fig. 7 show on Cu and glass baseplate relative to graphene oxide (GO control) and redox graphene (rGO Control) graphene composite material (rGO/SMB) according to the present invention bonding and wear characteristic comparison characterization.Part (a-d) the cross-hatching scratch band adhesiveness for showing the coating being deposited on Cu and glass baseplate tests (cross-cut scratch Tape adhesion test) (ASTM D3359-09e2), wherein (a and d) is GO (control), (b and e) is rGO (control), And (c and f) is rGO/SMB.Partially (a-d) shows the various adhesiveness between graphene composite material and substrate, wherein Partially (c and f) shows the best result after bonding test to graphene composite material almost without damage.Partially (g) Abrasion type after the wear test of micro-pits and parallel groove that combination identifies on the coated surface, part (h) are shown The weight loss behavior of the different abrasion length of coating surface is shown.
The present invention will be described with reference to following non-limiting example later herein.
Embodiment
The synthesis of graphene oxide (GO)
Graphite flake (flakes) (< 45 μm) is removed according to improved Hummers forensic chemistry.Use 9:1 ratio H2SO4/H3PO4The KMnO of (360:40ml) and 18g4It is reacted completely, so that the graphite flake of 3g be made to aoxidize.While agitating Removing 12h is carried out at 50 DEG C.Then solution is cooled to room temperature and is come down in torrents to the 30%H with 3ml2O2Ice cube On (300ml).Finally, mixture is repeatedly centrifuged 2h at 4000rpm, to use distilled water (twice), 32% respectively HCl (twice) and ethyl alcohol (twice) washing, to obtain GO, by the GO at 40 DEG C oven drying 12h.
Composite-material formula -1
The reduction of graphene oxide (GO) and the formation for being hydrated kodalk (SMB): the GO (rGO) of reduction by it is following come Preparation: by a certain amount of NaBH as reducing agent of aqueous dispersions (3.5mg/ml) of the GO of 50ml4Reduction is to form 0.1mol L-1NaBH4Mixture, then at 60 DEG C flow back and stir 8hr.The reaction is produced by solution simultaneously NaBH4Hydrolysis caused by be hydrated kodalk (being shown in formula 1).
Final solution includes rGO and hydration SMB, and it is multiple that they form graphene system when solidifying and with heat to remove water Condensation material.
Composite-material formula -2
Graphene oxide (GO) method according to provided in document is made in the aqueous solution (GO of 3mg in 1 μ l) of GO With hydrazine (N2H4) chemically restore.Then, hydration kodalk is mixed from external source, to prepare GO and the dissolution of reduction It is hydrated the aqueous solution of SMB, percentage composition changes between 40 to 80 weight %.
The preparation of graphene composite material coating
By the rGO/SMB solution of preparation by drop coating or spraying method in copper plate (3cm × 3cm × 0.2cm) and covering It is deposited on substrate on the glass slide (2.5cm × 3.5cm) of whole region (from edge-to-edge), then in 60 DEG C of baking Dry 3h in case.The comparison coating of the contrast solution with GO, rGO is prepared using the same terms.For wear test, by institute The graphene system surface of coating is placed under Taber Abrasion Tester (ASTM D4060).
Characterization
Scanning electron microscope (SEM-FEI QUANTA 450, Japan) is for analyzing GO and rGO configuration of surface, Yi Ji The coating layer thickness of the sample of vertical arrangement is measured under the acceleration voltage of 5KV.Energy dispersion X-ray (EDX) unit is for capturing The element peak of the rGO coating comprising kodalk crystal under 5.0KV.High-resolution Philips CM200, transmission electron microscopy Mirror (TEM), Japan, for the GO piece of peeling to be imaged at 200KV.By the way that the GO dispersion of synthesis is equal to be formed in ethanol Even dispersion prepares TEM sample.Nikon optics petrographic microscope (LV100POL, USA) draws lattice surface for analyzing to mark Bond grade.By Fourier Transform Infrared Spectroscopy (FTIR) (Nicolet 6700Thermo Fisher, USA) study GO and The vibration stretch mode of different oxygen functional group in rGO.It is analyzed in air atmosphere by TA instrument (Q-500, Tokyo, Japan) It is handled and the TGA (thermogravimetric analysis) and DTG of untreated sawdust (derivative thermogravimetric analysis).When burning in air environment, temperature Degree rises to 600 DEG C from environment temperature with the speed of 5 DEG C/min.For analyzing a variety of gas phase chemical combination discharged from burning sample in real time The thermogravimetric analysis (TGA-FTIR) in conjunction with Fourier transform infrared of object is by being connected to the PerkinElmer TG- of TL 8000 IR EGA system (TG-IR EGA, PerkinElmer Ltd, UK) is completed.The operation is in air atmosphere with the speed of 6 DEG C/min Degree completes the sample quality of about 16mg.
The test of cross-hatching adhesiveness
It is (micro- to metal (Cu) and glass that rGO/SMB coating is measured according to standard adhesive tape test ASTM D3359-09e2 Mirror glass slide) substrate adhesiveness.Cross-hatching adhesiveness test kit (QFH-HG600) is purchased from Biuged Laboratory Instruments (Guangzhou, China).Coated cutting tool includes 11 teeth for being spaced 1.0mm.Using cutting tool it Before, the substrate of coating is placed in the laboratory workbench by guide supporting.After applying stroke grid pattern (about 90 °), with examination The brush of agent box removes the piece of any removing of coating, and the mild pressure of adhesive tape (scotch tape) is placed On drawing lattice.Cutting sample is checked with high-power microscope (Nikon-Petrographic Microscope), and according to ASTM Rating scheme grading.
Abrasion performance test
Carry out standard (ASTM D4060) Taber abrasion machine (Dongguan bridge construction detection device Co., Ltd, model JQ-802A) Test is to evaluate progressive abrasion of the rGO/SMB coating of bonding under 250g load under a pair of of abrasive wheel of diameter 52mm.For It is tested, copper and the print of vitreous coating (10cm × 10cm) is placed on platform and assembled on platform, thus with 60rpm Constant speed rotate 3000 times circulation.By smooth swiped through to remove every ≈ after the discrete particles on lapped face 300 circulations weigh sample to measure abrasion loss.Abrasion sample is shot at SEM and Raman Imaging System, to observe Wear pattern and shared molecular area percentage after abrasion.
Antibacterium test
According to AATCC test method 100-2004, to gramnegative bacterium Escherichia coli (E.coli) (ATCC 25922) qualitative assessment of the antibacterium efficiency of the glass sample of GO, rGO and rGO/SMB coating is carried out.Naked glass slide and GO are applied The glass slide covered is carried out as primary and secondary control.About the sample of coating, with the original concentration 3mg/ of Graphene derivative The 0.8ml solution drop coating glass slide (2.5cm × 2.0cm) of ml.Coating and uncoated sample are individually positioned in sterile microplate In (sterile micro plate) (6 holes), and the bacterial suspension (10 being incubated overnight with 0.35mL7CFU/mL it) is inoculated with. After inoculation, each sample is placed in 50mL salting liquid (0.85% (w/v)) and is aggressively shaken 1 minute.In order to when measuring zero Sample is placed in salting liquid by bacterial population immediately after inoculation.Through serial dilution and pour plate method use at 37 DEG C Incubate Luria-Bertani agar medium plate (10g peptone, 5g yeast extract, 10g NaCl and distillation in 48 hours Water is to 1L；PH-7), total bacteria is measured.The antibacterium efficiency of all samples is calculated using equation (2).
Wherein, R is that bacterium reduces percentage, C0And C24Respectively be inoculation after at once with inoculation 24 hours after bacterium meter Number.
Borate dipping and composite coating
Prepared rGO/SMB aqueous solution generates the uniform mixture that wherein SMB is dissolved state.It, will for dipping (500 μm to 1mm) handle that into beaker and at 70 DEG C to be kept stirring 5 small with 50ml rGO/SMB to the pine tree sawdust of 2.6g purifying When.Dry sawdust sample is impregnated with SMB, and it was found that be coated with rGO/SMB composite material well.
The inhibition of volatile matter and flame retardant test
The test that smog and volatile matter inhibit is carried out in the glass cylinder closed at one end that internal diameter is 4cm, so that can be with Visually observation smog and volatile matter.By two small burnings of preheating (at 80 DEG C) sawdust (being handled and untreated) comprising 300mg Cup (10ml) is placed on hot surface (300 DEG C).Make hot plate thermostabilization 10 minutes at 300 DEG C before placing sample.Have The beaker of sample is by two similar glass cylinder coverings for observation.The immediate reaction for the sample being placed on hot plate is passed through High-definition camera (Sony HDR-PJ260) records 30 minutes.
In order to carry out the test of pyrophorisity, both untreated and processed sawdust (80mg) are placed on good setting and are existed To contact flame on the sieve of (apart from burner tip 3cm) above Bunsen burner.The gentle circulation of the flame height of bunsen burner The stomata that keeps half-open is crossed to set, which is all centre that is constant and being placed on flame for two kinds of samples.Pass through High-definition camera (Sony HDR-PJ260), record combustion phenomena (spontaneous combustion, flame propagation) is for further analysis.
Having a size of 120mm × 13mm × 3.5mm pellet by untreated and processed sawdust system under 5 tons hydraulic At.The fire-retardant behavior of these pellets is assessed by the vertical burn test of UL-94 standard.Measure five prints of every kind of sample To ensure the reproducibility of data and by its flammability classification.The time extinguished until flame itself and combustion propagation are measured Distance, then show that linear burning rate, unit are mm/min.
In order to detect the combustibility for applying rGO/SMB material as the rag paper (rag-paper) of coating, by fiber base paper (fibre based paper) dip-coating simultaneously solidifies for several times at 50 DEG C, and material loading is increased to 15 weight %.Make have and not Have cated sample and carry out flame retardant test (referring to Fig. 3).
As a result
Peeling of the GO piece from graphite is measured by transmission electron microscope (TEM).Pass through NaBH4Hydrolysis restore GO simultaneously The aqueous solution of rGO/SMB is formd with formation SMB.(intercalation) and the hydration on it between rGO piece are confirmed by TEM The presence of SMB.The EDX (energy dispersion X-ray) for being formed by graphene composite material is shown 0.185,0.277,0.523 With boron under 1.040KeV (B), carbon (C), oxygen (O) and sodium (Na) element peak, confirmed depositing for the SMB on the surface rGO respectively ?.
The sample of rGO/SMB composite material is obtained under FTIR spectrum to study the characteristic peak of synergistic effect.It is using NaBH4Reduction process in almost remove the oxygen functional group of GO, show the successful reduction of GO.In 692cm-1And 783cm-1Place The appearance for the new peak observed in the sample shows the asymmetric bending of O-B-O ring.The asymmetric stretching vibration of ring B-O goes out strongly Present 932cm-1、1083cm-1、1248cm-1And 1432cm-1Place.Further, 3353cm-1The peak at place show metaboric acid root yin from Hydrogen bond between the hydroxyl and water of son.
Thermogravimetric analysis (the N of GO and rGO/SMB composite material2Atmosphere, with 5 DEG C/min heating) display mass loss curve Significant difference.GO sample is shown as caused by the evaporation of hydrone in GO structure from environment temperature to 100 DEG C of first stage Mass loss (14.45%), the loss are slightly above rGO/SMB at this stage.In second stage between 100 DEG C to 250 DEG C, GO sample has a large amount of mass loss (54.68%), is mainly due to the removing of oxygen functional group, and rGO/SMB shows origin From 25.72% loss caused by the release of the additional water molecule of hydration SMB.When temperature is more than 350 DEG C, there are anhydrous inclined boron Sour sodium and rGO.
Anti-flammability
The modification and coating of pine tree sawdust are realized by the solution processing of the aqueous rGO of the SMB containing dissolution.Passing through will Sawdust is dipped into rGO/SMB solution and is loaded.The dry mass of processed sample increases ≈ 14.67%, this will not make Pass through high pressure (3000KPa) oxygen of both untreated and processed sawdust in bomb calorimeter (bomb calorimeter) It is big to change total amount of heat (the ≈ 460Cal/ gram) difference discharged between the sample of burning measurement.
The differentiation of gaseous products and the inhibition of volatile matter are analyzed by FTIR.It is fired in untreated and processed pine tree sawdust FTIR spectrum during burning at different selected temperature (100 DEG C, 200 DEG C, 250 DEG C, 300 DEG C, 325 DEG C, 350 DEG C) (4000-500cm-1) show that gaseous products are varied with temperature and developed.Presence higher than the water at 250 DEG C is by aliphatic hydroxyl Cracking caused by, this is by 4000-3500cm-1The appearance of the band at place is confirmed.In 3000-2730cm-1The characteristic peak at place shows Due to methoxyl group (OCH3) and methyl (CH3) cracking and the presence of methane developed between 250 DEG C to 300 DEG C.Under high temperature Methylene (- CH2) also generate methane (CH4).As temperature is increased to 350 DEG C, in 2400-2260cm-1The carbon dioxide at place (CO2) intensity peak reinforce.A large amount of CO2Cracking and carbonization charcoal at such a temperature of the release by cellulose and lignin Burning causes.Between 300 DEG C to 350 DEG C of temperature, the imperfect combustion of pine tree sawdust is also generated such as in 2260-1990cm-1 The carbon monoxide (CO) that place recognizes.1900-1660cm-1And 1500cm-1The absorption band at place relates separately to aldehydes or ketones compound C=O is flexible, phenolic group C-O-C bending is flexible.900cm-1And 650cm-1The absorption and distribution at place is flexible to the C-H of aromatic hydrocarbons. Under raised temperature (350 DEG C), organic volatile compound (aldehydes or ketones, phenols, alkanes, olefines and aromatic hydrocarbons) starts acute Strong release.
Since 100 to 350 DEG C of heating processes start, in 4000-500cm-1Place recognizes water content, because processed Sawdust contains relatively more hydrones due to there is hydration kodalk.In conjunction with hydrone discharge in two steps；It is primary to be situated between Between 83 and 155 DEG C, second between 249 and 280 DEG C.However, the other gases discharged from processed sample (CH4、CO2, CO, organic compound) intensity significantly reduce at a temperature selected, this may be attributed to graphene composite material Impermeability gas barrier effect.300 are set in when that will be handled to be placed on after 80 DEG C of preheatings with untreated sample DEG C hot plate on 30 minutes to ensure when losing of extra water, the barriering effect of graphene composite material is also by visual inspection It looks into confirm.Untreated sawdust started to discharge smog at 3 minutes (to may be CO2) and moisture (coming from aliphatic hydroxyl), And the release of other organic volatiles (yellow and brown) is also observed between 10 to 20 minutes, and processed sawdust does not have There is the significant release for showing observable organic volatile.
When 80mg sample is placed on the sieve apart from burner tip 3cm above bunsen burner, coating and Modified loose sawdust also shows brilliant flame propagation resistant performance.Untreated sawdust started to propagate fire between 15 to 20 seconds Flame was strengthened at 25 seconds, is finally burnt out in 70 seconds.On the other hand, processed sawdust sample is during burning 100 seconds without aobvious Show spontaneous combustion behavior.
In addition, using the sample made of uncoated and coated sawdust (120mm × 13mm × 3.5mm), by vertical Combustion testing (UL-94) further assesses fire-retardant behavior.The wooden pellet of coating shows following excellent anti-flammability: for by passing through Wooden pellet made of the sawdust of processing does not have flame propagation behavior.Each of print processed for five, does not have Observe flame and scorching hot burning；Therefore material is classified as V-0.Each burning of processed print all stops immediately and does not have There is the vertical raising of flame, and untreated sawdust pellet shows the combustibility of higher degree: with about linear burning velocity 0.5mm/s lasts up to end (reaching holding jig).
Also tested with prove wherein cloth waste paper (rag paper) be used as model substrate rGO/SMB coating it is fire-retardant Property.With untreated original paper (pristine paper) and with by N2H4In the comparative experiments of the paper of the rGO processing of preparation, The cloth waste pattern product impregnated with natural gas (methane) flame ignition (referring to Fig. 3).Original cloth waste paper is complete using most 20 seconds Burning, almost without the trace of sample, and the time for loading sample several elongated segments during kindling of rGO only show it is insignificant Patience and structural intergrity.On the other hand, rGO/SMB sample does not show the sign of flame propagation behavior during flame test. Sample limits its structure and shows self-extinguishment almost without discharge white cigarette, is hydrated the additional of SMB this is because being bound to Hydrone release.After introducing Flame of Natural Gas 60 seconds, the total mass loss of fire-retardant sample is ≈ 25%.Coating and coating Cloth waste paper air atmosphere in TGA show different mass loss curves.The mass loss curve of untreated cloth waste paper 78.69% loss being shown between 300 to 400 DEG C including the moisture content initially evaporated during burning, and The cloth waste paper of rGO/SMB processing also only has lost its gross mass although loss is bound to the additional water molecule of SMB 43.81%.After 1000 DEG C of combustion process, compared with untreated cloth waste paper, the sample coated with rGO/SMB is left Much general 14% residues.
Charcoal analysis discloses some additional anti-flammabilitys of material after burning.Initial tight fibers cloth waste paper becomes fluffy Ash and be not able to maintain its planform.On the other hand, the SMB containing rGO shows expansion effect, this, which is provided, is mainly due to The existing expansion character of hydration SMB between rGO layers.Material starts to discharge hydrone between 90 DEG C and 250 DEG C.Following Dissociating water molecule starts evaporation and volume growth during kindling, is forced through the outgoing (go of graphene layer of impermeability Out), coating expansion is eventually led to.This expansion effect has been identified in the whole surface of the sample of rGO/SMB processing, It can protect following fibrous paper from flame.
Prove the anti-flammability of rGO/SMB composite material display very high level when being applied to flammable cloth waste paper.Have The hydration SMB of graphene shows effective expansion effect and self-extinguishment, with protect for a long time the combustible material of bottom from Fire.These excellent flame retardant properties can contact the combustibility below coating by the anti-flammability of SMB nanocrystal and anti-block The synergistic effect of the barrier property of partial graphene film illustrates.
The preparation of composite-material formula-A (solution system)
The grapheme material of two kinds of forms passes through the oxygen reduction of electronation, thermal reduction or the preparation of any other method Graphite alkene (GO) or the graphene prepared artificial synthesizedly or by graphite by electrochemistry, thermal mechanical or any other method, For graphene flame retardant composite material solution to be made.The graphene aqueous solution that concentration is 2-10% is mixed with hydration kodalk It closes, the hydration SMB of dissolution is made, percentage composition changes between 10 to 80 weight %.
The preparation of composite-material formula-B (powder system)
Composite-material formula (powder system) is prepared by following: use solution system formula-A, by drying, then by Grinder or ball mill grinding are formed by product, so that being formed includes being repaired with inorganic metal hydrate such as SMB nano particle The fine powder of the graphene film of decorations.
The preparation of incombustibility polymer material (part A)
The water soluble polymer material (for example, polyvinyl alcohol (PVA)) and formula-A or powder of pellet, particle or powder type End is formula-B mixing, and is stirred at 90 DEG C 3 hours, and incombustibility polymerization is then made up of curtain coating or extrusion method Object (referring to Fig. 8).
The preparation of incombustibility polymer material (part B)
The solvent soluble polymers material (for example, polystyrene) of pellet, particle or powder type is dissolved in DMF simultaneously And mixed with formula-A or powder system formula-B, concentration is the 20 weight % to 50 weight % of mixture.By mixture at 115 DEG C Lower stirring 3 hours, is then made incombustibility polymer by curtain coating or extrusion method (referring to Fig. 9).
Mechanical adhesion and abrasivity
It is determined by optical profile method and SEM, for the overall thickness for the rGO/SMB coating that cross-hatching bonds test and makes It is≤2 μm.Table 1, which is shown, has different comparisons for what both copper (Cu) and glass baseplate were graded according to standard ASTM grade The bond properties of the coated sample of formulation for coating material.These results, which show rGO/SMB coating, has most both Cu and glass surface Good bonding, also as by shown in the test of cross-hatching adhesiveness then Fig. 7 (b) and (e) of the measurement of adhesive tape process.Preparation pair According to (N2H4Reduction) rGO coating with rGO/SMB coating to be compared, to check material consolidating for Cu and glass substrate It is adhesive.By sample (rGO-N2H4) made of coating cannot show for the considerable of any of Cu and glass baseplate Minimal adhesion power (ASTM grade 0B).
The bond properties that table 1 passes through the ASTM D-3359-02 coating measured
As by the way that determined by cross-hatching bonding test, the deposition of the rGO with and without SMB, which discloses, does not have SMB Coating do not have any bond properties.It was found that GO and rGO (the reducing agent N on Cu and glass baseplate the two2H4) ASTM it is viscous It is combined into 0B (being considered not limit or without bonding), and rGO/SMB sample shows the ASTM bonding for both Cu and glass baseplate It is rated 4B (proving that less than 5% stroke lattice region is impacted).Further, rGO/SMB coating is also applied to other metals The confirmation bonding of (that is, aluminium (Al), stainless steel) and result is independent of metal base.Adhesive strength between metal plate and coating It may be formed between native metal oxide and borate interface.
After completing ≈ 3000 times circulations under the load of each wheel 250g, wear test obtains the smallest weight loss (6.33mg/cm2, maxm).The configuration of surface of rGO/SMB sample before and after wear test is shown in Fig. 7 (g and h) Out for comparing, wherein discovery SMB- crystal is evenly distributed in abrasion and the surface the two not worn away.In Fig. 7 (h) Shown in red arrow, the pattern of wear damage can clearly be classified as parallel groove and multiple dents.Micro pits are surveyed in abrasion It is generated during examination by the loss of SMB crystal.The Raman mapping on the surface worn away is shared in interior coating to analyze component Area percentage, it is 29% that display, which occupies about 71%, SMB crystal by rGO,.
The excellent adhesiveness of graphene composite material film is 4B grades by standard ASTM measurements determination, with height Abrasion performance.There are SMB crystal inside interface and graphene layer for characterization result confirmation, this shows that promoting stratiform significantly answers The mechanical strength of condensation material and bonding for external substrate (metal and glass).Between graphene film and surface (metal plate) The possibility mechanism of the bonding of raising may be to tie by force between natural (native) metal oxide and borate (SMB nanocrystal) Close the result of interaction.
Bacteria resistance
Uncoated (glass slide) and coating (GO, rGO-N2H4And rGO/SMB) sample bacteria resistance pass through AATCC test Method 100-2004 is evaluated.Bacterium bacterial strain similarly good growth in all test samples at zero, and after 24 hours It only grows and further enhances on uncoated (control) sample.Other samples comprising Graphene derivative are being made after 24 hours To show strong antibacterial activity (Fig. 6) under the GO (3mg/ml) of the uniform concentration of starting material.It was found that GO reduces 85.34% E. coli clones, and rGO-N2H4Effect is lower (54.47%) compared with GO.The antibacterium ability (99.9%) of rGO/SMB Better than GO and rGO-N2H4Coating.
Sem analysis is carried out to study the interaction between coating surface and bacterium qualitatively to confirm potential antibacterium Effect.The formation of thick biomembrane is recognized on the glass slide that wherein Escherichia coli are easy to be proliferated.It was found that the surface of GO coating It is interacted with bacterial cell to reduce proliferation.Under higher enlargement ratio, what is observed is single bacterial cell and GO piece It tangles so as to cause film disturbance, it was reported that this is one of several possible mechanism of the bacteria resistance of GO.Further, for comprising The sample of rGO/SMB observes bacterium membrane damage and cytoplasm leakage, wherein discovery bacterial cell is random distribution.
With rGO-N2H4Coating (84 ° of WCA of ≈) is compared, rGO on piece/in SMB exist increase rGO/SMB composite coating Wetability (32 ° of WCA of ≈), this can reinforce the interaction between graphene film and bacterium.
The strong anti-bacterial effect of verified graphene composite material shows that almost 100% anti-Escherichia coli colonize Patience, have be used as control GO and rGO compared with significant better performance.The result shows that surface wettability should conduct It will affect the reactivity parameter of the bacteria resistance of graphene composite material and use.Together with the intrinsic bacteria resistance of SMB, it is believed that Increase the hydrophily on surface, this may be such that Bacillus coli cells and sharp graphene film are in close contact, thus cause bacterium thin Born of the same parents destroy towards active membrane.
In the whole instruction and the attached claims, unless the context otherwise requires, otherwise word " comprising " and all As the variant of " comprising " and "comprising" will be appreciated that imply the group for including the integer or step or integer or step, but not Exclude the group of any other integer or step or integer or step.
Be not to the reference of any existing publication (or the information therefrom obtained) or any known item in this specification, Also it is not construed as constituting technology involved in this specification to existing publication (or the information therefrom obtained) or known item A part of common knowledge in field recognize or approve or any type of introduction.

Claims (19)

1. a kind of graphene composite material comprising the graphene based material of hydration kodalk intercalation.
2. graphene composite material according to claim 1, wherein the graphene based material includes oxygen reduction fossil One or both of black alkene and graphene.
3. graphene composite material according to claim 1, wherein the hydration kodalk is with nano particle or film Form exist.
4. a kind of preparation method of graphene composite material, which comprises it includes graphene based material and water that (i), which is provided, The liquid composition of kodalk is closed, and (ii) removes liquid from the composition, to retain the institute in the composition Graphene based material and the hydration kodalk are stated, wherein the technique of the removing liquid in step (ii) promotes the hydration inclined Intercalation of the Boratex in the graphene based material, to provide the graphene composite material.
5. according to the method described in claim 4, wherein the liquid composition is water system liquid composition, and in step (ii) in, water is removed from the composition.
6. method according to claim 4 or 5, wherein the liquid including graphene based material and hydration kodalk Composition is by including that the water system liquid composition of graphene oxide and sodium borohydride provides, wherein the graphene oxide is by described Sodium borohydride reduction, to provide redox graphene and the hydration kodalk.
7. a kind of substrate comprising graphene composite material, the graphene composite material include that hydration kodalk is inserted The graphene based material of layer.
8. substrate according to claim 7, wherein the graphene composite material is coated on the surface of the substrate, Or it is distributed across base material substrate, or combinations thereof.
9. substrate according to claim 7 or 8, wherein the substrate include cellulosic material, polymer, metal, ceramics, Glass or combinations thereof.
10. substrate according to any one of claims 7 to 9, relative to there is no the graphene composite materials Substrate, show improved anti-flammability, improved abrasion performance, improvement microbial resistance, or combinations thereof.
11. a kind of method for more than one the performance for improving substrate, the method includes providing to have graphene system composite wood The substrate of material, wherein the graphene composite material includes the graphene based material for being hydrated kodalk intercalation.
12. according to the method for claim 11, wherein including the graphene composite material by using the substrate Liquid composition be coated or impregnated with, so that the substrate is provided with the graphene composite material.
13. according to the method for claim 11, wherein the substrate is provided with the graphene system in the following manner Composite material: substrate is coated or impregnated with by (i) with the liquid composition for including graphene based material and hydration kodalk, and (ii) remove liquid from the composition being coated with, thus retain be coated with or the composition that is impregnated in graphene based material Kodalk and the graphene composite material is formed with hydration.
14. according to the method for claim 13, wherein the liquid including graphene based material and hydration kodalk Composition is by including that the water system liquid composition of graphene oxide and sodium borohydride provides, wherein the graphene oxide is by described Sodium borohydride reduction, to provide redox graphene and the hydration kodalk.
15. according to the method for claim 11, wherein the substrate is thermoplastic polymer, and by by the polymerization Object and the graphene composite material melt-processed, make the substrate be provided with the graphene composite material.
16. according to the method for claim 11, wherein the substrate is thermosetting polymer, and by by graphene system Composite material is blended with the persursor material for the thermosetting polymer to be made, and the substrate is made to be provided with the graphene Composite material.
17. 1 to 16 described in any item methods according to claim 1, wherein the graphene based material includes oxygen reduction fossil One or both of black alkene and graphene.
18. 1 to 17 described in any item methods according to claim 1, wherein substrate is compound with the graphene system is not formed The hydration kodalk of a part of material impregnates.
19. a kind of graphene composite material is used to improve the purposes of more than one performance of substrate, wherein the graphene Composite material includes the graphene based material for being hydrated kodalk intercalation.
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