CN102627275A - Method for preparing graphene by melting carbon-containing alloy to separate out carbon in solidification process - Google Patents
Method for preparing graphene by melting carbon-containing alloy to separate out carbon in solidification process Download PDFInfo
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Abstract
The invention discloses a method for preparing graphene by melting carbon-containing alloy to separate out carbon in the solidification process. The method comprises the following steps of: firstly, preparing carbon-containing metal or alloy, wherein the content of carbon in the metal or the alloy is less than or equal to 10 percent; secondly, heating to melt or partially melt the carbon-containing metal or alloy; and thirdly, cooling at the speed of 0.1 to 109DEG C/s, solidifying the metal or the alloy and separating out the grapheme on the surface. The invention particularly discloses a single-roll preparation method similar to a preparation method for preparing amorphous metal or alloy. The melt carbon-containing metal or alloy melt is sprayed to the rotary metal roll surface, so that the melt is quickly cooled to obtain the grapheme. According to the method disclosed by the invention, the grapheme can be prepared in a large scale, high quality, high speed and low cost; and the method has important application for realizing industrialization and real application obtaining of the grapheme.
Description
Technical field:
The present invention relates to the Graphene preparation field, relate in particular to and a kind ofly in process of setting, separate out the method that carbon prepares Graphene through the fusion phosphorus-containing alloy.
Background technology:
(the Novoselov KS of Geim study group of Univ Manchester UK in 2004; Et al; Science; 2004,306:666) obtained mono-layer graphite-Graphene (Graphene) through the mechanically peel highly oriented pyrolytic graphite, theoretical and the perfect two-dirnentional structure of experimentally thinking can't obtain the Nobel Prize in physics in 2010 years in the understanding of non-zero absolute temperature stable existence before this work had been broken.Graphene is by individual layer sp
2The bi-dimensional cellular shape structure of the tightly packed one-tenth of hydridization carbon atom; Two-dirnentional structure that it is unique and splendid crystallography quality make Graphene have a lot of special character (Virendra S; Et al, Progress in Materials Science, 2011; 56:1178), like the high capacity of heat transmission (5000Wm
-1K
-1), outstanding mechanical property (Young's modulus reaches 1TPa), very high carrier mobility (250,000 cm
2/ Vs); High-specific surface area (2600m
2/ g); Because of the electrical type in the Graphene does not seemingly have the unusual quantum hall effect that quality dirac fermion shows; Complete single-layer graphene can not be through atom bigger than helium or the like.The special character of these of Graphene makes it aspect a lot of, obtain the potential application, makes the performance of some materials or device obtain greatly to improve or create brand-new material and device.For example, complete single-layer graphene can not can be used for making electrode materials, heat dissipation film, the ideal barrier film (Barrier Film) of battery through the characteristic of the atom bigger than helium; The high carrier mobility characteristic can be used to prepare ultra-high speed field-effect transistor and laser apparatus; High transparent and high conductivity make it possibly become good nesa coating and the alternative ITO material that generally uses at present, are used for aspects such as touch panel, flexible liquid crystal panel, solar cell; High specific surface area can improve the output power density of store battery and ultracapacitor; And its excellent mechanical property then makes it can make high performance composite, stretches into elevator of space or the like.
Graphene excellent properties and outstanding potential using value have excited people's research enthusiasm.Efficiently, conveniently, mass preparation goes out high-quality Graphene and can be the bases of realizing its application to its regulation and control of carrying out composition, structure, shape at an easy rate.So far, the method for preparing Graphene (is appointed literary talent etc., novel charcoal material, 2011,26 (1): 71) mainly contain: mechanically peel (Novoselov KS; Et al, Science, 2004,306:666), chemical stripping (Park S, Ruoff RS; Nature Nanotechnol, 2009,4:217) or chemosynthesis (Cai JM, et al, Nature; 2010,466:470), SiC epitaxy (Berger C, et al, Science, 2006; 312:1191), the epitaxy of single-crystal metal surface (Kevin FM, et al, Carbon, 2009,47:1806), chemical vapour deposition (CVD method; Li XS, et al, Science, 2009,324:1312) etc.These methods respectively have quality, the high-quality graphene film that the mechanically peel method is more difficult to get in the time of can obtaining to adopt additive method, and apparatus and process is simple, but is difficult for accomplishing scale production; Chemical peeling is realized the mass-producing of Graphene easily, but the Graphene of this method preparation contains more defective, to have a large amount of chemical functional group, subsequent disposal loaded down with trivial details; Chemical synthesis is not easy to obtain the bigger Graphene of area; The SiC epitaxy can obtain the single-layer graphene of big area better quality, but growth conditions is harsh and be difficult to transfer, has greatly limited this preparing method's popularization; The single-crystal metal epitaxial growth method is the method for preparing graphite flake layer in early days, but the making that metal epitaxial process cost is expensive and be difficult to mass-producing of single-crystal metal substrate and high vacuum; The CVD method; Be in the high temperature carbon-containing atmosphere, metal to be carried out carburizing earlier, afterwards metal cooled off fast a kind of method of preparation Graphene, this method preparation condition is simple, controlled; The Graphene quality that is obtained is high, area is big; Being easy to transfer on the needed substrate, is a kind of method of more promising scale preparation Graphene therefore, but on scale, quality and the controllability of preparation Graphene, still need develop raising at present.Therefore, to the research invention of the method for can high-efficiency large-scale producing Graphene, remaining rich challenge and need to be resolved hurrily, also is to realize its final key in application.
The mechanism for preparing Graphene from the CVD method can be known; Wherein Ni etc. has the metal of higher solubility to carbon; Be the difference that is utilized in carbon solubleness in metal under the high and low temperature; Separate out oversaturated carbon at low temperature and form Graphene, carburizing then is to make to be in for a long time under the metallic high temperature under the carbon-containing atmosphere under the high temperature, and carbon progressively infiltrates metal and accomplishes cementation process.High temperature carburizing process time wherein is longer, infiltrates a spot of carbon but its meaning just is metallic surface and shallow top layer, and this cementation process fully can prefabricated carbonaceous alloy and obtain.Simultaneously, show, when adopting the CVD method on the Ni tinsel, to produce Graphene though study; If cooling rate is too big, just can not obtain Graphene, still; Separating out with carbon atom of this carbon is diffused as the basis in solid metal; If carbon atom spreads in liquid or liquid and solid-state mixed state, carbon atom will be separated out at faster speed and can be generated Graphene in the shorter time, therefore can be with the Graphene of speed of cooling acquisition faster.Obtaining aspect the big speed of cooling, the preparation method of non-crystaline amorphous metal provides good reference, for example single rod preparation method and two roller preparing methods; The hammer anvil method is similar to single rod method, is suitable for high-meltiing alloy fusing and refrigerative molten drop method, centrifuging; Injection method; Melt is stained with method (Wang Juanjuan, non-crystalline solids and technology of preparing thereof (courseware)) or the like, and very high speed of cooling can be provided.And certain methods wherein like single-roller method, has become industrialized ordinary method.Therefore, if adopt the similar techniques means, might develop a kind of extensive, high quality, high-speed, the low-cost method for preparing Graphene.
Summary of the invention:
In view of this; The object of the present invention is to provide and a kind ofly in process of setting, separate out the method that carbon prepares Graphene through the fusion phosphorus-containing alloy; Be about to the phosphorus-containing alloy cooling of molten state, make it in process of setting, directly to produce Graphene, can realize the extensive Graphene of preparation continuously.
For achieving the above object, the present invention adopts following technical scheme:
A kind ofly in process of setting, separate out the method that carbon prepares Graphene, it is characterized in that: comprise the steps: the first step, preparation carbon containing metal or alloy, carbon content in the metal or alloy≤10% through the fusion phosphorus-containing alloy; In second step, heating makes fusing of carbon containing metal or alloy or partial melting; The 3rd step, cooling, speed of cooling is 0.1 ℃/s-10
9℃/s, metal or alloy solidifies and at surperficial indigenous graphite alkene.
Described metal and alloy can make its fusing through the whole bag of tricks, comprise middle and high frequency heating, irradiated heat, the heating of use resistance furnace, and directly energising heating, Heating temperature should make metal or alloy fusing partly occur at least.
The cooling of said metal and alloy melt; Comprise the present melt supercooled method of making amorphous metal or alloy of using; As methods such as the single rod method for preparing amorphous metal or alloy and two roller methods, metal or alloy melt coating method of the special proposition of the present invention institute or the like; Comprise that also other can make melt refrigerative method, for example naturally cooling under the room temperature, putting into holding furnace, to carry out stove according to certain speed of cooling cold, adopt alloy or alloy melt sprayed to form powder, melt evaporative condenser or the like.Refrigerative speed is according to requiring, can be from from 0.1 ℃/s to 10
9℃/s, mainly 10
2-10
7℃/the s scope, particularly 10
3-10
7℃/the interior best results of s scope.
Adopt the whole bag of tricks to make in the metal melt process of cooling carbon containing metal or alloy of molten state; No matter with alloy melting, still cooling can be carried out under vacuum state or particular pressure; Can under inert atmosphere, reducing atmosphere, carry out, also can directly under atmosphere, carry out.
Further, described carbon containing metal or alloy mainly comprises magnesium-yttrium-transition metal, or magnesium-yttrium-transition metal and other elements binary alloy or the multicomponent alloy formed.
Described fusion phosphorus-containing alloy, for carbon there being the metal or alloy of certain solubility, the phosphorus-containing alloy of forming with carbon.These have the metal or alloy of certain solubility to carbon, mainly comprise magnesium-yttrium-transition metal, or magnesium-yttrium-transition metal and other elements binary alloy or the multicomponent alloy formed, for example Ni, Fe, Pt, Ru, metal such as Cu/Ni and alloy or the like.Carbon is had the metal or alloy of certain solubility, can also contain nitrogen (N), boron (B), phosphorus (P), sulphur elements such as (S), these elements equally also can be separated out in the process that graphite is separated out, thereby realize the doping of Graphene.
Further, said second step can be put into the raw material for preparing the mineral compound pipe of crucible or band nozzle when heating, heat melting carbon containing metal or alloy then.
Nozzle can be designed to circular hole, strip, perforate (array is lined up in a plurality of holes) etc. on request, size according to the designs such as width, thickness of the sheet metal strip that will obtain.Further, when cooling off in said the 3rd step, fused carbon containing metal or alloy melt jet to the metal roll surface of rotation, is made the melt cooling and obtains Graphene; Employed processing parameter is: 1-200 centimetre of metallic roll diameter, 1-10000 rev/min of metallic roll rotating speed; Between metallic roll and the nozzle apart from 0.1-10 centimetre.
Further, when cooling off in said the 3rd step, earlier carbon containing metal or alloy melt jet is arrived between two metal roll surfaces of rotation, melt is sheet metal strip, the spontaneous formation Graphene on the two sides of band by metallic roll cooling and calendering; Employed processing parameter is: 1-200 centimetre of metallic roll diameter, 1-10000 rev/min of metallic roll rotating speed, between described two metallic roll and the nozzle apart from 0.1-10 centimetre.
Further, heating or the cooling in the 3rd step in said second step are carried out in rare gas element or reducing gas, and the pressure of said gas is 10
-6Pa is between the 10MPa.The employed gas of described rare gas element or reducing gas can be Ar, He, N
2, H
2, gas such as CO and composition thereof.
Further, in said the 3rd step when cooling off, phosphorus-containing alloy is applied or is injected on the metallic strip surface of motion and makes it cooling, Graphene is separated out from the alloy surface that solidifies in this process; The movement velocity of said metal strip is 0.1-100m/s.
Further; The metal strip of described motion adopts the mode of folding and unfolding metal coil tape that metal strip is moved, and phosphorus-containing alloy melt direct injection or be coated on the metal strip forms the phosphorus-containing alloy film above that; And in the alloy film forming process, also form Graphene simultaneously on its surface.
Further, in said the 3rd step when cooling off, carbon containing metal or alloy melt is adopted spray method or the solid surface that mode is coated to high heat conduction such as topples over, carbon containing metal or alloy melt solidifies and indigenous graphite alkene at this solid surface.
Further; In said the 3rd step when cooling off, carbon containing metal alloy melt droplets between two relative movement and heat conduction good metal surface, is cooled off rapidly after melt is squeezed and is pressed into sheet or specific shape; In this process, from the metal or alloy surface indigenous graphite alkene that solidifies.
Further; When in said the 3rd step, cooling off; To be in carbon containing metal or alloy melt jet in the cylinder intermediary silica tube of high speed rotating to the internal surface of cylinder; And with melt along the axial-movement of cylinder and obtain metal or alloy band, at this spiral helicine metal or alloy strip surface indigenous graphite alkene that solidifies at the cylinder inner wall curl; Said drum diameter 1-100 centimetre, velocity of rotation is 1-2000 rev/min, silica tube lift velocity 1-500 cm per minute.
Further; When in said the 3rd step, cooling off; Tinsel is skimmed over carbon containing metal or alloy melt; Or with rosette along carbon containing metal or alloy bath surface high speed rotating, thereby melt be stained with skim by tinsel or disk the carbon containing metal or alloy cooled off rapidly, be stained with indigenous graphite alkene on the skim phosphorus-containing alloy surface that at this.
Beneficial effect of the present invention is:
Advantage of the present invention is mainly can be on a large scale, high quality, prepare Graphene at a high speed, cheaply, to the industrialization that realizes Graphene with real obtain to use have important effect.Wherein for single roller method of similar preparation amorphous metal or alloy strip steel rolled stock and two these class methods of roller method; Be characterized in making molten metal or the condensation of alloy high speed get off to become solid metal or alloy through rapid quenching; And in this condensation process; Carbon will be separated out the formation Graphene from the metal or alloy surface; In the present invention, be referred to as the graphene preparation method of spontaneous the separating out of molten metal fast quenching carbon (Molten melt quenched-induced carbon self segregation-MMQCSS).For single rod method, its speed of cooling is 10
5℃/the s magnitude, maximum can reach 10
6℃/s, the rotating speed by the copper rod determines to a great extent.Single roller method is methods of sophisticated preparation of industrialization non-crystaline amorphous metal with two roller preparing methods; Product is tens microns of thickness; Width number centimetre is to tens of centimetres, and length then can reach tens of kilometers metal thin strip according to the amount of raw material, and the preparation speed of band can reach tens of meter per seconds; Therefore can obtain large-sized Graphene fast, its preparation speed is to adopt conventional CVD method to prepare thousands of times of speed of Graphene at present.And when adopting the metal or alloy melt jet or being coated in the sheet metal strip of high-speed motion, melt can be tiled on the sheet metal strip and cooling fast, in process of cooling, and indigenous graphite alkene.This kind method; Except having single roller method and two roller methods to prepare the advantage of Graphene; Can also prepare the higher Graphene of width; Because the own width of sheet metal strip that is used to carry the carbon containing metal or alloy is big (above 100 centimetres) very, so can obtain the very big coat of width, on the very big coat of this width, then can separate out the very big Graphene of width.And for the phosphorus-containing alloy particle that sprays, then indigenous graphite alkene in the process of solidifying forms the alloying pellet that is coated with Graphene.
Description of drawings:
Fig. 1 is the device synoptic diagram of single roller method of employed similar preparation amorphous metal or alloy strip steel rolled stock among the embodiment 1-3 among the present invention;
Fig. 2 is the device of two roller methods of employed similar preparation amorphous metal or alloy strip steel rolled stock among the embodiment 4 among the present invention;
Fig. 3 is sem (SEM) image that adopts the Ni/C alloy strip steel rolled stock surface of single-roller method preparation in the embodiment of the invention 1;
Fig. 4 adopts the Raman on the Ni/C alloy strip steel rolled stock surface of single-roller method preparation to detect collection of illustrative plates in the embodiment of the invention 1;
Fig. 5 in the embodiment of the invention 5 with the metal or alloy melt jet or be coated in the synoptic diagram of the metal foil roll coil of strip of folding and unfolding;
Fig. 6 is for using the synoptic diagram that centrifuging prepares Graphene in the embodiment of the invention 7.
Embodiment:
Below in conjunction with accompanying drawing and embodiment technical scheme of the present invention is further described:
Embodiment 1:
As shown in Figure 1, use single roller apparatus of preparation amorphous metal or alloy strip steel rolled stock (paper tinsel band) to prepare Graphene.Put into the quartz test tube that has nozzle to the nickel block of certain mass proportioning and carbon (carbon containing 1.5wt%); Through ruhmkorff coil heating melting; Obtaining the Ni/C alloy melt and it being ejected into velocity of rotation at about 1500 ℃ is on 2000 rev/mins the metal Cu roller, 32 centimetres of metal Cu roller diameters, and the high speed rotating through metallic roll solidifies melt quenching; Obtain long Ni/C Alloy Foil band, its speed of cooling is 10
5℃/the s magnitude, maximum can reach 10
6℃/s, the rotating speed by the copper rod determines to a great extent.On this paper tinsel band, the spontaneous generation Graphene of separating out of carbon, this method the present invention who prepares Graphene is referred to as the spontaneous separation method of molten metal quenching carbon.Sem (SEM) figure by Fig. 3 Ni/C alloy strip steel rolled stock surface is visible, and translucent membranoid substance is arranged on it, and fold is arranged on the membranoid substance; Fig. 4 then is that the Raman on Ni/C alloy strip steel rolled stock surface detects collection of illustrative plates, it is thus clear that have only G peak (about 1583cm
-1) and 2D peak (about 2699cm
-1) and do not have D peak (about 1350cm
-1) and the 2D peak height in the G peak, this explains that resulting membranoid substance is not amorphous carbon but Graphene or multilayer graphite flake, but because the 2D peak height in the G peak, more possibly be the less Graphene of the individual layer or the number of plies.
Embodiment 2:
Put into the quartz test tube that has nozzle to the nickel block of certain mass proportioning and carbon (carbon containing 1.0wt%); Through ruhmkorff coil heating melting, obtaining the Ni/C alloy melt and it being ejected into velocity of rotation at about 1550 ℃ is on 3500 rev/mins the metal Cu roller, realizes quenching through the high speed rotating of metallic roll; Obtain long Ni/C Alloy Foil band; On this paper tinsel band, also obtained translucent membranoid substance, fold is arranged on the membranoid substance; The Raman on alloy strip steel rolled stock surface also has only G peak and 2D peak and does not have D peak and 2D peak height in the G peak, and this explains that resulting membranoid substance is not amorphous carbon but the less Graphene of the single-layer graphene or the number of plies.
Embodiment 3:
Mix the nickel by powder of certain mass proportioning, copper powder and carbon dust by a certain percentage (carbon containing 1.0wt%, cupric 9.0wt%), adopt hydropress process annealing under green compact and the high temperature reduction atmosphere (1000 ℃, 5 hours; Hydrogen and argon gas total flux 300sccm-standard cubic centimeter per minute, volume ratio 1:9), obtain the base substrate of Ni/Cu/C, Ni and Cu and C have certain diffusion in this base substrate.This base substrate is put into the quartz test tube that has nozzle, also can select mineral compound pipes such as carbon tube, ZrO pipe for use.Obtaining the Ni/Cu/C alloy melt and it is ejected into velocity of rotation at about 1550 ℃ through ruhmkorff coil heating melting is on 3000 rev/mins the metal Cu roller; Realize quenching through the high speed rotating of metallic roll; Obtain long Ni/Cu/C Alloy Foil band; On this paper tinsel band, also obtained translucent membranoid substance, fold is arranged on the membranoid substance; The Raman on alloy strip steel rolled stock surface also has only G peak and 2D peak and does not have the D peak, and this explains that resulting membranoid substance is not amorphous carbon but the less Graphene of the number of plies.
Embodiment 4:
As shown in Figure 2, use the two roller apparatus that prepare amorphous metal or alloy strip steel rolled stock.Mix, put into the quartz test tube that has nozzle to the nickel of certain mass proportioning, Ni/C alloy by a certain percentage; Through ruhmkorff coil heating melting; Obtaining Ni/C alloy melt (carbon containing 1.2wt%) and at about 1500 ℃ it being ejected into velocity of rotation is 2000 rev/mins; But direction of rotation two metal Cu rollers between, two metal Cu roller diameters are 20 centimetres, the gap between two Cu rollers is 300 microns.The phosphorus-containing alloy melt is realized quenching and ejection downwards through the high speed rotating of metallic roll, obtains long Ni/C Alloy Foil band.On this paper tinsel band, also obtained translucent membranoid substance, fold is arranged on the membranoid substance; The Raman on alloy strip steel rolled stock surface also has only G peak and 2D peak and does not have D peak and 2D peak height in the G peak, and this explains that resulting membranoid substance is not amorphous carbon but Graphene.
Embodiment 5:
With Ni, Fe, the fusing of Ni/C master alloy, adopt the plumbago crucible fusing and, make the weight ratio of Ni in the alloy, Fe, C reach 92:7.6:0.4 1600 ℃ of insulations.Is that 50 centimetres Cu is with the phosphorus-containing alloy melt jet to high-speed motion (20m/s), width, and the Cu band is through the draw off gear motion, and the device synoptic diagram is seen Fig. 5, obtains thickness and is 30 microns, width and surpass 30 centimetres Ni/Fe/C alloy coat (film).On this mf, the SEM picture shows can separate out translucent membranaceous material, and the Raman spectrum shows equally, on alloy firm, has separated out single-layer graphene or multi-layer graphene.
Embodiment 6:
With Co, Ni/C master alloy fusing (weight ratio of Ni, Co, C is 87.5:11.7:0.8); And adopt spray method phosphorus-containing alloy to be ejected in the reaction chamber of Ar atmosphere with Ar; Obtain the Ni/Co/C nano particle, around nano particle, formed graphite linings.Because be to adopt spray method, speed of cooling is very high, and speed of cooling is 10
3-10
7℃/s, metal or alloy solidifies and at surperficial indigenous graphite alkene.
Embodiment 7:
Mix the nickel of certain mass proportioning, Ni/C alloy by a certain percentage; (but its nozzle direction is not downward vertically in ground to put into the quartz test tube that has nozzle; But be parallel to ground) in; Through ruhmkorff coil heating melting, obtain Ni/C alloy melt (carbon containing 0.5wt%) and adopt centrifuging to prepare spiral sheet metal strip at about 1500 ℃, the device synoptic diagram is seen Fig. 6.In the preparation process, 50 centimetres of drum diameters, velocity of rotation is 120 rev/mins, silica tube lift velocity 100 cm per minute.Also can see translucent membranaceous material through the SEM photo on the sheet metal strip that is obtained, the Raman spectrum also shows simultaneously, has obtained Graphene.
Embodiment 8:
With Ni, Fe, the fusing of Ni/C master alloy, under vacuum, adopt the plumbago crucible fusing and, make the weight ratio of Ni in the alloy, Fe, C reach 96:4.5:0.5 1650 ℃ of insulations.Afterwards it is poured over ground fast and is on the metal Cu plate of 20 degree, the metal melt of trickling forms zonal film, and SEM observes and to show, on this metallic membrane, has also obtained translucent membranoid substance, and the Raman spectrum shows equally, has obtained Graphene.
Embodiment 9:
The quick refrigerative hammer anvil of metal and alloy melt method is similar with making; Phosphorus-containing alloy (the Ni:C weight ratio is 99.7:0.3) is dropped on the metal Cu plate surface (squares that the length of side is 50 centimetres); The onesize Cu plate of another piece is pressed in rapidly to drip to be had on the Cu plate of molten drop; The melt back that is squeezed is cooled off rapidly and is pressed into thickness less than 100 microns thin slice, and speed of cooling is 10
5℃/the s magnitude.In this process, separated out Graphene from the phosphorus-containing alloy slice surfaces that solidifies.
Embodiment 10:
The alloy melt of melting Pt, C (Pt content 99wt%) immerses alloy melt and taking-up rapidly with Pt plate (2 millimeters) afterwards, on this Pt plate, obtains the semitransparent thin film of one deck carbon containing Pt alloy.Research shows, has also separated out Graphene on the film of this carbon containing Pt alloy.
Embodiment 11:
With rolling be the alloy sheet of 100 microns Ni/Fe/C (weight ratio 80:29.2:0.8), 1050 ℃ of heating are 1 hour under high vacuum condition, adopt the speed cooling of 50 ℃/s afterwards.SEM observes and can find on alloy sheet, to separate out semitransparent thin film.Raman shows that this film is a Graphene.
Embodiment 12:
Put into the ZrO that has nozzle to the iron block of certain mass proportioning and carbon (carbon containing 3wt%)
2In the test tube; Through ruhmkorff coil heating melting, obtaining the Fe/C alloy melt and it being ejected into velocity of rotation at about 1600 ℃ is on 4000 rev/mins the metal Cu roller, 50 centimetres of metal Cu roller diameters; High speed rotating through metallic roll makes melt quenching, and speed of cooling is approximately 10
5℃/the s magnitude, obtain long Fe/C Alloy Foil band, on this paper tinsel band, the spontaneous generation Graphene of separating out of carbon.
Embodiment 13:
Put into the plumbago crucible that has nozzle to the nickel block of certain mass proportioning and carbon (carbon containing 1wt%); Through the resistive heating melting, obtaining the Ni/C alloy melt and it being ejected into velocity of rotation at about 1550 ℃ is on 1500 rev/mins the metal Cu roller, 50 centimetres of metal Cu roller diameters; High speed rotating through metallic roll makes melt quenching; Obtain long Ni/C Alloy Foil band, on this paper tinsel band, the spontaneous generation Graphene of separating out of carbon.
Embodiment 14:
The nickel block of certain mass proportioning, silver bullion and carbon (carbon containing 0.8wt%; Argentiferous 10wt%) put into the plumbago crucible that has nozzle, through the resistive heating melting, obtaining the Ni/Ag/C alloy melt and it being ejected into velocity of rotation at about 1525 ℃ is on 150 rev/mins the metal Cu roller; 5 centimetres of metal Cu roller diameters; High speed rotating through metallic roll makes melt quenching, and speed of cooling is approximately 1000 ℃/s magnitude, obtains long Ni/C Alloy Foil band; On this paper tinsel band, the spontaneous generation Graphene of separating out of carbon.
Embodiment 15:
At first put into the graphite test tube that has nozzle to certain mass through the Ni/C (carbon containing 5wt%) of arc melting gained; Through the resistive heating melting; Obtaining the Ni/C alloy melt and it being ejected into velocity of rotation at about 1570 ℃ is on 500 rev/mins the metal Cu roller; 50 centimetres of metal Cu roller diameters, the high speed rotating through metallic roll makes melt quenching, and speed of cooling is approximately 10
5℃/the s magnitude, obtain Ni/C Alloy Foil band, on this paper tinsel band, the spontaneous generation Graphene of separating out of carbon.
Embodiment 16:
As shown in Figure 2, use the two roller apparatus that prepare amorphous metal or alloy strip steel rolled stock.Mix, put into the ZrO that has nozzle to the nickel of certain mass proportioning, platinum, Ni/C alloy by a certain percentage
2In the crucible; Through ruhmkorff coil heating melting; Obtaining Ni/Pt/C alloy melt (carbon containing 1.2wt%, platiniferous 3.8wt%) and at about 1600 ℃ it being ejected into velocity of rotation is 3000 rev/mins, but direction of rotation two metal Cu rollers between; Two metal Cu roller diameters are 20 centimetres, and the gap between two Cu rollers is 300 microns.The phosphorus-containing alloy melt is realized quenching and ejection downwards through the high speed rotating of metallic roll, obtains long Ni/Pt/C Alloy Foil band.On this paper tinsel band, also obtained translucent membranoid substance, fold is arranged on the membranoid substance; The Raman on alloy strip steel rolled stock surface also has only G peak and 2D peak and does not have the D peak, and this explains that resulting membranoid substance is not amorphous carbon but Graphene.
Claims (12)
1. in process of setting, separate out the method that carbon prepares Graphene through the fusion phosphorus-containing alloy for one kind, it is characterized in that: comprise the steps:
The first step, preparation carbon containing metal or alloy, carbon content in the metal or alloy≤10%;
In second step, heating makes fusing of carbon containing metal or alloy or partial melting;
The 3rd step, cooling, speed of cooling is 0.1 ℃/s-10
9℃/s, metal or alloy solidifies and at surperficial indigenous graphite alkene.
2. as claimed in claim 1ly a kind ofly in process of setting, separate out the method that carbon prepares Graphene through the fusion phosphorus-containing alloy; It is characterized in that: described carbon containing metal or alloy mainly comprises magnesium-yttrium-transition metal, or magnesium-yttrium-transition metal and other elements binary alloy or the multicomponent alloy formed.
3. as claimed in claim 2ly a kind ofly in process of setting, separate out the method that carbon prepares Graphene through the fusion phosphorus-containing alloy; It is characterized in that: said second step is when heating; Can the raw material that prepare be put into the mineral compound pipe of crucible or band nozzle, heat melting carbon containing metal or alloy then.
4. describedly a kind ofly in process of setting, separate out the method that carbon prepares Graphene like claim 1,2 or 3 through the fusion phosphorus-containing alloy; It is characterized in that: when cooling off in said the 3rd step; Fused carbon containing metal or alloy melt jet to the metal roll surface of rotation, is made the melt cooling and obtains Graphene; Employed processing parameter is: 1-200 centimetre of metallic roll diameter, 1-10000 rev/min of metallic roll rotating speed; Between metallic roll and the nozzle apart from 0.1-10 centimetre.
5. describedly a kind ofly in process of setting, separate out the method that carbon prepares Graphene like claim 1,2 or 3 through the fusion phosphorus-containing alloy; It is characterized in that: when cooling off in said the 3rd step; Earlier carbon containing metal or alloy melt jet is arrived between two metal roll surfaces of rotation; Melt is sheet metal strip, the spontaneous formation Graphene on the two sides of band by metallic roll cooling and calendering; Employed processing parameter is: 1-200 centimetre of metallic roll diameter, 1-10000 rev/min of metallic roll rotating speed, between described two metallic roll and the nozzle apart from 0.1-10 centimetre.
6. describedly a kind ofly in process of setting, separate out the method that carbon prepares Graphene like claim 4 or 5 through the fusion phosphorus-containing alloy; It is characterized in that: heating or the cooling in the 3rd step in said second step are carried out in rare gas element or reducing gas, and the pressure of said gas is 10
-6Pa is between the 10MPa.
7. according to claim 1 or claim 2 a kind of separates out the method that carbon prepares Graphene through the fusion phosphorus-containing alloy in process of setting; It is characterized in that: when cooling off in said the 3rd step; Phosphorus-containing alloy is applied or is injected on the metallic strip surface of motion and makes it cooling, and Graphene is separated out from the alloy surface that solidifies in this process; The movement velocity of said metal strip is 0.1-100m/s.
8. as claimed in claim 7ly a kind ofly in process of setting, separate out the method that carbon prepares Graphene through the fusion phosphorus-containing alloy; It is characterized in that: the metal strip of described motion adopts the mode of folding and unfolding metal coil tape that metal strip is moved; Phosphorus-containing alloy melt direct injection or be coated on the metal strip; Form the phosphorus-containing alloy film above that, and in the alloy film forming process, also form Graphene simultaneously on its surface.
9. according to claim 1 or claim 2 a kind of separates out the method that carbon prepares Graphene through the fusion phosphorus-containing alloy in process of setting; It is characterized in that: when in said the 3rd step, cooling off; Carbon containing metal or alloy melt is adopted spray method or the solid surface that mode is coated to high heat conduction such as topples over, and carbon containing metal or alloy melt solidifies and indigenous graphite alkene at this solid surface.
10. according to claim 1 or claim 2 a kind of separates out the method that carbon prepares Graphene through the fusion phosphorus-containing alloy in process of setting; It is characterized in that: when in said the 3rd step, cooling off; With carbon containing metal alloy melt droplets between two relative movement and heat conduction good metal surface; Cool off rapidly after melt is squeezed and be pressed into sheet or specific shape, in this process, from the metal or alloy surface indigenous graphite alkene that solidifies.
11. according to claim 1 or claim 2 a kind of separates out the method that carbon prepares Graphene through the fusion phosphorus-containing alloy in process of setting; It is characterized in that: when in said the 3rd step, cooling off; To be in the internal surface of the carbon containing metal or alloy melt jet cylinder in the cylinder intermediary silica tube of high speed rotating; And with melt along the axial-movement of cylinder and obtain metal or alloy band, at this spiral helicine metal or alloy strip surface indigenous graphite alkene that solidifies at the cylinder inner wall curl; Said drum diameter 1-100 centimetre, velocity of rotation is 1-2000 rev/min, silica tube lift velocity 1-500 cm per minute.
12. according to claim 1 or claim 2 a kind of separates out the method that carbon prepares Graphene through the fusion phosphorus-containing alloy in process of setting; It is characterized in that: when in said the 3rd step, cooling off; Tinsel is skimmed over carbon containing metal or alloy melt; Or with rosette along carbon containing metal or alloy bath surface high speed rotating, thereby melt be stained with skim by tinsel or disk the carbon containing metal or alloy cooled off rapidly, be stained with indigenous graphite alkene on the skim phosphorus-containing alloy surface that at this.
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