CN107354420A - Prepare the preparation method that residual stress coating is modified hot spray powder with graphene - Google Patents

Prepare the preparation method that residual stress coating is modified hot spray powder with graphene Download PDF

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CN107354420A
CN107354420A CN201710508243.XA CN201710508243A CN107354420A CN 107354420 A CN107354420 A CN 107354420A CN 201710508243 A CN201710508243 A CN 201710508243A CN 107354420 A CN107354420 A CN 107354420A
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powder
graphene
residual stress
coating
preparation
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CN107354420B (en
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汤智慧
田浩亮
郭孟秋
王长亮
崔永静
高俊国
张欢欢
周子民
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AECC Beijing Institute of Aeronautical Materials
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AECC Beijing Institute of Aeronautical Materials
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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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7792—Aluminates

Abstract

The present invention, which provides, prepares the preparation method that residual stress coating is modified hot spray powder with graphene, prepare residual stress sensitive coating using plasma spray technology the residual stress in the range of coat inside through thickness can change in real time, due to residual stress concentrations failure can be caused to play forewarning function coating, monitor coating integrity and safe duty status.Compared to applications of the single rare earth ion Eu3+ in residual stress sensitive coating, the weak problem of fluorescence intensity signals be present, the present invention can induce the highly sensitive response of luminous intensity by the synergy mechanism of Dy3+/Eu3+ codopes realizing residual stress of the preparation residual stress sensitive coating in the range of through thickness.High using such scheme, dusty spray epigranular, purity, graphene content is high in powder, and residual stress sensitive coating is prepared available for plasma spray technology.

Description

Prepare the preparation method that residual stress coating is modified hot spray powder with graphene
Technical field
The CaAl2Si2O8 of the graphene modification of residual stress sensitive coating is prepared the invention belongs to plasma spray technology:Eu3 +, Dy3+ codopes WC-Co sprayed on material technical field, more particularly to one kind prepare residual stress coating graphene The preparation method of modified hot spray 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 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.
Wear-resistant coating is typically in long service under the bad working environments such as high load, alternate load, and residual stress in coating is not Disconnected change eventually results in coating and the failure such as deformed, ftracture and come off.Therefore to estimate after thermal spraying remanufactures The secondary service life of part, just the residual stress in coat system and its distribution situation accurately must be assessed and had The control of effect.Up to the present, to remanufacture Parts Surface Coating complete machine military service during residual stress with the change of operating mode The research work changed and carry out inline diagnosis is difficult to carry out, and typically only ability when large areas of pitting or spalling failure occurs in coating There is obvious signal prompt, belong to " judging afterwards ".This failure has sudden and is difficult to foreseeability, often in material safety Just failed suddenly when being on active service under coefficient, it is possible to serious damage, or even the line operator of serious threat one are produced to equipment The safety of member.In addition, residual stress be difficult to obtain Accurate Prediction and control essentially consist in residual stress caused by coating bullet occurs The microcosmic progressive accumulated damage process such as plastic deformation, crack initiation, extension, connection and the fracture of material, the basic nothing of naked eyes Method is directly observed.Therefore, develop high sensitivity, effectively and can monitor on-line residual stress in coating develop and coating be on active service The visualizing monitor technology of microscopic damage process is extremely necessary in journey.
Stress-induced fluorescent material is a kind of new luminous energy and the functional material of mechanical energy conversion, has luminous intensity and material The characteristics of stress is proportional suffered by material.Its principle of luminosity is that extraneous stress is applied on solid material, makes material internal Residual stress is produced, residual stress causes deformation and launches the phenomenon of light extraction.The present invention is directed to propose a kind of have residual stress Induce fluorescence from quick intelligent wear-resistant coating, coating under arms during residual stress and induce real-time between fluorescence intensity Feedback and sensitive response, so as to carry out on-line monitoring in situ to sprayed coating residual stress and remanufacture in part friction process The visual analyzing that the failures such as the peeling of coating, micro-crack develop, it is real in engineer applied that wear-resistant coating is remanufactured to thermal spraying Existing healthy self diagnosis and early warning failure have great theory and real value.
At this stage, for thermal spraying remanufacture coating residual stress primary evaluation technology have boring method, x-ray diffraction method, Supercritical ultrasonics technology etc., although every kind of detection method has its characteristic and advantage, measured result still has its limitation, such as drills Method is destructive detection method, and each parts can not be detected in engineering practice.Penetration depth of the X ray to metal It is limited, can only be without skin stress be devastatingly detected, X-ray diffraction method is combined with layer stripping can determine coating along thickness side To residual stress distribution, deep layer stress can be detected using the method, but part need to be destroyed.Ultrasonic detection technology is non-broken Bad property detection method, have the advantages that penetration power is strong, sound beam direction is good, but the result of supercritical ultrasonics technology detection stress is ultrasonic wave The average value in certain path is passed through inside sample, although without destructiveness, the overall stress distribution of structure can not be obtained.Cause This, up to the present also it is a kind of go for for thermal spraying remanufacture part coating it is lossless, it is online, monitor in real time Technology.
In recent years, a kind of new residual stress detection method based on stress-induced fluorescent material increasingly causes people's Gaze at extensively.Stress-induced fluorescence process is that material surface is caused internal residual stress to become by the effect of mechanical stress Change, so as to excite the matrix for being compounded in material internal, sensitizer, activator（Generally compound rare-earth ion Eu2+, Er2+, Dy3 +, Sm2+ etc. compound）Deng absorption energy, the energy absorbed is shifted by some modes to the centre of luminescence, by the centre of luminescence Excite to excitation state, the centre of luminescence and return to ground state from excitation state and light.
Separately there are some researches show, Eu3+, if Dy3+ applied in coating due to the sensitivity in coat inside excitation signal It has been declined that, its characteristics of luminescence can be influenceed, there are some researches show graphene oxide（GO）It is the derivative of graphene, its surface contains There is substantial amounts of oxygen-containing functional group, it is exactly caused oxygen-containing function in graphene oxidizing process that graphene, which has the principle of fluorescent characteristic, Group causes π tracks that defect occurs and causes.Also there are some researches prove GO surface oxygen functional groups can influence fluorescence intensity and position Change.To sum up analyze, the composition that Dy 3+/Eu3+ are modified using graphene regulates and controls and prepared enhancing Dy 3+/Eu3+ can be achieved The problem weak applied to fluorescence intensity in residual stress sensitivity wear-resistant coating.
Therefore, the prior art is defective, it is necessary to improve.
The content of the invention
The present invention proposes that a kind of graphene for being used to prepare residual stress sensitive coating is modified hot spray powder and preparation side Method, powder provided by the invention can prepare sensitive the applying with residual stress response fluorescence intensity characteristic using hot painting technology Layer, coat inside Dispersed precipitate have residual stress to excite the graphene of the characteristics of luminescence to be modified CaAl2Si2O8：Dy 3+/Eu3+ization Compound, analysis coating under arms during residual stress and induce the Real-time Feedback between fluorescence intensity and sensitive response, from And on-line monitoring in situ can be carried out to sprayed coating residual stress and remanufactures the peeling of part friction process floating coat, micro-crack The visual analyzing developed Deng failure, it is expected to realize that to remanufacture residual stress of the part wear-resistant coating in Life cycle real-time Monitoring, reaches the purpose to coating failure early warning, wear-resistant coating is remanufactured to thermal spraying healthy autodiagnosis is realized in engineer applied Disconnected and early warning failure has great theory and real value.
The technical problems to be solved by the invention are in view of the shortcomings of the prior art, there is provided one kind prepares residual stress coating The preparation method of hot spray powder is modified with graphene, is comprised the following steps：
Step 1：Weigh a certain amount of strontium carbonate（CaCO3）, aluminum oxide（Al2O3）, silica（SiO2）, weigh a certain amount of wine Essence, mixed-powder is placed in progress ball milling mixing certain time in planetary ball mill with alcohol, until alcohol volatilizees completely；Then Transposition is placed in high-temperature vacuum furnace held for some time under certain temperature in corundum boat；
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 CaAl that the graphene of about 1 μm ~ 3 μm of powder diameter is modified2Si2O8: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.
In above-mentioned, in the step 1, strontium carbonate（CaCO3）:Aluminum oxide（Al2O3）:Silica（SiO2）Mass ratio For 2.5 ~ 3:1.5:1, alcohol and strontium carbonate（CaCO3）, aluminum oxide（Al2O3）, silica（SiO2）Mixed-powder mass ratio is 2~3:1, Ball-milling Time about 70 min ~ 100min, powder treatment temperature in high temperature furnace is 940 DEG C ~ 1080 DEG C after ball milling mixing, Processing time is 4 h ~ 7h.
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, supersonic frequency 15Hz.
In above-mentioned, in the step 3, europium oxide（Eu2O3）And dysprosia（Dy2O3）Mixed using watery hydrochloric acid, wherein aoxidizing Europium is 2 ~ 2.5 with dysprosia mass percent:1, distilled water is 25 ~ 30 with europium oxide combined oxidation dysprosium mixture quality ratio:1, Homogenizer is with 500rpm/min speed, and stir processing 50min ~ 90min.
In above-mentioned, in the step 4, by the europium oxide and dysprosia mixed solution of the processing that stirred in the step 3 The graphene oxide dispersion that the step 2 of different content obtains constantly is instilled, the ratio of two of which mixed liquor is controlled in quality Percentage is 6 ~ 10:1, under vacuum, it is stirred continuously with 600rpm/min speed, heating-up temperature is 400 DEG C ~ 600 DEG C, Mixing time is 50 ~ 90min, while constantly instills 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%H2+95%N2）In high temperature process furnances, treatment temperature is 1480 DEG C ~ 1640 DEG C, processing time For 4h ~ 6h, ball mill crushing processing is then carried out, what the graphene that screening obtains about 1 μm ~ 3 μm of powder diameter was modified CaAl2Si2O8:Eu3+,Dy3+Powder.
In above-mentioned, in the step 6, weigh step 5 and obtain the CaAl that graphene is modified2Si2O8:Eu3+,Dy3+Powder with The WC-Co powder qualities ratio that particle diameter is 1 μm ~ 3 μm is 1% ~ 3%, and obtaining powder with step 3 mixes, and adds a certain amount of polyvinyl alcohol, 60 ~ 80 DEG C of heating, stir 60 ~ 90min, the rpm/min of stir speed (S.S.) 500 ~ 700；By the liquid material after being stirred in vacuum condition Lower carry out mist projection granulating, obtain the CaAl that the graphene that particle diameter is 30 μm ~ 45 μm is modified2Si2O8:Eu3+,Dy3+Codope WC-Co Dusty spray.
Compared with immediate prior art, the invention has the advantages that：
1）Compared to traditional WC-Co powder, WC-Co wear-resistant coatings prepared by thermal spraying can not assess residual stress in coating change Problem, the CaAl that graphene provided by the invention is modified2Si2O8:Eu3+,Dy3+Codope WC-Co dusty spray, using heat Spraying technology prepares the residual stress change that residual stress sensitive coating can in real time in the range of coat inside through thickness, can be right Coating monitors coating integrity and safe duty status because residual stress concentrations cause failure to play forewarning function.
2）Compared to single rare earth ion Eu3+, it is weak to there are fluorescence intensity signals in the application in residual stress sensitive coating Problem, the present invention pass through Dy3+/Eu3+The synergy mechanism of codope, it can realize that preparing residual stress sensitive coating exists Residual stress in the range of through thickness induces the highly sensitive response of luminous intensity.
3）Technical scheme provided by the invention can be modified CaAl in Sheet Graphite alkene2Si2O8:Eu3+,Dy3+, pass through control Content ratio between reactant, 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 that enhancing rare earth ion is optical The purpose of energy.
4）The residual stress sensitive coating for being directly appended to dusty spray preparation not modified compared to graphene, institute of the present invention The graphene of acquisition, which is modified dusty spray and reduces to be blown by high speed, the spraying flame stream of high temperature in spraying process, to fly and loses, and has Effect remains the component content of graphene in the coating and is uniformly distributed.
5）The CaAl that graphene provided by the invention is modified2Si2O8:Eu3+,Dy3+Codope WC-Co dusty spray, is adopted Residual stress sensitive coating is prepared with plasma spray technology, on the one hand graphene can improve the intensity and toughness of coating, sharp in addition With graphene/Dy3+/Eu3+Dispersed precipitate in coat inside as secondary phase toughening coating, while play to coating occur crackle There is suppression and stress relaxation, made great sense to improving residual stress sensitive coating military service performance.
Brief description of the drawings
Fig. 1 is the CaAl that graphene is modified2Si2O8:Eu3+,Dy3+Codope WC-Co dusty spray low power ESEM Figure.
Fig. 2 is the CaAl that graphene is modified2Si2O8:Eu3+,Dy3+Codope WC-Co dusty spray high power ESEM Figure.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1：
The present invention provides a kind of preparation method for preparing residual stress coating graphene and being modified hot spray powder, including step （1）Weigh 30g strontium carbonate（CaCO3）, 20g aluminum oxide（Al2O3）, 10g silica（SiO2）, 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 in In corundum boat, treatment temperature is 940 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 300ml 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 1g 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 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 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 1480 DEG C, processing time 4h, then carries out ball Break process is ground, screening obtains the CaAl that the graphene of about 1 μm ~ 3 μm of powder diameter is modified2Si2O8: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 CaAl2Si2O8:Eu3+,Dy3+Powder mixes, and adds a certain amount of binding agent polyvinyl alcohol, heats 60 DEG C, stirs 60min, stirring speed The rpm/min of rate 500.Liquid material after being stirred is subjected to mist projection granulating under vacuum, it is 30 μm ~ 45 μm to obtain particle diameter Graphene be modified CaAl2Si2O8:Eu3+,Dy3+Codope WC-Co dusty spray.
The CaAl being modified as shown in Figure 1 for graphene prepared by the example2Si2O8:Eu3+,Dy3+Codope WC-Co spray Apply powder low power scanning electron microscope (SEM) photograph.As can be seen that prepare powder particle epigranular, reunion is preferable, spherical size is complete Whole, good fluidity.
It is illustrated in figure 2 the CaAl that the graphene of example preparation is modified2Si2O8:Eu3+,Dy3+Codope WC-Co spray Powder high power scanning electron microscope (SEM) photograph is applied, as shown by arrows in FIG. it can be seen that the transparence graphene oxide of nano thin-layer is embedded in ball Inside shape particle, particle surface is adhered to, also apposition growth has the europium oxide and dysprosia particle of nanoscale to graphenic surface.
Embodiment 2：
On the basis of above-described embodiment, in the present embodiment, step（1）Weigh 60g strontium carbonate（CaCO3）, 30g aluminum oxide （Al2O3）, 20g silica（SiO2）, 1000ml alcohol is weighed, mixed-powder is placed in planetary ball mill with alcohol and carried out Ball milling mixing 80min, until alcohol volatilizees completely.Subsequent transposition is in corundum boat, and treatment temperature is 1000 DEG C in high temperature furnace, Processing time is 5 h.
Step（2）Weigh 2g graphene oxides and be dispersed in ultrasonic vibration in 600ml absolute ethyl alcohols and prepare graphene oxide point Dispersion liquid.The ultrasonic disperse time is 140min, supersonic frequency 15Hz.
Step（3）Weigh 4g europium oxides（Eu2O3）With 2g dysprosias（Dy2O3）, 600ml diluted hydrochloric acid dissolutions are added, are added simultaneously Enter 600ml distilled water, homogenizer is with 500rpm/min speed, and stir processing 70min, 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 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 1520 DEG C, processing time 5h, then carries out ball Break process is ground, screening obtains the CaAl that the graphene of about 1 μm ~ 3 μm of powder diameter is modified2Si2O8: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 CaAl2Si2O8:Eu3+,Dy3+Powder mixes, and adds a certain amount of binding agent polyvinyl alcohol, heats 70 DEG C, stirs 70min, stirring speed The rpm/min of rate 600.Liquid material after being stirred is subjected to mist projection granulating under vacuum, it is 30 μm ~ 45 μm to obtain particle diameter Graphene be modified CaAl2Si2O8:Eu3+,Dy3+Codope WC-Co dusty spray.
Embodiment 3：
On the basis of above-described embodiment, in the present embodiment, step（1）Weigh 80g strontium carbonate（CaCO3）, 60g aluminum oxide （Al2O3）, 20g silica（SiO2）, 1000ml alcohol is weighed, mixed-powder is placed in planetary ball mill with alcohol and carried out Ball milling mixing 90min, until alcohol volatilizees completely.Subsequent transposition is in corundum boat, and treatment temperature is 1040 DEG C in high temperature furnace, Processing time is 7 h.
Step（2）Weigh 4g 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 160min, supersonic frequency 15Hz.
Step（3）Weigh 3g europium oxides（Eu2O3）With 1.5g dysprosias（Dy2O3）, 600ml diluted hydrochloric acid dissolutions are added, simultaneously 600ml distilled water is added, homogenizer is with 500rpm/min speed, and stir processing 80min, 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 500 DEG C, mixing time 80min, 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 1600 DEG C, processing time 5h, then carries out ball Break process is ground, screening obtains the CaAl that the graphene of about 1 μm ~ 3 μm of powder diameter is modified2Si2O8:Eu3+,Dy3+Powder.
Step（6）The WC-Co powder 7000g that particle diameter is 1 μm ~ 3 μm are weighed, with step（5）Obtain what graphene was modified CaAl2Si2O8:Eu3+,Dy3+Powder mixes, and adds a certain amount of binding agent polyvinyl alcohol, heats 70 DEG C, stirs 80min, stirring speed The rpm/min of rate 600.Liquid material after being stirred is subjected to mist projection granulating under vacuum, it is 30 μm ~ 45 μm to obtain particle diameter Graphene be modified CaAl2Si2O8:Eu3+,Dy3+Codope WC-Co dusty spray.
Example 4：
On the basis of above-described embodiment, in the present embodiment, step（1）Weigh 90g strontium carbonate（CaCO3）, 60g aluminum oxide （Al2O3）, 30g silica（SiO2）, 1200ml alcohol is weighed, mixed-powder is placed in planetary ball mill with alcohol and carried out Ball milling mixing 90min, until alcohol volatilizees completely.Subsequent transposition is in corundum boat, and treatment temperature is 1080 DEG C in high temperature furnace, Processing time is 6 h.
Step（2）Weigh 4g 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 4g europium oxides（Eu2O3）With 2g dysprosias（Dy2O3）, 1000ml diluted hydrochloric acid dissolutions are added, simultaneously 600ml distilled water is added, homogenizer is with 500rpm/min speed, and stir processing 90min, 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 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 600 DEG C, mixing time 90min, 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 1640 DEG C, processing time 6h, then carries out ball Break process is ground, screening obtains the CaAl that the graphene of about 1 μm ~ 3 μm of powder diameter is modified2Si2O8: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 CaAl2Si2O8:Eu3+,Dy3+Powder mixes, and adds a certain amount of binding agent polyvinyl alcohol, heats 80 DEG C, stirs 90min, stirring speed The rpm/min of rate 700.Liquid material after being stirred is subjected to mist projection granulating under vacuum, it is 30 μm ~ 45 μm to obtain particle diameter Graphene be modified CaAl2Si2O8:Eu3+,Dy3+Codope WC-Co dusty spray.
Compared with immediate prior art, the invention has the advantages that：
1）Compared to traditional WC-Co powder, WC-Co wear-resistant coatings prepared by thermal spraying can not assess residual stress in coating change Problem, the CaAl that graphene provided by the invention is modified2Si2O8:Eu3+,Dy3+Codope WC-Co dusty spray, using heat Spraying technology prepares the residual stress change that residual stress sensitive coating can in real time in the range of coat inside through thickness, can be right Coating monitors coating integrity and safe duty status because residual stress concentrations cause failure to play forewarning function.
2）Compared to single rare earth ion Eu3+, it is weak to there are fluorescence intensity signals in the application in residual stress sensitive coating Problem, the present invention pass through Dy3+/Eu3+The synergy mechanism of codope, it can realize that preparing residual stress sensitive coating exists Residual stress in the range of through thickness induces the highly sensitive response of luminous intensity.
3）Technical scheme provided by the invention can be modified CaAl in Sheet Graphite alkene2Si2O8:Eu3+,Dy3+, pass through control Content ratio between reactant, 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 that enhancing rare earth ion is optical The purpose of energy.
4）The residual stress sensitive coating for being directly appended to dusty spray preparation not modified compared to graphene, institute of the present invention The graphene of acquisition, which is modified dusty spray and reduces to be blown by high speed, the spraying flame stream of high temperature in spraying process, to fly and loses, and has Effect remains the component content of graphene in the coating and is uniformly distributed.
5）The CaAl that graphene provided by the invention is modified2Si2O8:Eu3+,Dy3+Codope WC-Co dusty spray, is adopted Residual stress sensitive coating is prepared with plasma spray technology, on the one hand graphene can improve the intensity and toughness of coating, sharp in addition With graphene/Dy3+/Eu3+Dispersed precipitate in coat inside as secondary phase toughening coating, while play to coating occur crackle There is suppression and stress relaxation, made great sense to improving residual stress sensitive coating 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 (7)

1. it is a kind of prepare residual stress coating graphene be modified hot spray powder preparation method, it is characterised in that including with Lower step：
Step 1：Weigh a certain amount of strontium carbonate（CaCO3）, aluminum oxide（Al2O3）, silica（SiO2）, weigh a certain amount of wine Essence, mixed-powder is placed in progress ball milling mixing certain time in planetary ball mill with alcohol, until alcohol volatilizees completely；Then Transposition is placed in high-temperature vacuum furnace held for some time under certain temperature in corundum boat；
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 CaAl that the graphene of about 1 μm ~ 3 μm of powder diameter is modified2Si2O8: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.
2. preparation method according to claim 1, it is characterised in that in the step 1, strontium carbonate（CaCO3）:Aluminum oxide （Al2O3）:Silica（SiO2）Mass ratio is 2.5 ~ 3:1.5:1, alcohol and strontium carbonate（CaCO3）, aluminum oxide（Al2O3）, two Silica（SiO2）Mixed-powder mass ratio is 2 ~ 3:1, Ball-milling Time about 70 min ~ 100min, powder is in height after ball milling mixing Treatment temperature is 940 DEG C ~ 1080 DEG C in warm stove, and processing time is 4 h ~ 7h.
3. 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, 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 2 ~ 2.5:1, distilled water is compound with europium oxide Dysprosia mixture quality ratio is 25 ~ 30:1, homogenizer with 500rpm/min speed, the processing 50min that stirs ~ 90min。
5. preparation method according to claim 1, it is characterised in that equal by being stirred in the step 3 in the step 4 The europium oxide and dysprosia mixed solution of even processing constantly instill the graphene oxide dispersion that the step 2 of different content obtains, It is 6 ~ 10 that the ratio of two of which mixed liquor, which is controlled in mass percent,:1, under vacuum, with 600rpm/min speed It is stirred continuously, heating-up temperature is 400 DEG C ~ 600 DEG C, and mixing time is 50 ~ 90min, 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%H2+95%N2）In high temperature process furnances, place It is 1480 DEG C ~ 1640 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 CaAl that 1 μm ~ 3 μm of graphene is modified2Si2O8: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 CaAl2Si2O8: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 mixing is obtained, adds a certain amount of polyvinyl alcohol, heats 60 ~ 80 DEG C, stirs 60 ~ 90min, the rpm/ of stir speed (S.S.) 500 ~ 700 min；Liquid material after being stirred is subjected to mist projection granulating under vacuum, the graphene that particle diameter is 30 μm ~ 45 μm is obtained and changes The CaAl of property2Si2O8:Eu3+,Dy3+Codope WC-Co dusty spray.
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