CN107352534A - The graphene oxide that a kind of nanometer tungsten carbide is modified - Google Patents
The graphene oxide that a kind of nanometer tungsten carbide is modified Download PDFInfo
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- CN107352534A CN107352534A CN201710506520.3A CN201710506520A CN107352534A CN 107352534 A CN107352534 A CN 107352534A CN 201710506520 A CN201710506520 A CN 201710506520A CN 107352534 A CN107352534 A CN 107352534A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
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- 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
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The present invention provides a kind of modified graphene, and the precursor mixture that tungstenic is mixed into by a certain proportion of graphene oxide, absolute ethyl alcohol, deionized water, ammonium metatungstate and tungsten carbonyl mixes.The present invention has been effectively kept the content for obtaining coat inside graphene, self-lubricating property of the graphene applied to graphene inside self-lubricating wear-resistant coating has been played to a greater extent, the coefficient of friction of thermal spraying tungsten carbide coating is reduced, the present invention, which expands, is applied to the harsher part self-lubricating abrasion-resistant protection of friction duty in empty day field.
Description
Technical field
The invention belongs to graphene/nanometer tungsten carbide composite technical field, more particularly to a kind of modified graphite
Alkene.
Background technology
Through studying for a long period of time, analyzing, it is found that graphene is that carbon atom is tightly packed into individual layer bi-dimensional cellular shape lattice structure
A kind of carbonaceous new material, it is the elementary cell of the most frequently used kollag-graphite of structure, there is the friction system lower than graphite
Number, is a kind of new self-lubricant anti-friction coating additive.
But graphene lighter weight, belong to a kind of carbonaceous material of individual layer bi-dimensional cellular shape lattice structure, it is as profit
Lubrication prescription is applied to the loss that graphene in hot-spraying coating in powder process and coating preparation process is prepared be present.
It is primarily due to the carbon material that graphene is nanoscale single layer structure, lighter weight, ceramic-like tungsten carbide dusty spray
Quality is big, if graphene is directly appended in tungsten carbide dusty spray, graphene and tungsten-carbide powder compatibility extreme difference, very
It is difficult with powder effectively uniformly mix and adulterate, therefore due to spraying particle flight flame stream higher speed in thermal spray process
Degree can cause the graphene mass loss of very light weight, and spraying particle line temperature is higher in addition, will also result in the heat of graphene
Deformation and heat loss.
In addition, the graphene applied to self-lubricating wear-resistant coating is modified tungsten carbide self-lubricating additive, graphene is spraying
During can by high speed flame stream blow fly and lose, it is difficult in resurfacing reservation graphene composition.In addition, graphene specific surface area compared with
Greatly, activity is high, easily reunites with tungsten carbide dusty spray compound tense, it is difficult to ensure that uniformly mixed in dusty spray, so as to
It is difficult to ensure for preparing coating has self-lubricating abrasion-resistant characteristic.
The content of the invention
Modified graphene surface in situ of the present invention grows nano silicon carbide tungsten particle, and nanometer is realized by controlling reaction condition
Tungsten carbide particle regulates and controls in the yardstick, pattern, distribution of surface of graphene oxide, prepares with certain weight proportion, and can be with
Tungsten-carbide powder preferably reaches the modified graphene oxide of preferable com-patibilising effect, and carbonization is compounded in as self-lubricating additive application
, can be preferable with dusty spray compatibility in tungsten dusty spray, alternatively, it is also possible to obtain uniformly mixing and mixing well with powder
It is miscellaneous, ensure that graphene reaches certain Qian He with powder, reach certain bond strength, ensure in spraying process in powder
The graphene in portion will not be sprayed-on high temperature, high speed flame stream and weight loss or fire damage.It has been effectively kept acquisition coat inside
The content of graphene, the self-lubricating for having played graphene to a greater extent applied to graphene inside self-lubricating wear-resistant coating are special
Property, the coefficient of friction of thermal spraying tungsten carbide coating is reduced, the present invention expands harsher applied to friction duty in empty day field
Part self-lubricating abrasion-resistant protection.
The technical problems to be solved by the invention are in view of the shortcomings of the prior art, there is provided a kind of modified graphene.
Technical scheme is as follows:
A kind of modified graphene, wherein, by a certain proportion of graphene oxide, absolute ethyl alcohol, deionized water, ammonium metatungstate and carbonyl
The precursor mixture that base tungsten is mixed into tungstenic mixes.
In above-mentioned, 1g-6g graphene oxides are weighed, add 1000g absolute ethyl alcohols, uniform stirring mixing;Add 50-
800g deionized waters are mixed, in ultrasonic disperse instrument, from 10mm vibration amplitude arms, and sonication treatment time 30-180min,
Supersonic frequency is 10-15Hz, obtains the mixed liquor of graphene dispersion.
In above-mentioned, the forerunner that mass percent is mixed into tungstenic for 99% ammonium metatungstate and 1% tungsten carbonyl is weighed respectively
Body mixture, weigh 1g tungstenic precursor mixtures and be added in graphene dispersion solution, stir 30-60min;Whipping process
In constantly instill absolute ethyl alcohol, infusion volume 18-324g, then by obtained precipitation filter, heat 70-90 in an oven
DEG C, 10-60min is dried, obtains drying powder.
In above-mentioned, the drying powder that will obtain is placed in alumina crucible, and a certain amount of H2, H2 are led in tubular reduction furnace
Flow is l00sccm, with 5-70 DEG C/min heating rate, is heated to 700-900 DEG C;Soaking time is 1-3h, is finally led to
H2 is cooled to room temperature, obtains modified graphene.
Usefulness of the present invention:For modified graphene, modified graphene surface in situ grows nano silicon carbide tungsten particle,
Realize that nano silicon carbide tungsten particle regulates and controls in the yardstick, pattern, distribution of surface of graphene oxide by controlling reaction condition,
Prepare with certain weight proportion, and can preferably reach the modified graphene oxide of preferable com-patibilising effect with tungsten-carbide powder, as
Self-lubricating additive application is compounded in tungsten carbide dusty spray, can be preferable with dusty spray compatibility, alternatively, it is also possible to
Powder obtains well uniformly mixing and doping, ensures that graphene reaches certain Qian He with powder, the combination for reaching certain is strong
Degree, ensure that the graphene in spraying process inside powder will not be sprayed-on high temperature, high speed flame stream and weight loss or fire damage.
The content for obtaining coat inside graphene has been effectively kept, graphene has been played to a greater extent and has been applied applied to self-lubricating abrasion-resistant
The self-lubricating property of the internal graphene of layer, the coefficient of friction of thermal spraying tungsten carbide coating is reduced, the present invention, which expands, is applied to empty day
The part self-lubricating abrasion-resistant protection that friction duty is harsher in field.
Brief description of the drawings
Fig. 1 is the X-ray diffractogram that graphene is modified tungsten carbide self-lubricating abrasion-resistant additive.
Fig. 2 is the scanning electron microscope (SEM) photograph that graphene is modified tungsten carbide self-lubricating abrasion-resistant additive.
Fig. 3 is the high power scanning electron microscope (SEM) photograph that graphene is modified tungsten carbide self-lubricating abrasion-resistant additive.
Fig. 4 is the transmission electron microscope picture that graphene is modified tungsten carbide self-lubricating abrasion-resistant additive.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
Modified graphene of the present invention, by a certain proportion of graphene oxide, absolute ethyl alcohol, deionized water, ammonium metatungstate
The precursor mixture that tungstenic is mixed into tungsten carbonyl mixes, and in above-mentioned, weighs 1g-6g graphene oxides, adds 1000g
Absolute ethyl alcohol, uniform stirring mixing;Add 50-800g deionized waters to be mixed, in ultrasonic disperse instrument, from 10mm
Vibration amplitude arm, sonication treatment time 30-180min, supersonic frequency 10-15Hz, obtain the mixed liquor of graphene dispersion.On
In stating, the precursor mixture that mass percent is mixed into tungstenic for 99% ammonium metatungstate and 1% tungsten carbonyl is weighed respectively, is claimed
Take 1g tungstenic precursor mixtures to be added in graphene dispersion solution, stir 30-60min;Nothing is constantly instilled in whipping process
Water-ethanol, infusion volume 18-324g, then obtained precipitation is filtered, heat 70-90 DEG C in an oven, dry 10-
60min, obtain drying powder.In above-mentioned, the drying powder that will obtain is placed in alumina crucible, is led in tubular reduction furnace
A certain amount of H2, H2 flow are l00sccm, with 5-70 DEG C/min heating rate, are heated to 700-900 DEG C;Soaking time is
1-3h, finally lead to H2 and be cooled to room temperature, obtain modified graphene.
Modified graphene preparation process of the present invention is as follows:1g graphene oxides are weighed, add 1000g absolute ethyl alcohols, uniformly
It is stirred, is mixed adding 50g deionized waters, in ultrasonic disperse instrument, from 10mm vibration amplitude arms, sonication treatment time
For 30min, supersonic frequency 10Hz, the mixed liquor of graphene dispersion is obtained, weighs the metatungstic acid that mass percent is 99% respectively
Ammonium and 1% tungsten carbonyl are mixed into the precursor mixture of tungstenic, weigh 1g tungstenic precursor mixtures and are added to graphene dispersion
In solution, 30min is stirred, absolute ethyl alcohol is constantly instilled in whipping process, infusion volume 18g, is then filtered obtained precipitation,
70 DEG C are heated in an oven, 10min is dried, the drying powder that will be obtained, is placed in alumina crucible, are led in tubular reduction furnace
A certain amount of H2, H2 flow are l00sccm, with 5 DEG C/min heating rate, are heated to 700 DEG C, soaking time 1h, finally lead to
H2 is cooled to room temperature, obtains modified graphene, and graphene can be used as to be modified tungsten carbide self-lubricating abrasion-resistant additive and used.
The modified graphene prepared as shown in Figure 1 for the example, wherein graphene are modified the addition of tungsten carbide self-lubricating abrasion-resistant
The XRD of agent, it can be seen that all characteristic peaks are mutually fitted like a glove with WC thing in figure, and surface graphenic surface is loaded with
WC thing phases.
The modified graphene of example preparation is illustrated in figure 2, graphenic surface growth in situ tungsten carbide nano particle
Scanning electron microscope (SEM) photograph, it can be seen that the tungsten carbide particle of white nanoscale is evenly distributed in graphenic surface, and does not destroy stone
The black original lamellar structure characteristic of alkene.
Fig. 3 is modified graphene prepared by the example, wherein, the high power of graphenic surface growth in situ tungsten carbide particle is swept
Retouch electron microscope, it can be seen that the size of tungsten carbide particle is between 10-20nm, it was demonstrated that tungsten carbide particle yardstick is small, is evenly distributed.
It can be seen that graphene, which is modified tungsten carbide self-lubricating abrasion-resistant additive, is closely adhered to spray coating powder shown in Fig. 4 arrows
Last surface, reach preferably compatible.
Embodiment 2:
On the basis of above-described embodiment, modified graphene provided by the invention, by a certain proportion of graphene oxide, anhydrous second
The precursor mixture that alcohol, deionized water, ammonium metatungstate and tungsten carbonyl are mixed into tungstenic mixes, and specific preparation process is such as
Under:2g graphene oxides are weighed, 1000g absolute ethyl alcohols is added, uniform stirring mixing, is mixed adding 60g deionized waters,
In ultrasonic disperse instrument, from 10mm vibration amplitude arms, sonication treatment time 60min, supersonic frequency 12Hz, graphene point is obtained
Scattered mixed liquor, weighs ammonium metatungstate that mass percent is 99% respectively and 1% tungsten carbonyl is mixed into the presoma of tungstenic and mixed
Compound, weigh 1g tungstenic precursor mixtures and be added in graphene dispersion solution, stir 40min, constantly dripped in whipping process
Enter absolute ethyl alcohol, infusion volume 84g, then filter obtained precipitation, heat 80 DEG C in an oven, dry 20min, will obtain
Drying powder, be placed in alumina crucible, in tubular reduction furnace lead to a certain amount of H2, H2 flows are l00sccm, with 20 DEG C/
Min heating rate, 700 DEG C, soaking time 1h are heated to, finally lead to H2 and be cooled to room temperature, obtain modified graphene, and can
Tungsten carbide self-lubricating abrasion-resistant additive is modified as graphene to use.
Embodiment 3:
On the basis of above-described embodiment, modified graphene provided by the invention, by a certain proportion of graphene oxide, anhydrous second
The precursor mixture that alcohol, deionized water, ammonium metatungstate and tungsten carbonyl are mixed into tungstenic mixes, and specific preparation process is such as
Under:3g graphene oxides are weighed, 1000g absolute ethyl alcohols is added, uniform stirring mixing, is mixed adding 700g deionized waters
Close, in ultrasonic disperse instrument, from 10mm vibration amplitude arms, sonication treatment time 120min, supersonic frequency 12Hz, obtain graphite
The scattered mixed liquor of alkene, the forerunner that mass percent is mixed into tungstenic for 99% ammonium metatungstate and 1% tungsten carbonyl is weighed respectively
Body mixture, weigh 1g tungstenic precursor mixtures and be added in graphene dispersion solution, stir 50min, in whipping process not
It is disconnected to instill absolute ethyl alcohol, infusion volume 168g, then obtained precipitation is filtered, heat 80 DEG C in an oven, dry 20min,
The drying powder that will be obtained, is placed in alumina crucible, and a certain amount of H2 is led in tubular reduction furnace, and H2 flows are l00sccm, with
30 DEG C/min heating rate, 800 DEG C, soaking time 2h are heated to, finally lead to H2 and be cooled to room temperature, obtain modified graphite
Alkene, and graphene can be used as to be modified tungsten carbide self-lubricating abrasion-resistant additive and used.
Example 4:
On the basis of above-described embodiment, modified graphene provided by the invention, by a certain proportion of graphene oxide, anhydrous second
The precursor mixture that alcohol, deionized water, ammonium metatungstate and tungsten carbonyl are mixed into tungstenic mixes, and specific preparation process is such as
Under:4g graphene oxides are weighed, 1000g absolute ethyl alcohols is added, uniform stirring mixing, is mixed adding 800g deionized waters
Close, in ultrasonic disperse instrument, from 10mm vibration amplitude arms, sonication treatment time 150min, supersonic frequency 15Hz, obtain graphite
The scattered mixed liquor of alkene, the forerunner that mass percent is mixed into tungstenic for 99% ammonium metatungstate and 1% tungsten carbonyl is weighed respectively
Body mixture, weigh 1g tungstenic precursor mixtures and be added in graphene dispersion solution, stir 60min, in whipping process not
It is disconnected to instill absolute ethyl alcohol, infusion volume 228g, then obtained precipitation is filtered, heat 90 DEG C in an oven, dry 40min,
The drying powder that will be obtained, is placed in alumina crucible, and a certain amount of H2 is led in tubular reduction furnace, and H2 flows are l00sccm, with
50 DEG C/min heating rate, 900 DEG C, soaking time 2h are heated to, finally lead to H2 and be cooled to room temperature, obtain modified graphite
Alkene, and graphene can be used as to be modified tungsten carbide self-lubricating abrasion-resistant additive and used.
Example 5:
On the basis of above-described embodiment, modified graphene provided by the invention, by a certain proportion of graphene oxide, anhydrous second
The precursor mixture that alcohol, deionized water, ammonium metatungstate and tungsten carbonyl are mixed into tungstenic mixes, and specific preparation process is such as
Under:5g graphene oxides are weighed, 1000g absolute ethyl alcohols is added, uniform stirring mixing, is mixed adding 800g deionized waters
Close, in ultrasonic disperse instrument, from 10mm vibration amplitude arms, sonication treatment time 150min, supersonic frequency 15Hz, obtain graphite
The scattered mixed liquor of alkene, the forerunner that mass percent is mixed into tungstenic for 99% ammonium metatungstate and 1% tungsten carbonyl is weighed respectively
Body mixture, weigh 1g tungstenic precursor mixtures and be added in graphene dispersion solution, stir 60min, in whipping process not
It is disconnected to instill absolute ethyl alcohol, infusion volume 286g, then obtained precipitation is filtered, heat 90 DEG C in an oven, dry 40min,
The drying powder that will be obtained, is placed in alumina crucible, and a certain amount of H2 is led in tubular reduction furnace, and H2 flows are l00sccm, with
50 DEG C/min heating rate, 900 DEG C, soaking time 2h are heated to, finally lead to H2 and be cooled to room temperature, obtain modified graphite
Alkene, and graphene can be used as to be modified tungsten carbide self-lubricating abrasion-resistant additive and used.
Example 6:
On the basis of above-described embodiment, modified graphene provided by the invention, by a certain proportion of graphene oxide, anhydrous second
The precursor mixture that alcohol, deionized water, ammonium metatungstate and tungsten carbonyl are mixed into tungstenic mixes, and specific preparation process is such as
Under:6g graphene oxides are weighed, 1000g absolute ethyl alcohols is added, uniform stirring mixing, is mixed adding 800g deionized waters
Close, in ultrasonic disperse instrument, from 10mm vibration amplitude arms, sonication treatment time 180min, supersonic frequency 15Hz, obtain graphite
The scattered mixed liquor of alkene, the forerunner that mass percent is mixed into tungstenic for 99% ammonium metatungstate and 1% tungsten carbonyl is weighed respectively
Body mixture, weigh 1g tungstenic precursor mixtures and be added in graphene dispersion solution, stir 60min, in whipping process not
It is disconnected to instill absolute ethyl alcohol, infusion volume 324g, then obtained precipitation is filtered, heat 90 DEG C in an oven, dry 40min,
The drying powder that will be obtained, is placed in alumina crucible, and a certain amount of H2 is led in tubular reduction furnace, and H2 flows are l00sccm, with
70 DEG C/min heating rate, 900 DEG C, soaking time 3h are heated to, finally lead to H2 and be cooled to room temperature, obtain modified graphite
Alkene, and graphene can be used as to be modified tungsten carbide self-lubricating abrasion-resistant additive and used.
Compared with immediate prior art, the invention has the advantages that:
1)Modified graphene acts not only as the self-lubricating abrasion-resistant additive in hot spray powder, improves the phase with dusty spray
Capacitive and uniform Combination, the chimeric intensity with dusty spray is improved, ensure that the higher of graphene contains inside dusty spray
Amount.In addition, modified graphene can also be applied to lubricating oil, inside lubricating grease, it is ensured that inside lubricating oil or lubricating grease
Dispersed and permanent storage-stable, it is ensured that lubricating oil or lubricating grease play reduction in wear Protection application process and rubbed
Wipe the effect of coefficient.
2)Technical scheme provided by the invention can obtain modified graphene, make nano-lamellar structure graphenic surface in situ
Growth, deposition have the tungsten carbide particle of nanoscale, by controlling the content ratio between reactant, and reaction condition, Ke Yishi
The size of existing graphenic surface growth in situ nano silicon carbide composition granule, pattern, content regulation and control.
3)Modified graphene prepared by the present invention had not both changed the characteristic of graphene sheet layer carbon structure unit, and graphene still has
There are larger specific surface area and greater activity, greatly enhance the weight of graphene again, area load has original
The nanometer tungsten carbide of position growth improves the phase that graphene is modified tungsten carbide self-lubricating abrasion-resistant additive and tungsten carbide dusty spray
Capacitive and uniformly mixing.
4)The tungsten carbide coating for being directly appended to the preparation of tungsten carbide dusty spray not modified compared to graphene, institute of the present invention
The graphene of acquisition, which is modified tungsten carbide self-lubricating agent and will not blown in spraying process by the spraying flame stream of high speed, high temperature, to fly and loses
Fall, be effectively kept the component content of graphene in the coating and be uniformly distributed.
5)The graphene that the present invention obtains is modified tungsten carbide self-lubricating abrasion-resistant additive application in wear-resistant coating, graphene
On the one hand the intensity and toughness of coating can be improved, the shearing force of graphene film interlayer is minimum in addition, the graphite in friction process
The relative relative slip slided, surface of friction pair metalwork can be replaced occurs between alkene lamella, realizes abrasive dust and friction subtabulation
The separation in face, greatly reduces coefficient of friction, reduces abrasion.
It should be appreciated that for those of ordinary skills, can according to the above description be improved or converted, and institute
There is the protection domain that these modifications and variations should all belong to appended claims of the present invention.
Claims (4)
1. a kind of modified graphene, it is characterised in that by a certain proportion of graphene oxide, absolute ethyl alcohol, deionized water, inclined tungsten
The precursor mixture that sour ammonium and tungsten carbonyl are mixed into tungstenic mixes.
2. modified graphene as claimed in claim 1, it is characterised in that weigh 1g-6g graphene oxides, add 1000g without
Water-ethanol, uniform stirring mixing;Add 50-800g deionized waters to be mixed, in ultrasonic disperse instrument, shaken from 10mm
Width bar, sonication treatment time 30-180min, supersonic frequency 10-15Hz, obtain the mixed liquor of graphene dispersion.
3. modified graphene as claimed in claim 2, it is characterised in that weigh the metatungstic acid that mass percent is 99% respectively
Ammonium and 1% tungsten carbonyl are mixed into the precursor mixture of tungstenic, weigh 1g tungstenic precursor mixtures and are added to graphene dispersion
In solution, 30-60min is stirred;Absolute ethyl alcohol is constantly instilled in whipping process, infusion volume 18-324g, will then be obtained
Precipitation filters, and heats 70-90 DEG C in an oven, dries 10-60min, obtains drying powder.
4. modified graphene as claimed in claim 3, it is characterised in that the drying powder that will be obtained, be placed in alumina crucible
In, a certain amount of H2 is led in tubular reduction furnace, H2 flows are l00sccm, with 5-70 DEG C/min heating rate, are heated to
700-900 DEG C;Soaking time is 1-3h, finally leads to H2 and is cooled to room temperature, obtains modified graphene.
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CN109957749B (en) * | 2019-04-29 | 2021-03-30 | 中国人民解放军陆军勤务学院 | Thermal spraying powder |
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