CN107354419A - A kind of graphene is modified the preparation method of visual wear-resistant coating - Google Patents
A kind of graphene is modified the preparation method of visual wear-resistant coating Download PDFInfo
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- CN107354419A CN107354419A CN201710507946.0A CN201710507946A CN107354419A CN 107354419 A CN107354419 A CN 107354419A CN 201710507946 A CN201710507946 A CN 201710507946A CN 107354419 A CN107354419 A CN 107354419A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
Abstract
The present invention provides the preparation method that a kind of graphene is modified visual wear-resistant coating, step 1：Weigh a certain amount of strontium carbonate（SrCO3）, aluminum oxide（Al2O3）, a certain amount of alcohol is weighed, is mixed；Step 2：Weigh a certain amount of graphene oxide and be dispersed in ultrasonic vibration in absolute ethyl alcohol；Step 3：By europium oxide（Eu2O3）And dysprosia（Dy2O3）Using diluted hydrochloric acid dissolution；Step 4：Realize graphene to Dy3+/Eu3+Modification and composition regulation and control；Step 5：Screening obtains the SrAl that the graphene of about 1 μm ~ 3 μm of powder diameter is modified2O4:Eu3+,Dy3+Powder；Step 6：Obtain the graphene codope Dy of certain particle size3+/Eu3+WC Co powder body materials；The SrAl of graphene modification is prepared using plasma spray technology2O4:Eu3+,Dy3+The visual wear-resistant coatings of codope WC Co.High using such scheme, sprayed on material epigranular, purity, graphene content is high in powder, and visual wear-resistant coating can be prepared using plasma spray technology.
Description
Technical field
The invention belongs to the SrAl that plasma spray technology prepares graphene modification2O4:Eu3+,Dy3+Codope WC-Co is visually resistance to
Coating technology field is ground, more particularly to a kind of graphene is modified the preparation method of visual wear-resistant coating.
Background technology
It is one of major technique of Rebuilding engineering application that thermal spraying, which prepares wear-resistant coating, both can be used for new product part
Surface abrasion resistance is lifted, and be can be used for the reparation of failure part geometry size, is assigned waste and old part new life cycle, is saved
The energy and waste of material caused by saving manufacture new product, have in the high-tech such as Aero-Space, petrochemical industry, nuclear power station engineering field extensive
Application potential.
Up to the present, there is large area to remanufacturing Parts Surface Coating typically only coating during complete machine military service
Just there is obvious failure when spot corrosion or spalling failure, belong to " judging afterwards ".This failure has sudden and is difficult to
Foreseeability, just failed suddenly when being often on active service under material factor, it is possible to serious damage is produced to equipment, very
To the safety of the line operating personnel of serious threat one.In addition, friction process floating coat is by internal residual stress, external forces etc.
The microcosmic progressive accumulated damages such as elastic-plastic deformation, crack initiation, extension, connection and the fracture of material occur for caused coating
Process, naked eyes can not be observed directly at all.Therefore, develop high sensitivity, effectively and can monitor on-line coating be on active service during it is micro-
The visualizing monitor technology for seeing damage process is extremely necessary.
All is at present the various signals detected by using advanced instrument equipment, carries out indirect monitoring workpiece surface and interior
Portion's wear condition, such as the technology such as sound emission, ultrasonic vibration and machine vision, but tester used by these monitoring means
Cost is at a relatively high, and not only requirement to external environment is high, and is difficult to real-time operation and test process is not directly perceived etc. enough
Problem.Luminescent coating is because its intuitive can be efficiently applied to indication coating, in the 1990s, with SrAl2O4：Eu3+, Dy3+For
Novel rare-earth ion co-activation is represented, is irradiated by excitaton source, Eu3+, Dy3+Transition from ground state to excitation state, jump occur for electronics
Energy is absorbed during moving, after stopping excites, electronics returns ground state from excitation state transition and can released energy, and is detected so as to luminous
Arrive, current this material is widely used in the form of coating in fields such as fire-fighting, building, military affairs, but coat is deposited
Bond strength is low, coating failure easy to aging the problem of.Luminescent coating is applied to wear monitoring technology at present, rarely has report so far
Road.In addition, Eu3+, Dy3+If applied to, due to having declined in the sensitivity of coat inside excitation signal, being influenceed in coating
Its characteristics of luminescence, there are some researches show graphene oxide（GO）It is the derivative of graphene, substantial amounts of oxygen-containing function is contained on its surface
Group, graphene have the principle of fluorescent characteristic be exactly in graphene oxidizing process caused oxygen-containing functional group cause π tracks occur
Defect and cause.Also there are some researches prove GO surface oxygen functional groups can influence the change of fluorescence intensity and position.To sum up analyze,
Dy is modified using graphene 3+/Eu3+Composition regulation and control and prepare can be achieved enhancing Dy 3+/Eu3+Applied in visual wear-resistant coating
The weak problem of fluorescence intensity.
Therefore, the prior art is defective, it is necessary to improve.
The content of the invention
The present invention proposes a kind of SrAl for being used to prepare graphene modification2O4:Eu3+,Dy3+Codope WC-Co's is visual resistance to
Mill coating and thermal jet coating preparation method, the visual wear-resistant coating of preparation have photoluminescence property, and coat inside Dispersed precipitate has
Can photoluminescence property graphene be modified SrAl2O4：Dy 3+/Eu3+Compound, coating is in the monitoring process that works by addition
If irradiation coating is local unglazed, illustrates that coating wears totally in a certain position, expose matrix.Therefore, can be by dilute
Native fluorescent element characteristics of luminescence on-line identification goes out coating integrity situation.It is expected to realize that abrasion of the coating in Life cycle becomes
The real-time monitoring changed, reaches the purpose to coating failure early warning.
In addition, another potential market that graphene is modified visual coating is exactly that equipment build-up member is false proof, such as by field
On part be modified visual coated marker with graphene by production batch, gone out with the mark position of this part of light irradiation in addition,
Can firmly believes the authenticity of part.
It is an object of the invention to provide be modified SrAl for preparing graphene2O4:Eu3+,Dy3+Codope WC-Co is sprayed
Powder and thermal spraying prepare the preparation method that graphene is modified visual wear-resistant coating.
To achieve the above object, the present invention uses following technical scheme：
A kind of graphene is modified the preparation method of visual wear-resistant coating, comprises the following steps：
Step 1：Weigh a certain amount of strontium carbonate（SrCO3）, aluminum oxide（Al2O3）, weigh a certain amount of alcohol, mixed-powder and wine
Essence is placed in progress ball milling mixing certain time in planetary ball mill, until alcohol volatilizees completely；Subsequent transposition in corundum boat,
Held for some time under certain temperature is placed in high-temperature vacuum furnace；
Step 2：Weigh a certain amount of graphene oxide and be dispersed in ultrasonic vibration preparation graphene oxide dispersion in absolute ethyl alcohol；
Step 3：By europium oxide（Eu2O3）And dysprosia（Dy2O3）Using diluted hydrochloric acid dissolution, while a certain amount of distilled water is added, stirred
Processing certain time is mixed, final mixed liquor is in suspended state；
Step 4：Europium oxide is obtained in step 3（Eu2O3）And dysprosia（Dy2O3）The oxidation of different content is instilled in mixed solution
Graphene dispersing solution, by controlling reaction time and temperature, realize graphene to Dy3+/Eu3+Modification and composition regulation and control, finally
Drying obtains graphene modification/Dy in vacuum atmosphere3+/Eu3+Powder；
Step 5：Step 1 is obtained into mixed-powder and obtains graphene modification/Dy with step 43+/Eu3+Powder, which is placed in, is connected with reduction
Atmosphere（5%H2+95%N2）In high temperature process furnances, certain time is handled under certain temperature, then carries out ball mill crushing processing, screening
Obtain the SrAl that the graphene of about 1 μm ~ 3 μm of powder diameter is modified2O4:Eu3+,Dy3+Powder；
Step 6：The WC-Co powder that particle diameter is 1 μm ~ 3 μm is weighed, obtaining powder with step 5 mixes, and adds a certain amount of binding agent and gathers
Vinyl alcohol, under certain temperature, certain time is stirred in the range of certain stir speed (S.S.), by the liquid material after being stirred in vacuum bar
Spraying granulation is carried out under part, obtains the graphene codope Dy of certain particle size3+/Eu3+WC-Co powder body materials；Using thermal spraying
Technology prepares the SrAl of graphene modification2O4:Eu3+,Dy3+The visual wear-resistant coatings of codope WC-Co.
In above-mentioned, in the step 1, strontium carbonate（SrCO3）With aluminum oxide（Al2O3）Mass ratio is 1.5 ~ 2.5:1, alcohol
With mixed-powder（SrCO3With Al2O3）Mass ratio is 1.5 ~ 2:1, Ball-milling Time about 60 min ~ 90min, powder after ball milling mixing
Treatment temperature is 900 DEG C ~ 1000 DEG C in high temperature furnace, and processing time is 4 h ~ 6h.
In above-mentioned, in the step 2, graphene oxide is 1 with absolute ethyl alcohol mass percent:100 ~ 300, ultrasound point
It is 120min ~ 180min, supersonic frequency 15Hz to dissipate the time.
In above-mentioned, in the step 3, europium oxide（Eu2O3）And dysprosia（Dy2O3）Mixed using watery hydrochloric acid, wherein aoxidizing
Europium is 1.5 ~ 2 with dysprosia mass percent:1, distilled water is 20 ~ 30 with europium oxide combined oxidation dysprosium mixture quality ratio:1,
Homogenizer is with 500rpm/min speed, and stir processing 30min ~ 60min.
In above-mentioned, in the step 4, by the step 3 stir processing europium oxide and dysprosia mixed solution not
The graphene oxide dispersion that the disconnected step 2 for instilling different content obtains, the ratio of two of which mixed liquor are controlled in quality hundred
Divide than being 6 ~ 10:1, under vacuum, it is stirred continuously with 600rpm/min speed, heating-up temperature is 400 DEG C, mixing time
For 30 ~ 60min, while constantly instill concentrated ammonia liquor.
In above-mentioned, in the step 5, step 1 obtained into mixed-powder and obtains graphene modification/Dy with step 43+/Eu3+
Powder, which is placed in, is connected with reducing atmosphere（5%H3+95%N2）In high temperature process furnances, treatment temperature is 1360 DEG C ~ 1580 DEG C, processing time
For 4h ~ 6h, ball mill crushing processing is then carried out, screening obtains the SrAl that the graphene of about 1 μm ~ 3 μm of powder diameter is modified2O4:
Eu3+,Dy3+Powder.
In above-mentioned, in the step 6, weigh step 5 and obtain the SrAl that graphene is modified2O4:Eu3+,Dy3+Powder and particle diameter
WC-Co powder qualities ratio for 1 μm ~ 3 μm is 1% ~ 3%, and obtaining powder with step 3 mixes, and adds a certain amount of polyvinyl alcohol, heats
60 ~ 80 DEG C, stir 60 ~ 90min, the rpm/min of stir speed (S.S.) 500 ~ 700.Liquid material after being stirred is entered under vacuum
Row mist projection granulating, obtain the SrAl that the graphene that particle diameter is 30 μm ~ 45 μm is modified2O4:Eu3+,Dy3+Codope WC-Co spraying
Material.
In above-mentioned, in the step 6, plasma spray technology prepares the visual wear-resistant coating of graphene modification and includes but is not limited to adopt
With explosive spray coating, HVAF technology, plasma spraying technology, HVAS.When using blast
During spraying technology：Nitrogen is powder feeding gas and cleans gas, and oxygen and acetylene are heat source gas, and the gas flow ratio of oxygen and acetylene is
1.0 ~ 1.5, gas fills rifle amount for 60 ~ 90%, and regulation detonation frequency is 3 ~ 7 times/second, and spray distance is 250 ~ 300mm, powder feeding rate
For 0.2 ~ 0.7g/s.
Compared with immediate prior art, the invention has the advantages that：
1）Compared to traditional WC-Co powder, thermal spraying prepare WC-Co wear-resistant coatings can not learn its when the difficulty of wear out failure
Topic, the SrAl that graphene provided by the invention is modified2O4:Eu3+,Dy3+Codope WC-Co dusty spray, using thermal spraying skill
Art prepares the abrasion change that visual wear-resistant coating can in real time in the range of coat inside through thickness, coating failure can be played pre-
Alert effect, monitors coating integrity and safe duty status.
2）Compared to single rare earth ion Eu3+Application in visual wear-resistant coating, the weak problem of fluorescence intensity, this hair be present
It is bright to pass through Dy3+/Eu3+The synergy mechanism of codope, visual wear-resistant coating can be prepared in the range of through thickness realizing
The highly sensitive response of fluorescence developing.
3）Technical scheme provided by the invention can be modified SrAl in Sheet Graphite alkene2O4:Eu3+,Dy3+, it is anti-by controlling
Answer the content ratio between thing, and reaction condition, it is possible to achieve graphenic surface co-doped nano europium oxide and dysprosia particle
Size, pattern, content regulation and control, using graphene to Dy3+/Eu3+Ion is modified, and realizes enhancing rare earth ion optical property
Purpose.
4）The visual wear-resistant coating for being directly appended to dusty spray preparation not modified compared to graphene, the present invention are obtained
Graphene be modified dusty spray in spraying process will not by a high speed, the spraying flame stream of high temperature blow and fly and lose, effectively
Remain the component content of graphene in the coating and be uniformly distributed.
5）The SrAl that graphene provided by the invention is modified2O4:Eu3+,Dy3+Codope WC-Co dusty spray, using heat
Spraying technology prepares visual wear-resistant coating, on the one hand graphene can improve the intensity and toughness of coating, furthermore with graphene/
Dy3+/Eu3+Dispersed precipitate in coat inside as secondary phase toughening coating, while play to coating occur crackle have suppress and
The effect of stress relaxation, made great sense to improving visual wear-resisting military service performance.
Brief description of the drawings
Fig. 1 is the SrAl that graphene is modified2O4:Eu3+,Dy3+Codope WC-Co dusty spray low power scanning electron microscope (SEM) photograph.
Fig. 2 is the SrAl that graphene is modified2O4:Eu3+,Dy3+Codope WC-Co dusty spray high power scanning electron microscope (SEM) photograph.
Fig. 3 is the SrAl that graphene prepared by explosive spray coating is modified2O4:Eu3+,Dy3+Codope WC-Co is visually wear-resisting
Coating Fracture scan electron microscope
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1：
On the basis of above-described embodiment, a kind of graphene that the present embodiment provides is modified the preparation method of visual wear-resistant coating,
Comprise the following steps：
Step（1）Weigh 20g strontium carbonate（SrCO3）, 10g aluminum oxide（Al2O3）, weigh 300ml alcohol, mixed-powder with
Alcohol is placed in progress ball milling mixing 60min in planetary ball mill, until alcohol volatilizees completely.Subsequent transposition in corundum boat,
Treatment temperature is 900 DEG C in high temperature furnace, and processing time is 4 h.
Step（2）Weigh 1g graphene oxides and be dispersed in ultrasonic vibration in 100ml absolute ethyl alcohols and prepare graphene oxide point
Dispersion liquid.The ultrasonic disperse time is 120min, supersonic frequency 15Hz.
Step（3）Weigh 2g europium oxides（Eu2O3）With 2g dysprosias（Dy2O3）, 300ml diluted hydrochloric acid dissolutions are added, are added simultaneously
Enter a 300ml distilled water, homogenizer is with 500rpm/min speed, and stir processing 30min ~ 60min, final mixed liquor
In suspended state.
Step（4）In step（3）Obtain europium oxide（Eu2O3）And dysprosia（Dy2O3）Different content is instilled in mixed solution
Graphene oxide dispersion, it is 6 that the ratio of two of which mixed liquor, which is controlled in mass percent,:1, under vacuum, with
600rpm/min speed is stirred continuously, and heating-up temperature is 400 DEG C, mixing time 30min, while constantly instills concentrated ammonia liquor.
Realize graphene to Dy3+/Eu3+Modification and composition regulation and control, finally in vacuum atmosphere drying obtain graphene modification/Dy3+/
Eu3+Powder.
Step（5）By step（1）Obtain mixed-powder and step（4）Obtain graphene modification/Dy3+/Eu3+Powder is placed in
It is connected with reducing atmosphere（5%H2+95%N2）In high temperature process furnances, treatment temperature is 1360 DEG C, processing time 4h, then carries out ball
Break process is ground, screening obtains the SrAl that the graphene of about 1 μm ~ 3 μm of powder diameter is modified2O4:Eu3+,Dy3+Powder.
Step（6）The WC-Co powder 3000g that particle diameter is 1 μm ~ 3 μm are weighed, with step（5）Obtain what graphene was modified
SrAl2O4:Eu3+,Dy3+Powder mixes, and adds a certain amount of binding agent polyvinyl alcohol, heats 60 DEG C, stirs 60min, stir speed (S.S.)
500 rpm/min.Liquid material after being stirred is subjected to mist projection granulating under vacuum, it is 30 μm ~ 45 μm to obtain particle diameter
The SrAl that graphene is modified2O4:Eu3+,Dy3+Codope WC-Co sprayed on material.
Step（7）The gas stream of the visual wear-resistant coating of graphene modification, oxygen and acetylene is prepared using explosive spray coating
Amount is than being 1.0, and it is 60% that gas, which fills rifle amount, and regulation detonation frequency is 3 times/second, spray distance 250mm, and powder feeding rate is 0.2g/
s。
The SrAl being modified as shown in Figure 1 for graphene prepared by the example2O4:Eu3+,Dy3+Codope WC-Co spraying material
Expect low power scanning electron microscope (SEM) photograph.As can be seen that the powder particle epigranular prepared, preferable, spherical size of reuniting are complete, stream
Dynamic property is good.
It is illustrated in figure 2 the SrAl that the graphene of example preparation is modified2O4:Eu3+,Dy3+Codope WC-Co spraying material
High power scanning electron microscope (SEM) photograph is expected, as shown by arrows in FIG. it can be seen that the transparence graphene oxide of nano thin-layer is embedded in spherical
Intragranular portion, is adhered to particle surface, and also apposition growth has the europium oxide and dysprosia particle of nanoscale to graphenic surface.
The high power scanning electron microscope (SEM) photograph as existing for Fig. 3 is graphene " embedded " inside the visual wear-resistant coating of graphene modification,
As shown by arrows in FIG. it can be seen that the transparence graphene of nano thin-layer is embedded in inside coating structure, illustrate that detonation flame spraying has
Effect remains the presence of graphene in the coating.
Embodiment 2：
On the basis of above-described embodiment, a kind of graphene that the present embodiment provides is modified the preparation method of visual wear-resistant coating,
Comprise the following steps：
Step（1）Weigh 30g strontium carbonate（SrCO3）, 15g aluminum oxide（Al2O3）, weigh 500ml alcohol, mixed-powder with
Alcohol is placed in progress ball milling mixing 70min in planetary ball mill, until alcohol volatilizees completely.Subsequent transposition in corundum boat,
Treatment temperature is 1000 DEG C in high temperature furnace, and processing time is 5 h.
Step（2）Weigh 2g graphene oxides and be dispersed in ultrasonic vibration in 200ml absolute ethyl alcohols and prepare graphene oxide point
Dispersion liquid.The ultrasonic disperse time is 120min, supersonic frequency 15Hz.
Step（3）Weigh 3g europium oxides（Eu2O3）With 1.5g dysprosias（Dy2O3）, 500ml diluted hydrochloric acid dissolutions are added, simultaneously
500ml distilled water is added, homogenizer is with 500rpm/min speed, and stir processing 40min, and final mixed liquor is in suspension
State.
Step（4）In step（3）Obtain europium oxide（Eu2O3）And dysprosia（Dy2O3）Different content is instilled in mixed solution
Graphene oxide dispersion, it is 7 that the ratio of two of which mixed liquor, which is controlled in mass percent,:1, under vacuum, with
600rpm/min speed is stirred continuously, and heating-up temperature is 500 DEG C, mixing time 40min, while constantly instills concentrated ammonia liquor.
Realize graphene to Dy3+/Eu3+Modification and composition regulation and control, finally in vacuum atmosphere drying obtain graphene modification/Dy3+/
Eu3+Powder.
Step（5）By step（1）Obtain mixed-powder and step（4）Obtain graphene modification/Dy3+/Eu3+Powder is placed in
It is connected with reducing atmosphere（5%H2+95%N2）In high temperature process furnances, treatment temperature is 1400 DEG C, processing time 5h, then carries out ball
Break process is ground, screening obtains the SrAl that the graphene of about 1 μm ~ 3 μm of powder diameter is modified2O4:Eu3+,Dy3+Powder.
Step（6）The WC-Co powder 4000g that particle diameter is 1 μm ~ 3 μm are weighed, with step（5）Obtain what graphene was modified
SrAl2O4:Eu3+,Dy3+Powder mixes, and adds a certain amount of binding agent polyvinyl alcohol, heats 70 DEG C, stirs 70min, stir speed (S.S.)
500 rpm/min.Liquid material after being stirred is subjected to mist projection granulating under vacuum, it is 30 μm ~ 45 μm to obtain particle diameter
The SrAl that graphene is modified2O4:Eu3+,Dy3+Codope WC-Co sprayed on material.
Step（7）The gas stream of the visual wear-resistant coating of graphene modification, oxygen and acetylene is prepared using explosive spray coating
Amount is than being 1.2, and it is 70% that gas, which fills rifle amount, and regulation detonation frequency is 4 times/second, spray distance 265mm, and powder feeding rate is 0.4g/
s。
Embodiment 3：
On the basis of above-described embodiment, a kind of graphene that the present embodiment provides is modified the preparation method of visual wear-resistant coating,
Comprise the following steps：
Step（1）Weigh 60g strontium carbonate（SrCO3）, 40g aluminum oxide（Al2O3）, weigh 600ml alcohol, mixed-powder with
Alcohol is placed in progress ball milling mixing 80min in planetary ball mill, until alcohol volatilizees completely.Subsequent transposition in corundum boat,
Treatment temperature is 1000 DEG C in high temperature furnace, and processing time is 6 h.
Step（2）Weigh 1g graphene oxides and be dispersed in ultrasonic vibration in 100ml absolute ethyl alcohols and prepare graphene oxide point
Dispersion liquid.The ultrasonic disperse time is 120min, supersonic frequency 15Hz.
Step（3）Weigh 3g europium oxides（Eu2O3）With 2g dysprosias（Dy2O3）, 300ml diluted hydrochloric acid dissolutions are added, are added simultaneously
Enter 300ml distilled water, homogenizer is with 500rpm/min speed, and stir processing 50min, and final mixed liquor is in suspension
State.
Step（4）In step（3）Obtain europium oxide（Eu2O3）And dysprosia（Dy2O3）Different content is instilled in mixed solution
Graphene oxide dispersion, it is 8 that the ratio of two of which mixed liquor, which is controlled in mass percent,:1, under vacuum, with
600rpm/min speed is stirred continuously, and heating-up temperature is 400 DEG C, mixing time 50min, while constantly instills concentrated ammonia liquor.
Realize graphene to Dy3+/Eu3+Modification and composition regulation and control, finally in vacuum atmosphere drying obtain graphene modification/Dy3+/
Eu3+Powder.
Step（5）By step（1）Obtain mixed-powder and step（4）Obtain graphene modification/Dy3+/Eu3+Powder is placed in
It is connected with reducing atmosphere（5%H2+95%N2）In high temperature process furnances, treatment temperature is 1500 DEG C, processing time 5h, then carries out ball
Break process is ground, screening obtains the SrAl that the graphene of about 1 μm ~ 3 μm of powder diameter is modified2O4:Eu3+,Dy3+Powder.
Step（6）The WC-Co powder 6000g that particle diameter is 1 μm ~ 3 μm are weighed, with step（5）Obtain what graphene was modified
SrAl2O4:Eu3+,Dy3+Powder mixes, and adds a certain amount of binding agent polyvinyl alcohol, heats 80 DEG C, stirs 80min, stir speed (S.S.)
600 rpm/min.Liquid material after being stirred is subjected to mist projection granulating under vacuum, it is 30 μm ~ 45 μm to obtain particle diameter
The SrAl that graphene is modified2O4:Eu3+,Dy3+Codope WC-Co sprayed on material.
Step（7）The gas stream of the visual wear-resistant coating of graphene modification, oxygen and acetylene is prepared using explosive spray coating
Amount is than being 1.3, and it is 80% that gas, which fills rifle amount, and regulation detonation frequency is 5 times/second, spray distance 270mm, and powder feeding rate is 0.5g/
s。
Example 4：
On the basis of above-described embodiment, a kind of graphene that the present embodiment provides is modified the preparation method of visual wear-resistant coating,
Comprise the following steps：
Step（1）Weigh 80g strontium carbonate（SrCO3）, 60g aluminum oxide（Al2O3）, weigh 1200ml alcohol, mixed-powder with
Alcohol is placed in progress ball milling mixing 90min in planetary ball mill, until alcohol volatilizees completely.Subsequent transposition in corundum boat,
Treatment temperature is 1000 DEG C in high temperature furnace, and processing time is 6 h.
Step（2）Weigh 3g graphene oxides and be dispersed in ultrasonic vibration in 1000ml absolute ethyl alcohols and prepare graphene oxide point
Dispersion liquid.The ultrasonic disperse time is 180min, supersonic frequency 15Hz.
Step（3）Weigh 6g europium oxides（Eu2O3）With 4g dysprosias（Dy2O3）, 1000ml diluted hydrochloric acid dissolutions are added, simultaneously
1000ml distilled water is added, homogenizer is with 500rpm/min speed, and stir processing 60min, and final mixed liquor is in outstanding
Floating state.
Step（4）In step（3）Obtain europium oxide（Eu2O3）And dysprosia（Dy2O3）Different content is instilled in mixed solution
Graphene oxide dispersion, it is 10 that the ratio of two of which mixed liquor, which is controlled in mass percent,:1, under vacuum, with
600rpm/min speed is stirred continuously, and heating-up temperature is 400 DEG C, mixing time 60min, while constantly instills concentrated ammonia liquor.
Realize graphene to Dy3+/Eu3+Modification and composition regulation and control, finally in vacuum atmosphere drying obtain graphene modification/Dy3+/
Eu3+Powder.
Step（5）By step（1）Obtain mixed-powder and step（4）Obtain graphene modification/Dy3+/Eu3+Powder is placed in
It is connected with reducing atmosphere（5%H2+95%N2）In high temperature process furnances, treatment temperature is 1580 DEG C, processing time 6h, then carries out ball
Break process is ground, screening obtains the SrAl that the graphene of about 1 μm ~ 3 μm of powder diameter is modified2O4:Eu3+,Dy3+Powder.
Step（6）The WC-Co powder 10000g that particle diameter is 1 μm ~ 3 μm are weighed, with step（5）Obtain what graphene was modified
SrAl2O4:Eu3+,Dy3+Powder mixes, and adds a certain amount of binding agent polyvinyl alcohol, heats 80 DEG C, stirs 90min, stir speed (S.S.)
700 rpm/min.Liquid material after being stirred is subjected to mist projection granulating under vacuum, it is 30 μm ~ 45 μm to obtain particle diameter
The SrAl that graphene is modified2O4:Eu3+,Dy3+Codope WC-Co sprayed on material.
Step（7）The gas stream of the visual wear-resistant coating of graphene modification, oxygen and acetylene is prepared using explosive spray coating
Amount is than being 1.5, and it is 90% that gas, which fills rifle amount, and regulation detonation frequency is 7 times/second, spray distance 300mm, and powder feeding rate is 0.7g/
s。
Compared with immediate prior art, the invention has the advantages that：
1）Compared to traditional WC-Co powder, thermal spraying prepare WC-Co wear-resistant coatings can not learn its when the difficulty of wear out failure
Topic, the SrAl that graphene provided by the invention is modified2O4:Eu3+,Dy3+Codope WC-Co dusty spray, using thermal spraying skill
Art prepares the abrasion change that visual wear-resistant coating can in real time in the range of coat inside through thickness, coating failure can be played pre-
Alert effect, monitors coating integrity and safe duty status.
2）Compared to single rare earth ion Eu3+Application in visual wear-resistant coating, the weak problem of fluorescence intensity, this hair be present
It is bright to pass through Dy3+/Eu3+The synergy mechanism of codope, visual wear-resistant coating can be prepared in the range of through thickness realizing
The highly sensitive response of fluorescence developing.
3）Technical scheme provided by the invention can be modified SrAl in Sheet Graphite alkene2O4:Eu3+,Dy3+, it is anti-by controlling
Answer the content ratio between thing, and reaction condition, it is possible to achieve graphenic surface co-doped nano europium oxide and dysprosia particle
Size, pattern, content regulation and control, using graphene to Dy3+/Eu3+Ion is modified, and realizes enhancing rare earth ion optical property
Purpose.
4）The visual wear-resistant coating for being directly appended to dusty spray preparation not modified compared to graphene, the present invention are obtained
Graphene be modified dusty spray in spraying process will not by a high speed, the spraying flame stream of high temperature blow and fly and lose, effectively
Remain the component content of graphene in the coating and be uniformly distributed.
5）The SrAl that graphene provided by the invention is modified2O4:Eu3+,Dy3+Codope WC-Co dusty spray, using heat
Spraying technology prepares visual wear-resistant coating, on the one hand graphene can improve the intensity and toughness of coating, furthermore with graphene/
Dy3+/Eu3+Dispersed precipitate in coat inside as secondary phase toughening coating, while play to coating occur crackle have suppress and
The effect of stress relaxation, made great sense to improving visual wear-resisting military service performance.
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 (9)
1. a kind of graphene is modified the preparation method of visual wear-resistant coating, it is characterised in that comprises the following steps：
Step 1：Weigh a certain amount of strontium carbonate（SrCO3）, aluminum oxide（Al2O3）, weigh a certain amount of alcohol, mixed-powder and wine
Essence is placed in progress ball milling mixing certain time in planetary ball mill, until alcohol volatilizees completely；Subsequent transposition in corundum boat,
Held for some time under certain temperature is placed in high-temperature vacuum furnace；
Step 2：Weigh a certain amount of graphene oxide and be dispersed in ultrasonic vibration preparation graphene oxide dispersion in absolute ethyl alcohol；
Step 3：By europium oxide（Eu2O3）And dysprosia（Dy2O3）Using diluted hydrochloric acid dissolution, while a certain amount of distilled water is added, stirred
Processing certain time is mixed, final mixed liquor is in suspended state；
Step 4：Europium oxide is obtained in step 3（Eu2O3）And dysprosia（Dy2O3）The oxidation stone of different content is instilled in mixed solution
Black alkene dispersion liquid, by controlling reaction time and temperature, realize graphene to Dy3+/Eu3+Modification and composition regulation and control, finally exist
Drying obtains graphene modification/Dy in vacuum atmosphere3+/Eu3+Powder；
Step 5：Step 1 is obtained into mixed-powder and obtains graphene modification/Dy with step 43+/Eu3+Powder, which is placed in, is connected with also Primordial Qi
Atmosphere（5%H2+95%N2）In high temperature process furnances, certain time is handled under certain temperature, then carries out ball mill crushing processing, screening obtains
Obtain the SrAl that the graphene of about 1 μm ~ 3 μm of powder diameter is modified2O4:Eu3+,Dy3+Powder；
Step 6：The WC-Co powder that particle diameter is 1 μm ~ 3 μm is weighed, obtaining powder with step 5 mixes, and adds a certain amount of binding agent and gathers
Vinyl alcohol, under certain temperature, certain time is stirred in the range of certain stir speed (S.S.), by the liquid material after being stirred in vacuum bar
Spraying granulation is carried out under part, obtains the graphene codope Dy of certain particle size3+/Eu3+WC-Co powder body materials；Using thermal spraying
Technology prepares the SrAl of graphene modification2O4:Eu3+,Dy3+The visual wear-resistant coatings of codope WC-Co.
2. preparation method according to claim 1, it is characterised in that in the step 1, strontium carbonate（SrCO3）With aluminum oxide
（Al2O3）Mass ratio is 1.5 ~ 2.5:1, alcohol and mixed-powder（SrCO3With Al2O3）Mass ratio is 1.5 ~ 2:1, Ball-milling Time is about
60 min ~ 90min, powder treatment temperature in high temperature furnace is 900 DEG C ~ 1000 DEG C after ball milling mixing, processing time be 4 h ~
6h。
3. preparation method according to claim 1, it is characterised in that in the step 2, graphene oxide and anhydrous second
Alcohol mass percent is 1:100 ~ 300, the ultrasonic disperse time is 120min ~ 180min, supersonic frequency 15Hz.
4. preparation method according to claim 1, it is characterised in that in the step 3, europium oxide（Eu2O3）And dysprosia
（Dy2O3）Mixed using watery hydrochloric acid, wherein europium oxide and dysprosia mass percent are 1.5 ~ 2:1, distilled water is compound with europium oxide
Dysprosia mixture quality ratio is 20 ~ 30:1, homogenizer with 500rpm/min speed, the processing 30min that stirs ~
60min。
5. preparation method according to claim 1, it is characterised in that in the step 4, the step 3 is stirred
The europium oxide and dysprosia mixed solution of processing constantly instill the graphene oxide dispersion that the step 2 of different content obtains, its
In two kinds of mixed liquors ratio control mass percent be 6 ~ 10:1, under vacuum, with 600rpm/min speed not
Disconnected stirring, heating-up temperature are 400 DEG C, and mixing time is 30 ~ 60min, while constantly instills concentrated ammonia liquor.
6. preparation method according to claim 1, it is characterised in that in the step 5, step 1 is obtained into mixed-powder
Graphene modification/Dy is obtained with step 43+/Eu3+Powder, which is placed in, is connected with reducing atmosphere（5%H3+95%N2）In high temperature process furnances, place
It is 1360 DEG C ~ 1580 DEG C to manage temperature, and processing time is 4h ~ 6h, then carries out ball mill crushing processing, and screening obtains powder diameter about
The SrAl that 1 μm ~ 3 μm of graphene is modified2O4:Eu3+,Dy3+Powder.
7. preparation method according to claim 1, it is characterised in that in the step 6, weigh step 5 and obtain graphene
Modified SrAl2O4:Eu3+,Dy3+The WC-Co powder qualities ratio that powder is 1 μm ~ 3 μm with particle diameter is 1% ~ 3%, is obtained with step 3
Powder mixes, and adds a certain amount of polyvinyl alcohol, heats 60 ~ 80 DEG C, stirs 60 ~ 90min, the rpm/min of stir speed (S.S.) 500 ~ 700；
Liquid material after being stirred is subjected to mist projection granulating under vacuum, obtains what the graphene that particle diameter is 30 μm ~ 45 μm was modified
SrAl2O4:Eu3+,Dy3+Codope WC-Co sprayed on material.
8. preparation method according to claim 1, it is characterised in that in the step 6, plasma spray technology prepares graphene
Modified visual wear-resistant coating includes but is not limited to using explosive spray coating, HVAF technology, plasma spraying skill
Art, HVAS.
9. preparation method according to claim 8, it is characterised in that when using explosive spray coating：Nitrogen is powder feeding
Gas and gas is cleaned, oxygen and acetylene be heat source gas, and the gas flow ratio of oxygen and acetylene is 1.0 ~ 1.5, and gas fills rifle amount and is
60 ~ 90%, regulation detonation frequency is 3 ~ 7 times/second, and spray distance is 250 ~ 300mm, and powder feeding rate is 0.2 ~ 0.7g/s.
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