CN107245686A - Prepare the preparation method that graphene is modified the hot spray powder of visual wear-resistant coating - Google Patents
Prepare the preparation method that graphene is modified the hot spray powder of visual wear-resistant coating Download PDFInfo
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- CN107245686A CN107245686A CN201710509682.2A CN201710509682A CN107245686A CN 107245686 A CN107245686 A CN 107245686A CN 201710509682 A CN201710509682 A CN 201710509682A CN 107245686 A CN107245686 A CN 107245686A
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/026—Spray drying of solutions or suspensions
Abstract
The present invention provides a kind of preparation method for the hot spray powder for preparing the visual wear-resistant coating of graphene modification, 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 preparation graphene oxide dispersion in absolute ethyl alcohol；Step 3：By europium oxide（Eu2O3）And dysprosia（Dy2O3）Using diluted hydrochloric acid dissolution；Step 4：By controlling reaction time and temperature, 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.Using such scheme, purity is high, and graphene content is high in powder, and visual wear-resistant coating is prepared available for plasma spray technology.
Description
Technical field
The SrAl that the graphene for preparing visual wear-resistant coating the invention belongs to plasma spray technology is modified2O4:Eu3+,Dy3+It is co-doped with
Miscellaneous WC-Co sprayed on material technical field, more particularly to a kind of thermal spraying for preparing the visual wear-resistant coating of graphene modification
The preparation method of powder.
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 can be used for the reparation of failure part geometry size, assigns waste and old part new life cycle, section
The energy and waste of material that manufacture new product is caused are saved, is had 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 fails 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 one line operating personnel of serious threat.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, development sensitivity is high, effective and can monitor on-line micro- during coating is on active service
The visualizing monitor technology for seeing damage process is extremely necessary.
All it is at present the various signals detected by using advanced instrument equipment, carries out indirect monitoring workpiece surface and interior
Portion's wear condition, the technology such as sound emission, ultrasonic vibration and machine vision, but the tester that these monitoring means are used
Cost is at a relatively high, and not only the requirement of environment is high to external world, and be difficult to real-time operation and test process it is not directly perceived enough in terms of
Problem.Luminescent coating can be efficiently applied to indication coating because of its intuitive, 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 is excited, electronics returns ground state from excitation state transition and can released energy, so that luminous be detected
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 easy ageing failure 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
There is group, graphene the oxygen-containing functional group produced in the principle exactly graphene oxidizing process of fluorescent characteristic to cause π tracks to 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
Invention proposes that a kind of graphene for being used to prepare visual wear-resistant coating is modified SrAl2O4：Dy 3+/Eu3+Compound WC-Co
Hot spray powder and preparation method, can using plasma spray technology prepare with photoluminescence property visual wear-resistant coating,
Coat inside Dispersed precipitate have can photoluminescence property graphene be modified SrAl2O4：Dy 3+/Eu3+Compound, coating is in work
If local unglazed by this external exposure coating in monitoring process, illustrate that coating weares and teares totally in a certain position, expose base
Body.It therefore, it can go out coating integrity situation by rare-earth fluorescent element characteristics of luminescence on-line identification.It is expected to realize coating complete
The real-time monitoring of abrasion change in life cycle, reaches the purpose to coating failure early warning.
The technical problems to be solved by the invention be in view of the shortcomings of the prior art there is provided one kind prepare graphene be modified can
Depending on the preparation method of the hot spray powder of wear-resistant coating.
Technical scheme is as follows：
It is a kind of to prepare the preparation method that graphene is modified the hot spray powder of visual wear-resistant coating, comprise 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 adding a certain amount of distilled water, stir
Mix processing certain time, 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, realizes 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 step 4 obtains graphene modification/Dy3+/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, ball mill crushing processing, screening is then carried out
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
Under vinyl alcohol, certain temperature, certain time is stirred in the range of certain stir speed (S.S.), mixed liquid material will be stirred in vacuum bar
Spraying granulation is carried out under part, the graphene codope Dy of certain particle size is obtained3+/Eu3+WC-Co powder body materials.
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:Powder after 1, Ball-milling Time about 60 min ~ 90min, 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, ultrasonic disperse
Time is 120min ~ 180min, and supersonic frequency is 15Hz.
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 is obtained, the ratio of two of which mixed liquor is 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 instilling concentrated ammonia liquor.
In above-mentioned, in the step 5, step 1 obtained into mixed-powder and step 4 obtains graphene modification/Dy3+/Eu3+
Powder, which is placed in, is connected with reducing atmosphere（5%H2+95%N2）In high temperature process furnances, treatment temperature be 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
It is 1% ~ 3% for 1 μm ~ 3 μm of WC-Co powder qualities ratios, obtaining powder with step 3 mixes, and adds a certain amount of polyvinyl alcohol, heating
60 ~ 80 DEG C, stir 60 ~ 90min, the rpm/min of stir speed (S.S.) 500 ~ 700；Mixed liquid material will be stirred under vacuum to enter
Row mist projection granulating, obtains SrAl of the particle diameter for 30 μm ~ 45 μm of graphene modification2O4:Eu3+,Dy3+Codope WC-Co spraying
Material.
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 the graphene that the present invention is provided 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, can play pre- to coating failure
Alert effect, monitoring coating integrity and safe duty status.
2）Compared to single rare earth ion Eu3+, there is the weak problem of fluorescence intensity, this hair in the application in visual wear-resistant coating
It is bright to pass through Dy3+/Eu3+The synergy mechanism of codope, can prepare visual wear-resistant coating in the range of through thickness realizing
The highly sensitive response of fluorescence developing.
3）The technical scheme that the present invention is provided can be modified SrAl in Sheet Graphite alkene2O4:Eu3+,Dy3+, it is anti-by control
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 is 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 the graphene that the present invention is provided is modified2O4:Eu3+,Dy3+Codope WC-Co dusty spray, using heat
Spraying technology prepares visual wear-resistant coating, and 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, makes 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.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
The present embodiment provides a kind of preparation method for the hot spray powder for preparing the visual wear-resistant coating of graphene modification, specific step
Suddenly it is：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, and supersonic frequency is 15Hz.
Step（3）Weigh 2g europium oxides（Eu2O3）With 2g dysprosias（Dy2O3）, 300ml diluted hydrochloric acid dissolutions are added, while plus
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, and mixing time is 30min, while constantly instilling 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, and processing time is 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 is mixed, and adds a certain amount of binding agent polyvinyl alcohol, heats 60 DEG C, stirs 60min, stir speed (S.S.)
500 rpm/min.Mixed liquid material will be stirred and carry out 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.
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, sticks to particle surface, and also apposition growth has the europium oxide and dysprosia particle of nanoscale to graphenic surface.
Embodiment 2
It is on the basis of above-described embodiment, the step of the present embodiment：Step（1）Weigh 30g strontium carbonate（SrCO3）, 15g's
Aluminum oxide（Al2O3）, 500ml alcohol is weighed, mixed-powder is placed in progress ball milling mixing 70min in planetary ball mill with alcohol,
Until alcohol volatilizees completely.Subsequent transposition is in corundum boat, and 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, and supersonic frequency is 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, and mixing time is 40min, while constantly instilling 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, and processing time is 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 is mixed, and adds a certain amount of binding agent polyvinyl alcohol, heats 70 DEG C, stirs 70min, stir speed (S.S.)
500 rpm/min.Mixed liquid material will be stirred and carry out 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.
Embodiment 3
It is on the basis of above-described embodiment, the step of the present embodiment：Step（1）Weigh 60g strontium carbonate（SrCO3）, 40g's
Aluminum oxide（Al2O3）, 600ml alcohol is weighed, mixed-powder is placed in progress ball milling mixing 80min in planetary ball mill with alcohol,
Until alcohol volatilizees completely.Subsequent transposition is in corundum boat, and 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, and supersonic frequency is 15Hz.
Step（3）Weigh 3g europium oxides（Eu2O3）With 2g dysprosias（Dy2O3）, 300ml diluted hydrochloric acid dissolutions are added, while plus
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, and mixing time is 50min, while constantly instilling 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, and processing time is 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 is mixed, and adds a certain amount of binding agent polyvinyl alcohol, heats 80 DEG C, stirs 80min, stir speed (S.S.)
600 rpm/min.Mixed liquid material will be stirred and carry out 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.
Embodiment 4
It is on the basis of above-described embodiment, the step of the present embodiment：Step（1）Weigh 80g strontium carbonate（SrCO3）, 60g's
Aluminum oxide（Al2O3）, 1200ml alcohol is weighed, mixed-powder is placed in planetary ball mill with alcohol and carries out ball milling mixing
90min, until alcohol volatilizees completely.Subsequent transposition is in corundum boat, and treatment temperature is 1000 DEG C, processing time in high temperature furnace
For 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, and supersonic frequency is 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, and mixing time is 60min, while constantly instilling 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, and processing time is 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 is mixed, and adds a certain amount of binding agent polyvinyl alcohol, heats 80 DEG C, stirs 90min, stir speed (S.S.)
700 rpm/min.Mixed liquid material will be stirred and carry out 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.
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 the graphene that the present invention is provided 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, can play pre- to coating failure
Alert effect, monitoring coating integrity and safe duty status.
2）Compared to single rare earth ion Eu3+, there is the weak problem of fluorescence intensity, this hair in the application in visual wear-resistant coating
It is bright to pass through Dy3+/Eu3+The synergy mechanism of codope, can prepare visual wear-resistant coating in the range of through thickness realizing
The highly sensitive response of fluorescence developing.
3）The technical scheme that the present invention is provided can be modified SrAl in Sheet Graphite alkene2O4:Eu3+,Dy3+, it is anti-by control
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 is 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 the graphene that the present invention is provided is modified2O4:Eu3+,Dy3+Codope WC-Co dusty spray, using heat
Spraying technology prepares visual wear-resistant coating, and 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, makes 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 all these modifications and variations should all belong to the protection domain of appended claims of the present invention.
Claims (8)
1. a kind of prepare the preparation method that graphene is modified the hot spray powder of visual wear-resistant coating, it is characterised in that including with
Lower step：
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.
2. subsequent transposition is 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 adding a certain amount of distilled water, stir
Mix processing certain time, 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, realizes 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 step 4 obtains graphene modification/Dy3+/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, ball mill crushing processing is then carried out, screening is obtained
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
Under vinyl alcohol, certain temperature, certain time is stirred in the range of certain stir speed (S.S.), mixed liquid material will be stirred in vacuum bar
Spraying granulation is carried out under part, the graphene codope Dy of certain particle size is obtained3+/Eu3+WC-Co powder body materials.
3. 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
After 60 min ~ 90min, ball milling mixing powder in high temperature furnace treatment temperature be 900 DEG C ~ 1000 DEG C, processing time be 4 h ~
6h。
4. preparation method according to claim 1, it is characterised in that in the step 2, graphene oxide and absolute ethyl alcohol
Mass percent is 1:100 ~ 300, the ultrasonic disperse time is 120min ~ 180min, and supersonic frequency is 15Hz.
5. 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 combined with europium oxide
Dysprosia mixture quality ratio is 20 ~ 30:1, homogenizer with 500rpm/min speed, stir processing 30min ~
60min。
6. 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 is obtained, 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 is 400 DEG C, and mixing time is 30 ~ 60min, while constantly instilling concentrated ammonia liquor.
7. 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%H2+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.
8. preparation method according to claim 1, it is characterised in that in the step 6, weighs step 5 and obtains graphene
Modified SrAl2O4:Eu3+,Dy3+Powder is 1% ~ 3% with the WC-Co powder qualities ratio that particle diameter is 1 μm ~ 3 μm, is obtained with step 3
Powder is mixed, 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；
Mixed liquid material will be stirred and carry out mist projection granulating under vacuum, it is 30 μm ~ 45 μm of graphene modification to obtain particle diameter
SrAl2O4:Eu3+,Dy3+Codope WC-Co sprayed on material.
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