CN104114738B - Reactive gas shroud or flame sheath for suspension plasma spray processes - Google Patents
Reactive gas shroud or flame sheath for suspension plasma spray processes Download PDFInfo
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- CN104114738B CN104114738B CN201280069723.6A CN201280069723A CN104114738B CN 104114738 B CN104114738 B CN 104114738B CN 201280069723 A CN201280069723 A CN 201280069723A CN 104114738 B CN104114738 B CN 104114738B
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Classifications
-
- 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
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Coating By Spraying Or Casting (AREA)
- Nozzles (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Plasma Technology (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
A system and method for producing thermal spray coatings on a substrate from a liquid suspension is disclosed. The disclosed system and method include a thermal spray torch for generating a plasma and a liquid suspension delivery subsystem for delivering a flow of liquid suspension with sub-micron particles to the plasma to produce a plasma effluent. The liquid suspension delivery subsystem comprises an injector or nozzle which can produce a reactive gas shroud surrounding the plasma effluent. A flame envelope can also be used to isolate injection of the liquid suspension. The shroud or flame envelope can retain the sub-micron particles entrained within the plasma effluent and substantially prevent entrainment of ambient gases into the plasma effluent. The liquid suspension delivery subsystem can be arranged as an axial injection system, a radial internal injection system or an external radial injection system.
Description
Invention field
The present invention relates to the plasma spraying that suspends, relates more specifically to use reactant gas and/or flame building enclosure
（flame envelope）Surround suspension plasma spraying effluent and/or surround liquid suspension injection stream, with promote and
The method and system that control effluent interacts with suspension.
Background
Traditional plasma spraying technology is mainly sent into the plasma of plasma torch by powder-type coating using powder feeder
In body jet.But, this technology is typically limited to using at least+350 mesh（I.e. about 45 microns of median particle, wherein 50%
Particle be less than the median particle, in addition 50% particle be more than the median particle）Or bigger particle.Be down to granularity+
Below 325 mesh, powder-type coating is introduced directly in plasma jet can become more and more difficult.Particulate tends to tightly packed
And agglomeration, improve the blocking possibility in traditional powder feed system.
In addition to blocking, conventional plasma spraying technology also is not suitable for using particulate because of other reasons.It is low due to particulate
When quality, very fast combination with plasma jet, particulate tends to deviate plasma jet during being radially injected
Boundary layer and do not penetrate boundary layer.Speed needed for the penetrating of thin coating particle is too big so that effluent itself cannot not disturbed
In the case of physics realization.Speed is brought up to into this degree and there is actual restriction.
Thinner coating particle is desirable in thermal barrier coating.Thinner particle typically results in closeer coating and thinner
Microstructure appearance, including for example less lamelliform shred（lamellar splats）And particle.Thinner particle is also inclined to
In coated components of the generation with improved micro-structural.Because relative to the high surface area of its little quality, particulate is also easier to melt
Melt.
Suspension plasma spraying（SPS）Occur as the means of deposition more fine particle.SPS is in plasma spraying technology
Relatively new progress, its by the use of paint ingredient or the sub-micron grade particle of microparticle material liquid suspension rather than dry powder as
Coating medium.The liquid serves as the carrier of sub-micron grade particle, and the otherwise particle tends to agglomeration to limit or hinder powder stream
To spray gun.The liquid also shows and serves as thermal activation solution, and it makes solids of sedimentation or reacts with suspended particles.Mainly due to using outstanding
Floating minimum particle in a liquid carrier, it is micro- that suspension plasma spraying method shows manufacture unique coating with unique properties
The ability of structure.Drop also provides extra quality to provide the momentum being radially injected needed for entrainment.
Although SPS has these to improve compared with conventional plasma spraying technology, existing SPS system and method are still under
Various shortcomings.For example, traditional SPS generally produces what is grown with uncontrolled granular micro-structure degree and/or shortage directional orientation
Coating, both of which causes poor coating performance.Adverse chemical reaction can occur between substrate and the coating of deposition, this makes micro-
Structure problem is further complicated.
Furthermore, it may be necessary to the longer correlation gauge between nozzle location and saltation point from（stand-off distances）
With the geometry that fully coating is complicated, such as turbine blade.But, longer correlation gauge is from may cause the excessive of paint ingredient
The resident or time of staying, thereby result in paint ingredient and cooled down and solidified again before substrate is reached.Reducing standoff distance can cause
Underheat, so that particulate can not absorb enough heat and fully melt.In both of these case, final result is that particulate does not glue
Close in substrate, thus reduce the deposition efficiency of the material.The finer grain of paint ingredient improve surface area so that can with than
Common faster speed quickly heating and cooling in standard plasma body technique.Therefore, compared with fine particles raising surface area
Beyond example challenge is brought to optimizing correct standoff distance.
Further, the turbulent flow that plasma gas flows out thing is discharged from the nozzle of spray gun.Plasma flow out thing with it is big
The turbulence type of gas interacts and causes effluent temperature quickly to reduce and quickly orientation flow direction change, this cause paint particles from
Evict from the flow path of directed toward substrate.Therefore, the particulate evicted from causes the deposition efficiency for reducing.
The problems referred to above are only the new challenge classes brought using the increasingly thinner coating medium composition of SPS system and method deposition
Some examples of type.In view of continual challenge, needs to improve existing suspension plasma spraying method and system.
Summary of the invention
Following article is described in more detail, and embodiment of the present invention is devoted to solving some shortcomings and providing by using encirclement
Plasma effluent stream and liquid suspension contained therein（" effluent ", " stream are referred to as herein with specification full text
Effluent stream ", " plasma " or " plasma outflow thing " or " plasma effluent stream "）Reactant gas shield control
The technology of above-mentioned interaction.The present invention is uniquely by reactant gas shield and the sub-micron transmitted using Jing liquid suspensions
The plasma spraying method of particle is combined to improve existing suspension plasma spraying ability, and by controlling suspension injection and fragmentation
（fragmentation）And the interaction between effluent and suspension and bring the possibility of new coating micro-structural.
The present invention may include any following aspect of various combinations, may also include following described in written description or accompanying drawing
Any other aspect.
The present invention may be characterized as being manufactured the thermal spray system of coating in substrate by liquid suspension, and it is included：For
Generate the thermal jet torch of plasma；For the liquid suspension transmission subsystem of liquid suspension stream of the transmission containing submicron particle
System；With the nozzle assembling for liquid suspension will to be sent to from the plasma of thermal jet torch to produce plasma outflow thing
Part, the nozzle assembly is adapted to produce the reactant gas shield for surrounding the plasma outflow thing substantially；The reaction
Property gas shroud be configured for making submicron particle to keep being entrained in plasma substantially and flow out in thing, and prevent gas substantially
Into and with plasma flow out thing reaction；It is outstanding to strengthen that wherein described reactant gas shield flows out thing reaction with plasma
The fragmentation of supernatant liquid droplet simultaneously flows out the evaporation species that submicron particle is manufactured in thing in plasma.
The present invention may also be characterized as that coating is manufactured in substrate using the liquid suspension of the submicron particle that is wherein scattered here and there
Method, the method comprising the steps of：Plasma is generated by thermal jet torch；By the liquid of the submicron particle that is wherein scattered here and there
Suspension flow is sent to plasma or it is neighbouring to produce plasma effluent stream；With reactant gas shield surround etc. from
Daughter effluent is so that submicron particle keeps being entrained in plasma outflow thing, and prevents environmental gas to be entrained to substantially
In gas ions effluent；Make shroud air and plasma flow out thing reaction to strengthen the fragmentation of suspension droplets and in plasma
The evaporation species of manufacture submicron particle in body effluent；With by the besieged plasma stream wherein containing submicron particle
Go out thing directed toward substrate with coating substrate.
Brief description
Become apparent from finding out from the contact following more detailed description that is given of drawings below the present invention it is above and other in terms of,
Feature and advantage, wherein：
Fig. 1 is the schematic diagram of the prior art suspension plasma spraying method of the axial injection for using liquid suspension；
Fig. 2 is the schematic diagram of the prior art suspension plasma spraying method for using the inner radial of liquid suspension to inject；
Fig. 3 is the schematic diagram of the prior art suspension plasma spraying method for using the outer radial of liquid suspension to inject；
Fig. 4 is the suspension plasma spraying of the axial injection that an embodiment of the invention uses liquid suspension
The schematic diagram of the reactant gas shield of method；
Fig. 5 is the suspension plasma that another embodiment of the invention uses the inner radial of liquid suspension to inject
The schematic diagram of the reactant gas shield of spraying process；
Fig. 6 is the suspension plasma that still another embodiment of the invention uses the outer radial of liquid suspension to inject
The schematic diagram of the reactant gas shield of spraying process；
Fig. 7 is shown using encirclement suspension plasma spraying method by interior reactant gas layer and outer inert gas barrier
（shield）The a further embodiment of the invention of the double gas shrouds for constituting；
Fig. 8 is shown using encirclement suspension plasma spraying method by the first reactant gas layer and the second reactant gas layer
The a further embodiment of the invention of the double gas shrouds for constituting；
Fig. 9 is that an embodiment of the invention uses the liquid suspension that gas blanket or gas are coated axially to note
The schematic diagram of the suspension plasma spraying method for entering；
Figure 10 is that another embodiment of the invention is used inside the liquid suspension that gas blanket or gas are coated
The schematic diagram of the suspension plasma spraying method being radially injected；With
Figure 11 is that still another embodiment of the invention is used outside the liquid suspension that gas blanket or gas are coated
The schematic diagram of the suspension plasma spraying method being radially injected.
Describe in detail
The present invention relates to be used for the new SPS system and method for coating deposition.The SPS system and method for the present invention are especially fitted
For depositing submicron particle.Illustrate this in various embodiments and with reference to various aspects and feature of the invention herein
It is open.
By the relation and function that more fully understand the various key elements of the present invention as detailed below.The detailed description is considered in this public affairs
The key element under various arrangements and combination, aspect and embodiment in the range of opening.Therefore the disclosure is defined as comprising this
Any such combination of a little key element, aspect and embodiments or wherein selected key element, aspect and embodiment and row
Row, are made up of any such combination and permutation or are made up of any such combination and permutation substantially.
Present invention recognizes that the shortcoming of existing SPS system and method.Reference picture 1-3 preferably recognizes these shortcomings.Fig. 1-3
Show respectively using the axial injection of liquid suspension；The inner radial injection of liquid suspension and the outside footpath of liquid suspension
To the prior art suspension plasma spray system and several schematic diagrames of method 100,200 and 300 of injection.In each prior art
In system, there is many physics and chemical interaction, many of which is uncontrolled.For example, figures 1 and 2 show that due to effluent
In turbulent flow and the fragmentation of liquid-carrier that occurs in region 110 and 201 with unacceptable random fashion
（fragmentation）.There is the fragmentation soon after plasma flows out thing and liquid suspension contact.Art used herein
Language " effluent " and " plasma outflow thing " be used interchangeably and be intended to indicate that plasma gas, paint ingredient or particle and
Any combinations of liquid-carrier, each of which flows out from the outlet of spray tip.For example, each of which spray gun each nozzle
105th, 205 and 305 immediate outlet, effluent 140,240 and 340 is very possible by plasma（I.e. due to being exposed to
The hot Cauldron gas ionized under the electric arc generated between negative electrode and anode）With the liquid-carrier droplet containing coating particle
（That is liquid suspension 109,209 and 309）Constitute.But, in the vicinity of substrate 108,208 and 308, effluent 140,240 and
340 it is main by paint particles and may substantially cooler effluents 140,240 and 340 constitute because to SPS rubbing methods 100,
200 and 300 this stage, basic all liq carrier evaporates.
Fig. 1 and 2 also show and evict the liquid of a part of fragmentation from from effluent 140 and 240 in region 110 and 210 respectively
The droplet of liquid suspension 109 and 209.
Fig. 1-3 be further illustrated near spray tip 105,205 and 305 outlet region in air entrainment 122,
222 and 322 to plasma is flowed out in thing 140,240 and 340.Atmospheric gas, including the infiltration of oxygen cause carry secretly air
With flammable liquid carrier（Such as ethanol）Accelerated combustion.Additionally, Fig. 1 shows, as shown in representative area 105, there is liquid to carry
Evacuator body, causes many sub-micron solids to coalesce and melt.If in effluent 140,240 and 340 internal memories in preferable heat
Condition, the sub-micron or superfine particle of certain percentage change into evaporation species, thus cause deposition efficiency and the base for reducing
The coating at bottom 108,208 and 308 is not enough.
These fragmentation droplets of suspension 109,209 and 309, molten particles and evaporation species and the combustion for being derived from air entrainment
Burn accessory substance be sent to substrate 108,208 and 308 with effluent stream 140,240 and 340 together, during this period such as region 105,
There is additional suspension-chemistry of particles reaction, including undesired reaction, such as particle oxidation shown in 205 and 305.Also exist
During the transport of effluent 140,240 and 340, many fragmentation droplets and grain are evicted in continuation from from suspension 109,209 and 309
Son, thus further reduces deposition efficiency.
Fig. 1-3 further shows, as effluent stream 140,240 and 340 is close to the substrate 108,208 and 308 to be coated with,
Temperature Distribution in effluent stream 140,240 and 340 changes, and causes some evaporation species for solidifying again and carrying secretly of colder particle
Condensation.Reach substrate 108,208 and 308 when, under various physical states coating collision substrate and formed coating 106,
206 and 306, including coating is physically joined in substrate.Substrate 108, the unfavorable chemistry between 208 and 308 and coating can occur
Reaction.
Existing suspension plasma spray system has three critical stages that cannot fully control suspension plasma spraying method
In these physics and chemically interactive shortcoming, these three critical stages are：I () suspension injects and fragmentation；(ii)
Effluent and suspension interact；(iii) interaction of substrate and effluent and coating are piled up.
As discussed in Fig. 4-11, embodiment of the present invention is devoted to solving many disadvantages mentioned above shown in Fig. 1-3.This
Invention is provided by using the reactant gas shield for surrounding effluent stream and/or liquid suspension injection phase（shroud）
And/or sheath（sheath）Control the technology of above-mentioned unfavorable interaction.
Turning now to Fig. 4 to 6, it is shown that the present invention different embodiments schematic diagram, i.e., respectively describe suspend etc. from
Sub- paint finishing and method 400,500 and 600.SPS system and method 400 use the axial injection of liquid suspension 409, its tool
There is encirclement effluent 440（That is plasma and liquid suspension 409）Extension reacting gas shield 401.Can use and appoint
What suitable reactant gas manufacture reacting gas shield 401, such as oxygen, hydrogen, carbon dioxide；Hydrocarbon fuel and in some feelings
Nitrogen in condition, or combinations thereof.By using reactant gas shield 401, effluent 440 can be precisely controlled and hanged
Supernatant liquid 409 interacts, so as to be created due to the chemical reaction occurred between suspension 409 and reactant gas shield 401
Make new coating microstructure possibility.
Fig. 4 to show and flow through encirclement inner nozzle with predetermined flow rate by making reacting gas（Liquid suspension 409 and Cauldron gas
416 relative to each other can in succession or jointly flow through inner nozzle）Outer nozzle and manufacture shield 401.Shield 401 surrounds effluent
402 stream positioning, is consequently formed the reactant gas protective case for surrounding effluent 440.Fig. 4 shows shield 401 from spray tip
Constantly extend to substrate surface 408 in 405 to produce the complete sheath of the effluent 440 being included in.
Liquid suspension 409 is left before the outlet of nozzle 405, as Cauldron gas 416 is from negative electrode 412 and anode 413
Between flow into generate electric arc region, produce plasma 419.Carrier gas conveys liquid suspension 409 and is shown as outstanding with liquid
Supernatant liquid 409 flows through together the center of nozzle 405.Electric arc is generated between negative electrode 412 and anode 413.Cauldron gas 416 is through electricity
Arc area and the internal ionization of nozzle 405 into gas ion and/or free radical hot plasma 419.Plasma 419 is provided in stream
Go out when thing 440 flows to substrate surface 408 and evaporate heat of the liquid-carrier simultaneously needed for the paint ingredient 415 of melt liquid suspension 409
The energy.Plasma 419 also provides energy source and be enough to make what paint ingredient or particle 415 accelerated towards substrate surface 408 to provide
Momentum.
After plasma 419 is made, liquid suspension 409（Liquid-carrier i.e. wherein containing paint ingredient 415 is micro-
Drop）With the outlet that plasma 419 leaves nozzle 405 as effluent 440.Throat meeting of the shroud air 401 in nozzle 405
It is poly-, hereafter leave nozzle 405.It should be understood that term " shield " and " shroud air " there are identical meanings and herein and
Used interchangeably in specification full text.
In a preferred embodiment, reactant gas shield 401 is oxygen-containing gas, such as oxygen or oxygen dilution
Admixture of gas.It is mixed with effluent 440 that oxygen-containing reactant gas shield 401 can be used to controlling or improve reactant gas 401
Conjunction degree and the locus of mixing, the thus burning degree and burning position and gained heat energy of more precise control effluent 440
Distribution.Enhanced burning or other thermal responses can be also improved in the fragmentation of the droplet of liquid suspension 409 and suspension 409
The evaporation of sub-micron coating particle 415.Oxygen-containing reactant gas shield 401 can be used together to produce with fuel base liquid-carrier
Life is more completely burnt, compared with the traditional inert gas shield without shield spraying process or encirclement plasma spraying effluent, can
To cause or realize the burning in more upstream or closer to the point of plasma source 419.The embodiment confirmation of Fig. 4,
Combustion process is towards plasma source 419 upstream in advance by more effectively using relatively low work(using the heat energy of plasma stream
Submicron particle 415 in the plasma torch melting and evaporation liquid-carrier of rate.
Reactant gas shield 401 is configured to be flowed with sufficient rate relative to the flow velocity of effluent 440, so as to be formed in
Continuously going along with sb. to guard him around effluent 440.Effluent 440 is characterised by the track of liquid suspension 409 or flow path at least portion
Divide and be defined to export to substrate surface 408 from nozzle 405, thus the flow path is partially or completely surrounded by reactive shield 401.
As illustrated in the embodiment of figure 4, the length of reactive shield 401 extends to substrate surface 408 from the outlet of nozzle 405, with
Effluent 440 is surrounded completely.The continuous encirclement generation of shield 401 is served as the heat of effective insulator and is gone along with sb. to guard him, so as to through from nozzle
The 405 longer flow path distance for exporting to substrate surface 408 keeps the heat in effluent stream 440.Base is exported to from spray gun 405
The controlled temperature at bottom 408 evaporates can the liquid-carrier of liquid suspension 409.After liquid-carrier evaporation, now by usual
It is included in the droplet of liquid suspension 409（They freely float and advance towards substrate surface 408 now）Interior paint ingredient 415
Realize the heat for evaporating liquid-carrier.Paint ingredient 415 partially or substantially melt when substrate surface 408 is flowed to without
There is significantly cooling.The paint ingredient 415 of melting collides substrate surface 408 to deposit as coating 403.In this way, this changes
The heat entered is gone along with sb. to guard him and therefore improve deposition efficiency.Additionally, the hot holding in effluent 440 improves the uniformity of Temperature Distribution, this
Can reduce over long distances（stand-off）Processing sensitiveness.Therefore, compared with using tradition SPS attainable before, such as Fig. 4
The SPS system and method 400 of the permission uniqueness of the invention shown in embodiment are with farther standoff distance coating complexity
Geometry, and do not cause notable solidification of the paint ingredient 415 when substrate surface 408 is collided.
Although the enhanced burning come using oxygen-containing gas and fuel base fluid body belt carrier is of system and method
Embodiment, but can promote other chemical reactions using reactive shroud air, the reactive shroud air will be with liquid
The change that various elements or compound reaction in medium causes spontaneous generation or occurs because plasma flows out the heat energy of thing
Learn reaction.Such chemical reaction can be designed and controlled to realize coating chemical composition, physical property or the improvement of micro-structural,
Including the oxide, carbide or the nitride that for example form particle.
Advantageously, flow out in plasma and made in effluent 440 using reactant gas shield 401 around thing 440
More heat are made and/or retained, for coating process bigger operation building enclosure is provided（operation envelope）.Bigger
Building enclosure is operated to mean bigger operating distance and submicron particle 415 between spray tip 405 and substrate 408 more
Good heat treatment.In other words, when submicron particle 415 keeps longer stop under operation temperature of its flow path track in regulation
Between, so as to realize that plasma flows out the improved melting of the particle in thing 440 and its increase of evaporation species.Reactant gas
The use of shield 401 also helps the environment and temperature near control substrate surface 408.
The use of the reactant gas shield 401 of encirclement suspension plasma spraying effluent 440 is opened and is developed for this
Many possibilities of the new liquid carrier of suspension 409 or solution of the class containing submicron particle.
Within various embodiments of the present invention, reactant gas shield can be constructed in a controlled manner.Most probable control
Means be related to adjust or manipulate the flow behavior of reactant gas shield, including the volume flow rate and/or speed of gas shroud with
And the concentration of the reactive element in reactant gas shield.In addition it is also possible to control the reactant gas shield turbulent flow and
Dispersing characteristic.Many these flow behaviors depend on the geometry for forming the nozzle of reactant gas shield and construction with
And reactive shroud air supply pressure and temperature.
The embodiment of Fig. 4 shows that shroud air 401 is configured to be layered the flowing of flow velocity situation.Laminar flow shield 401
Speed that is controlled and reducing can make the droplet of liquid suspension 409 through the fragmentation phenomenon of shield 401 and the tradition of Fig. 1-3
SPS system and method 100,200 are compared with 300 to be occurred in more-controlled fashion.Therefore the fragmentation droplet of liquid suspension 409 reaches
To improved particle size distribution.Therefore, paint ingredient 415 is deposited on substrate surface 408 to be formed with more controlled
The coating 403 of size distribution.
Shield 401 also resists the trend that the droplet of liquid suspension 409 is evicted from from effluent 440.In general, not
In the case of there is shield 401, effluent 440 is possible to be enough to that liquid droplet is broken into the turbulent flow conditions of less droplet, and
Undesirably give the excessive momentum of at least some droplet from effluent stream 440 to evict them from during so.Make
With shield 401 droplet and paint ingredient 415 of liquid suspension 409 can be promoted to stay in effluent 440.Therefore, paint ingredient
415 utilization rate is improved.
The combination of above-mentioned process benefit can cause the micro-structural for depositing to the coating 403 on substrate surface 408 to have crystal grain
Orientation and sufficiently small size distribution.Using the SPS system and method 400 of the novelty, these favourable micro-structural possibilities
Can control and can reproduce.
Another embodiment of the invention, Fig. 5 shows SPS system and method 500, wherein in spray tip 505
Inside injection liquid suspension 509.The inside injection of liquid suspension 509 can perpendicular in the nozzle 505 negative electrode 512 with
The axle of the plasma 519 generated between anode 513 is substantially radial to be carried out.It should be understood that liquid suspension can be changed
509 relative to plasma 519 injection angle.
Fig. 5 show Cauldron gas 516 through arc region and the internal ionization of nozzle 505 into gas ion hot plasma shape
State 519.By the inside of liquid suspension 509 injection heating region 519.It should be understood that the injection of suspension 509 can be with
Carry out in the downstream of plasma 519 in anode, this represents torch gas 516 and is cooled to overheated gas from plasmoid
Region.The turbulent flow of plasma 519 makes the liquid-carrier droplet of suspension 509 in nozzle 505 and in the exit of nozzle 505
Fragmentation and/or atomization.
As shown in the embodiment of figure 5, outlet of the length of reactive shield 501 in a continuous manner from nozzle 505 is prolonged
Reach substrate surface 508.Shield 501 provides heat and keeps going along with sb. to guard him and preventing the droplet of suspension 509 from stream to manufacture Continuous Heat
Go out in thing 540 and evict from.The embodiment of Fig. 5 shows that the reactant gas 501 of shield is configured to be layered the flowing of flow velocity situation.Point
Laminar flow shield 501 controlled and the speed for reducing can make the droplet of liquid suspension 509 through shield 501 fragmentation phenomenon with
Traditional SPS system and method 100,200 of Fig. 1-3 are compared with 300 to be occurred in more-controlled fashion.Liquid suspension 509 it is broken
Split droplet therefore reach improved particle size distribution.Therefore, paint ingredient 515 is deposited on substrate surface 508 to be formed
Coating 503 with more controlled size distribution.It should be understood that some coating applications may not require liquid suspension
The 509 notable fragmentation of droplet.Therefore, in another embodiment of the present invention, shield 501 can be configured to not make droplet broken
Split, but still other benefits for the utilization shield 501 for realizing having already mentioned above.
Principle of the invention contemplates other injection phases of liquid suspension.For example, Fig. 6 show SPS systems and
Method 600, wherein liquid suspension 609 are injected outside spray tip 605.The outside injection of liquid suspension 609 can hang down
The straight axle in plasma outflow thing 640 is substantially radial to be carried out.It should be understood that it is relative to change liquid suspension 609
The injection angle of thing 640 is flowed out in plasma.Similar to Fig. 5, reactive shroud air 601 is configured to be layered flow velocity situation stream
It is dynamic, to realize the evenly fragmentation of the droplet of liquid suspension 609.
Present invention contemplates other variants of reactant gas shield.For example, Fig. 7 is another embodiment of the present invention
Schematic diagram, it uses the interior reactant gas shield layer 701 and outer inert gas barrier by encirclement suspension plasma spraying method 700
（shield）The 702 double gas shrouds for constituting.Interior reactant gas shield layer 701 preferably laminar flow as shown in Figure 7.It is this
The use of the double shields in specific arrangements can further improve heat holding, the particle of droplet in the flow region of effluent 740
Fragmentation and the temperature homogeneity along substrate 708.Double shields can also improve paint particles 715 and be limited in effluent 740 along flow path,
Thus basic reduction or elimination paint particles 715 are evicted from from effluent 740.Therefore, sinking for the raising in substrate 708 is realized
Product efficiency.
In another design variable of reactant gas shield, Fig. 8 shows a kind of double reactive gas shroud, and it is by wrapping
Enclose the outer structure of reactant gas shield layer 801 of reactant gas shield layer 802 and second in the first of suspension plasma spraying method 800
Into.The preferably laminar flow as shown in Figure 8 of reactant gas shield layer 802 in first.Different from Fig. 7, the double reactive gas
Shield has two kinds of reactive shields.Separately control reactant gas shield 801 and 802（Such as independently controlled stream
Speed）.Gas for reactant gas shield 801 and 802 can be with identical or different.Two kinds of independent control reactive shields or
The presence of barrier contributes to improving the combustion reaction of the flow path along effluent 840.Except using double reactive gas shroud system and
Outside the enhanced burning that method 800 is brought, the use of double reactive shroud air may additionally facilitate other chemical reactions, wherein reacting
Property gas shroud 801 and 802 each preferentially with liquid suspension 809 in element-specific or compound reaction, cause spontaneous
Chemical reaction that is raw or occurring because plasma flows out the heat energy of thing 840.Can design and control such chemical reaction
To realize the improvement of the chemical composition, physical property or micro-structural of the coating 803 of deposition.
If using the double-deck shield using reactant gas and inert gas or mixing shield, inert gas is generally included
Argon gas, nitrogen and helium or its combination.
Other variants of reactant gas shield can be used.In an example, two or more can be constructed anti-
Answering property gas shroud, preferably independently of one another, to surround effluent.In another example, it is possible to use with inert gas shield knot
Two or more the reactant gas shields for closing.Inert gas shield can be arranged between reactant gas shield.Or,
Inert gas shield can be arranged to surround all reactant gas shields.As another design variable, inert gas shield or
Barrier may be additionally located in each reactant gas shield.In another embodiment, it is also possible to selective construction reactant gas shield
Cover only to surround a part for effluent to the flow path of substrate along it.
Process benefit --- some of them are as previously mentioned, the more controlled microstructure of the coating of deposition can be converted into.
Present invention recognizes that, determine that the micro-structural of coating and the parameter of property include temperature, size and the speed of paint ingredient or particle,
The degree reacted with surrounding environment in deposition process with particle or be exposed under surrounding environment.In the present invention, the reactivity
Gas shroud can keep heat and realize more uniform temperature and controlled Temperature Distribution when coating particle collides substrate surface.
In addition, laminar flow reactant gas shield contributes to manufacturing the coating particle of evenly fragmentation.Therefore the effluent for being shrouded produces
Improved micro-structural.
The micro-structural of the coating of deposition and other factors of property are affected to include sedimentation rate, collision angle and basilar
Matter, using the shield each factor can be to a greater extent controlled.Because paint ingredient or particle are by the gaseous flow of plasma
Go out thing heating and accelerate, the temperature and speed of coating particle depend on the physically and thermally characteristic and plasma spray of the effluent stream
Standoff distance between the outlet of coating device and substrate.The property of effluent stream is controlled by using the shield, can be more accurate
Ground controls the temperature and speed of coating particle to improve coating adhesion and coating microstructure.
The particular type that can be used for the reactant gas shield of the present invention is surrounded near decanting point or decanting point
The flame building enclosure of liquid suspension（flame envelope）.Turning now to Fig. 9 to 11, it is shown that flame building enclosure
The schematic diagram of the different embodiments of construction, i.e., respectively using the flame building enclosure of the liquid suspension for surrounding axial injection；
Surround the flame building enclosure of the liquid suspension of inner radial injection；With the fire of the liquid suspension for surrounding outer radial injection
The suspension plasma spray system and the diagram of method of flame building enclosure.Herein with the full term " flame used herein of specification
Building enclosure " refers to the burning stream formed by the burning of fuel and oxidant, and it extends along the axle of the suspension flow of injection.
Fig. 9 shows the suspension plasma spray of the flame building enclosure 910 using the liquid suspension 909 for surrounding axial injection
Apply system and method 900.Flame building enclosure 910 is extended up in negative electrode 912 from the distal end of injection nozzle 905 or nozzle face
The point of plasma 919 is generated and anode 913 between.It should be understood that flame building enclosure 910 can extend from nozzle
The whole length of the suspension flow sprayed in 905（Extend to the inlet point in plasma outflow thing from nozzle face）.Flame
Building enclosure 910 can provide sufficient heat energy so that liquid droplet is in the front evaporator for leaving nozzle 905.Therefore, can be used as outflow
Thing 940 introduces dry sub-micron paint particles 915 without agglomeration, also without the blocking in syringe.Flame building enclosure 910
May also provide sufficient kinetic energy to improve the fragmentation of the droplet of suspension 909 and the size distribution of coating particle 915.
Figure 10 shows another suspension plasma spray system and method 1000, its liquid suspension being radially injected using encirclement
The flame building enclosure 1010 of liquid 1009.Flame building enclosure 1010 extends and can make along the syringe of liquid suspension 1009
Front evaporator of the liquid droplet in effluent 1040 is introduced into.Flame building enclosure 1010 can also give the droplet of suspension 1009 and fill
Sufficient kinetic energy, thus improves the size distribution of fragmentation and coating particle 1015.
Flame building enclosure can also be constructed as shown in Figure 11 in nozzle exterior.Figure 11 shows suspension plasma spraying system
System and method 1100, it uses the flame building enclosure 1110 for surrounding the liquid suspension 1109 being radially injected.Flame goes along with sb. to guard him knot
Structure 1110 along liquid suspension 1109 syringe extend and can make liquid droplet be introduced into plasma outflow thing 1119 in
Front evaporator.Flame building enclosure 1110 can also give the droplet abundance kinetic energy of suspension 1109, thus improve fragmentation and coating
The size distribution of particle 1015.
As shown in the exemplary of Fig. 9-11, flame building enclosure 910,1010 and 1110 plays several work(
Energy.For example, flame building enclosure 910,1010 and 1110 may act as the shield of liquid suspension 909,1009 and 1109, and it is prevented
Environmental gas are entrained in the suspension flow 909,1009 and 1109 of injection and thus suppress undesired physical and chemical reaction,
Such as the oxidation of submicron particle contained in suspension 909,1009 and 1109.Prevent environmental gas entrainment from also suppressing suspension note
Enter the decay of speed and allow the liquid suspension 909,1009 and 1109 wherein containing submicron particle to keep injection basic
Penetrate in plasma 919,1019 and 1119 in the case of speed.
Additionally, flame building enclosure 910,1010 and 1110 acts also as reactive shield or partial reactive shield, its
During suitable control, can cause at decanting point or near decanting point in the liquid suspension 909,1009 and 1109 of each of which
Or in suspension 909, the required reaction between 1009 and 1109 and shroud air.For example, if liquid-carrier is fuel, such as second
Alcohol, the flame building enclosure causes the combustion reaction of liquid-carrier, and this improves note when being close in plasma outflow thing
The heat energy and kinetic energy of incoming event.This extra heat energy and kinetic energy bring improved droplet fragmentation and the sub-micro in the suspension
Rice corpuscles reaches enhanced melting or evaporation before plasma outflow thing.In liquid-carrier is not the application of fuel,
The flame building enclosure is provided to be evaporated liquid-carrier and suspended particles was melted before being entrained in plasma outflow thing,
Partial melting or or even evaporation the energy.
In general, by surrounding liquid suspension with flame building enclosure when plasma outflow thing is directed to,
Radical change entirely suspends plasma spraying（SPS）The operational characteristic of system.In short, surrounding the flame building enclosure of injection stream
Or the use of similar reactivity shield will transmit the control of sub-micron coating particle to SPS systems（This is by from supply container
Suspend and realize）The control being entrained to sub-micron coating particle in plasma（This can be suspension or non-suspended form）Effectively
Separate.
For example, a kind of SPS systems can be obtained using the disclosed flame building enclosure for surrounding suspension injection stream, it is adopted
It is with transmission suspension but such similar to APS powder injections（But under submicron particle size）Dry submicron particle is carried secretly or injected
Plasma is flowed out in thing.Or, surrounding the flame building enclosure of suspension injection stream can obtain a kind of SPS systems, and it is adopted
Delivering suspension but by the submicron particle entrainment of melting or inject plasma and flow out in thing, by the evaporant of submicron particle
Class injection plasma is flowed out in thing.Further, the disclosed flame building enclosure for surrounding suspension injection stream can be obtained
A kind of SPS systems, it adopts transmission liquid suspension simultaneously by the suspension droplets entrainment of height fragmentation or injection plasma
In effluent.Finally, if appropriately designed and control, flame building enclosure or reactive shield that disclosed encirclement injection is flowed
Liquid suspension can be transmitted, its sub-micron particle reaction in-situ with formed be entrained to plasma flow out thing in required pottery
Porcelain or metallized ceramic coating.
Additionally, above-mentioned transmission, injection and entrainment technology each allow more precise control to inject or be entrained in effluent simultaneously
The particle mean size and size distribution of substrate are subsequently collided, to provide required coating microstructure.Surround the flame of suspension injection stream
The use of building enclosure or reactive shield is the composition of SPS liquid suspensions（Including the composition and particle properties of liquid-carrier）
The new selection of offer or design option.
Finally, due to surround the flame building enclosure or reactive sheath/shield of liquid suspension injection stream referring to the drawings
With the potentiality that additional thermal energy and kinetic energy are provided for SPS spraying processes, system and method allows to use lower work(during SPS
The plasma torch of rate, and more effectively using the heat energy in plasma stream.The encirclement liquid suspension injection stream of the disclosure
Flame building enclosure or the use of reactive sheath/shield additionally provide the machine for further controlling and strengthening whole SPS processes
Meeting, including：Transmission operates suspension；Manufacture plasma jet；Coating is injected or is entrained in plasma jet；With
Coating is transmitted/collided in the substrate to be coated with.
By using this flame building enclosure or reactive sheath/shield and extra kinetic energy associated there, preferred control
In coating injection plasma jet processed, so that reaching the optimization position in effluent, and reduce in decanting point and effluent stream
Interaction.For example, near suspension decanting point or its, a part of effluent can be made to be partial to so that dry powder form, portion
The submicron particle for dividing melting form, melting form and/or evaporated form further extends into stream in controlled and uniform mode
In effluent stream.
Or, if flame building enclosure or sheath/shield are only used for preventing environmental gas from pressing from both sides as a part for SPS methods
In taking the suspension of injection to, and make liquid suspension deeper into penetrating in plasma effluent stream, the sheath/shield has
Suspension may be promoted further to be fragmented into droplet in a controlled manner and in controlled location.By making droplet fragmentation, the flame encloses
Protection structure or reactant gas shield contribute to controlling being injected into plasma and flow out the droplet size of suspension in thing and micro-
Drop Size Distribution.In this way, there is less fragmentation in plasma flows out thing, and droplet size and droplet size distribution are logical
The room and time change occurred when plasma outflow thing shifts to the substrate to be coated with often is not relied on.In other words, it is more smart
Really control droplet size and droplet size distribution, cause improved plasma spray coating process control and improved coating microstructure.
Fig. 9 shows the another embodiment of the present invention using the combustion flame shield for surrounding suspension plasma spraying method.
It should be appreciated that the encirclement effluent described in the use of the double gas shrouds described in Fig. 7 and Fig. 8 and Fig. 9
Combustion flame shield use be equally applicable to using inner radial injection construction, outer radial injection construction and axial injection
The suspension plasma spray system of construction.
As described above, the typical reaction gas as reactant gas shield includes oxygen, hydrogen, carbon dioxide；Hydrocarbon
Fuel and nitrogen or its combination.
It should be noted that the present invention can be in sub-micrometer range extensive a series of fine particle sizes deposition, this leads to before
Cross coating technique（Including conventional plasma spraying）Cannot realize.For example, in one embodiment, SPS systems of the invention
The paint particles less than 100 nanometers can be deposited with method.In another embodiment, the present invention can deposit 10 microns or more
Low paint particles, the undesirable agglomeration without causing the minuteness particle being commonly encountered in conventional spray system and method.
Advantageously, SPS systems as herein described can be prepared using suitable commercially available spray gun and nozzle assembly, therefore energy
It is enough to realize and the whole manufacture process of simplification.Plasma generation aspect can be carried out using standard technique or equipment.
Any suitable liquid suspension transmission subsystem can be used for the liquid suspension of the submicron particle that is wherein scattered here and there
Liquid is streamed in plasma.Liquid suspension source is liquid suspension distributor.The source generally includes reservoir, conveyance conduit
（Such as pipeline, valve etc.）And injection member（Such as nozzle, atomizer etc.）.Additionally, liquid suspension transmission subsystem can contain being somebody's turn to do
The measurement feedback of method（Such as flow velocity, density, temperature）And control method, can for example cooperate with each other or work independently mutually
Pump and actuator.The system can also contain additional flushing as known in the art or purging system, mixing and stirring system, add
Heat or cooling system.
From the above it should be appreciated that present invention accordingly provides the reactant gas shield of suspension plasma spraying and/or
The flame shield system of liquid suspension and method.Although describing this by specific embodiment and relative method
Invention disclosed herein, but the invention scope that can illustrate in without departing substantially from such as claim of those skilled in the art or do not sacrifice
Many modifications and variation are made to it in the case of its all feature and advantage.
Claims (19)
1. it is used to be manufactured the thermal spray system of coating in substrate by liquid suspension, it is included：
For generating the thermal jet torch of plasma；
For the liquid suspension transmission subsystem of liquid suspension stream of the transmission containing submicron particle；With
For will be sent to liquid suspension from the plasma of thermal jet torch to produce the nozzle assembling that plasma flows out thing
Part, the nozzle assembly is adapted to produce the reactant gas shield for surrounding the plasma outflow thing；
The reactant gas shield is constructed to make submicron particle keep being entrained in plasma outflow thing, and prevents gas
Into and with plasma flow out thing reaction；
Wherein described reactant gas shield and plasma flow out thing reaction, with strengthen suspension droplets fragmentation and wait from
The evaporation species of manufacture submicron particle in daughter effluent.
2. the thermal spray system of claim 1, wherein the shield extends to nozzle assembly from substrate surface.
3. the thermal spray system of claim 1, wherein the shield is the barrier of laminar flow.
4. the thermal spray system of claim 1, wherein the axial distance of the shield is less than the distance from nozzle to substrate surface.
5. the thermal spray system of claim 1, further includes the inert gas arranged around the reactant gas shield
Shield.
6. the thermal spray system of claim 1, further includes the first reactant gas shield and the second reactant gas shield.
7. the thermal spray system of claim 1, further includes to be adapted to produce the flame building enclosure for surrounding liquid suspension stream
Injector.
8. the thermal spray system of claim 1, wherein liquid suspension transmission subsystem is arranged on nozzle interior.
9. the thermal spray system of claim 1, wherein liquid suspension transmission subsystem is arranged on nozzle interior to transmit
The axial direction stream of liquid suspension.
10. the thermal spray system of claim 1, wherein liquid suspension transmission subsystem is arranged on nozzle exterior.
11. methods that coating is manufactured in substrate using the liquid suspension of submicron particle that is wherein scattered here and there, methods described bag
Include step：
Plasma is generated by thermal jet torch；
The liquid suspension of the submicron particle that is wherein scattered here and there is streamed to into plasma or it is neighbouring to produce plasma
Effluent stream；
Plasma is surrounded with reactant gas shield flow out thing so that submicron particle keeps being entrained in plasma outflow thing
It is interior, and prevent environmental gas to be entrained in plasma outflow thing；
Make shroud air flow out thing with plasma to react to strengthen the fragmentation of suspension droplets, and flow out in thing in plasma
The evaporation species of manufacture submicron particle；With
Besieged plasma wherein containing submicron particle is flowed out into thing directed toward substrate with coating substrate.
The method of 12. claims 11, further includes to prevent gas to be entrained to the step in besieged effluent.
The method of 13. claims 11, further includes through the reactive shield to make the step of liquid suspension droplet fragmentation
Suddenly.
The method of 14. claims 11, further includes the step of introducing the inert gas shield for surrounding the effluent.
The method of 15. claims 11, further includes the step for introducing the second reactive shroud air for surrounding the effluent
Suddenly.
The method of 16. claims 11, further includes the step of introducing the flame building enclosure for surrounding liquid suspension.
The method of 17. claims 11, further includes to inject liquid suspension in nozzle exterior.
The method of 18. claims 11, further includes to inject liquid suspension in nozzle interior.
The coating being deposited on made by 19. methods according to claim 11 in substrate.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201161570532P | 2011-12-14 | 2011-12-14 | |
| US201161570516P | 2011-12-14 | 2011-12-14 | |
| US61/570516 | 2011-12-14 | ||
| US61/570532 | 2011-12-14 | ||
| PCT/US2012/069807 WO2013090754A2 (en) | 2011-12-14 | 2012-12-14 | Reactive gas shroud or flame sheath for suspension plasma spray processes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104114738A CN104114738A (en) | 2014-10-22 |
| CN104114738B true CN104114738B (en) | 2017-05-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280069723.6A Active CN104114738B (en) | 2011-12-14 | 2012-12-14 | Reactive gas shroud or flame sheath for suspension plasma spray processes |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US20130156968A1 (en) |
| EP (1) | EP2791381B1 (en) |
| JP (1) | JP6165771B2 (en) |
| KR (1) | KR102106179B1 (en) |
| CN (1) | CN104114738B (en) |
| CA (1) | CA2859040C (en) |
| MX (1) | MX360218B (en) |
| PL (1) | PL2791381T3 (en) |
| RU (1) | RU2014128544A (en) |
| SG (1) | SG11201403108RA (en) |
| TR (1) | TR201819010T4 (en) |
| WO (1) | WO2013090754A2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9752223B2 (en) * | 2014-03-10 | 2017-09-05 | United Technologies Corporation | Equipment for plasma spray with liquid injection |
| CA2924476A1 (en) * | 2015-04-01 | 2016-10-01 | Rolls-Royce Corporation | Vacuum plasma sprayed coating including oxide dispersions |
| WO2016210336A1 (en) * | 2015-06-24 | 2016-12-29 | Khalifa University of Science, Technology & Research | Electrostatically manipulated flames for compact heat generation |
| US20180166311A1 (en) * | 2016-12-12 | 2018-06-14 | Applied Materials, Inc. | New repair method for electrostatic chuck |
| WO2021041115A1 (en) * | 2019-08-23 | 2021-03-04 | Lam Research Corporation | Near netshape additive manufacturing using low temperature plasma jets |
| CN114086107B (en) * | 2021-12-28 | 2023-07-14 | 河北复朗施纳米科技有限公司 | Nanometer antibacterial coating device |
| US20230366074A1 (en) * | 2022-05-16 | 2023-11-16 | Andrei V. Ivanov | Oxygen Interception for Air Plasma Spray Processes |
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|---|---|---|---|---|
| CN1119401A (en) * | 1994-08-08 | 1996-03-27 | 普拉塞尔技术有限公司 | Laminar flow shielding of fluid jet |
| WO2010037548A1 (en) * | 2008-10-01 | 2010-04-08 | Technische Universität Chemnitz | Method and device for thermally coating surfaces, particularly high-speed flame spraying |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5087434A (en) * | 1989-04-21 | 1992-02-11 | The Pennsylvania Research Corporation | Synthesis of diamond powders in the gas phase |
| US5372857A (en) * | 1992-12-17 | 1994-12-13 | Browning; James A. | Method of high intensity steam cooling of air-cooled flame spray apparatus |
| US6106903A (en) * | 1999-03-01 | 2000-08-22 | Plasma Technology, Inc. | Thermal spray forming of molybdenum disilicide-silicon carbide composite material |
| DE19958474A1 (en) * | 1999-12-04 | 2001-06-21 | Bosch Gmbh Robert | Process for producing functional layers with a plasma beam source |
| US20030049384A1 (en) * | 2001-09-10 | 2003-03-13 | Liu Jean H. | Process and apparatus for preparing transparent electrically conductive coatings |
| US8748785B2 (en) * | 2007-01-18 | 2014-06-10 | Amastan Llc | Microwave plasma apparatus and method for materials processing |
| US20110003084A1 (en) * | 2008-02-25 | 2011-01-06 | National Research Council Of Canada | Process of Making Ceria-Based Electrolyte Coating |
| WO2013074961A1 (en) * | 2011-11-18 | 2013-05-23 | Hitemco Medical Application Inc. | Porous coatings for orthopedic implants |
-
2012
- 2012-12-14 PL PL12812461T patent/PL2791381T3/en unknown
- 2012-12-14 US US13/715,361 patent/US20130156968A1/en not_active Abandoned
- 2012-12-14 WO PCT/US2012/069807 patent/WO2013090754A2/en active Application Filing
- 2012-12-14 MX MX2014007179A patent/MX360218B/en active IP Right Grant
- 2012-12-14 EP EP12812461.7A patent/EP2791381B1/en active Active
- 2012-12-14 CA CA2859040A patent/CA2859040C/en active Active
- 2012-12-14 KR KR1020147018567A patent/KR102106179B1/en active IP Right Grant
- 2012-12-14 SG SG11201403108RA patent/SG11201403108RA/en unknown
- 2012-12-14 CN CN201280069723.6A patent/CN104114738B/en active Active
- 2012-12-14 TR TR2018/19010T patent/TR201819010T4/en unknown
- 2012-12-14 RU RU2014128544A patent/RU2014128544A/en not_active Application Discontinuation
- 2012-12-14 JP JP2014547500A patent/JP6165771B2/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1119401A (en) * | 1994-08-08 | 1996-03-27 | 普拉塞尔技术有限公司 | Laminar flow shielding of fluid jet |
| WO2010037548A1 (en) * | 2008-10-01 | 2010-04-08 | Technische Universität Chemnitz | Method and device for thermally coating surfaces, particularly high-speed flame spraying |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2015507691A (en) | 2015-03-12 |
| WO2013090754A2 (en) | 2013-06-20 |
| MX2014007179A (en) | 2014-11-25 |
| CA2859040A1 (en) | 2013-06-20 |
| SG11201403108RA (en) | 2014-09-26 |
| WO2013090754A3 (en) | 2013-08-08 |
| CA2859040C (en) | 2018-01-02 |
| RU2014128544A (en) | 2016-02-10 |
| CN104114738A (en) | 2014-10-22 |
| KR102106179B1 (en) | 2020-04-29 |
| MX360218B (en) | 2018-10-25 |
| PL2791381T3 (en) | 2019-09-30 |
| KR20140106655A (en) | 2014-09-03 |
| EP2791381B1 (en) | 2018-10-17 |
| JP6165771B2 (en) | 2017-07-19 |
| EP2791381A2 (en) | 2014-10-22 |
| TR201819010T4 (en) | 2019-01-21 |
| US20130156968A1 (en) | 2013-06-20 |
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