CN1887443A - Cold air powered spraying method and device - Google Patents
Cold air powered spraying method and device Download PDFInfo
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- CN1887443A CN1887443A CN 200510027430 CN200510027430A CN1887443A CN 1887443 A CN1887443 A CN 1887443A CN 200510027430 CN200510027430 CN 200510027430 CN 200510027430 A CN200510027430 A CN 200510027430A CN 1887443 A CN1887443 A CN 1887443A
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Abstract
The present invention relates to cold gas powered spraying method and device for spraying metal powder to the surface of sample or workpiece to form coating. The present invention features that work gas is first heated, then fed to the converging section in the upstream of the nozzle flow passage, and expanded and speeded in the divergent section of the nozzle, while the metal powder to be sprayed is fed directly to the converging section in the upstream of the nozzle through the powder feeding channel and two powder exhausting holes in some angle with the axis of the nozzle. The present invention has no contamination and jamming of the nozzle caused by the sprayed powder and easy manufacture of the nozzle.
Description
(1) technical field
The present invention relates to a kind of method and apparatus for preparing coating, relate in particular to a kind of cold air power spraying and coating method that utilizes metal powder material is sprayed to sample or the surface of the work method and apparatus with the preparation coating.
(2) background technology
The conventional means of preparation coating is to adopt various heat spraying methods, and these methods comprise: flame-spraying, electric arc spraying, plasma spraying, high-velocity oxy-fuel spraying (HVOF).A kind of novel coating production based on aerodynamic principle has appearred in last century end---cold air power spraying and coating (being called for short the spraying of cold spraying or dynamics).In the cold air power spraying and coating process, powder particle to be sprayed is driven and accelerates to very high speed by certain " cold " gas spraying device, does not melt simultaneously.Have the very powder particle bump sample or the surface of the work to be sprayed of kinetic energy, form firm, fine and close adhesion layer.The plastic deformation of powder particle and produce thus and the heat that discharges provides adhesive force and the adhesion of coating at sample or surface of the work in the knockout process.Thereby the heating gas jet can improve the temperature of powder particle makes it be easier to take place plastic deformation in knockout process, and heated air has also improved the speed of the flow velocity and the powder particle of air-flow simultaneously.Gas temperature can be up to 800 ℃, but the fusing point that must be lower than the powder particle that is sprayed does not melt in air-flow to guarantee powder particle.Like this, just can avoid in the conventional thermal spray process problem, the problem includes: problems such as oxidation, phase transformation and thermal stress.
In the injection apparatus of cold air power spraying and coating, high-pressure air source provides gases at high pressure, and push the work forward gas and powder feeding carrier gas are quickened; Heater is provided with two covers, makes working gas and carrier gas be preheating to certain temperature respectively; Powder feeder is under state with pressure powder to be sent in the spray gun, and the spray gun rear portion links to each other with preceding thorax, and powder and working gas are mixed and fed into nozzle herein.Working gas is to produce medium at a high speed, is preheating to 100-600 ℃ at heater before the thorax before entering, to strengthen the particle flow velocity.Carrier gas is axially through powder feeder powder is sent into spray gun after another heater is heated.Nozzle arrangements is for converging-divergence form Raoul (Laval) nozzle, and wherein the stenosis of runner is the throat of nozzle, and the upstream of throat is the convergence section of nozzle, and the downstream is a divergent section.In the Raoul nozzle, working gas expand into normal pressure and acceleration from the pressure of 1.5～3.5MPa of convergence section through throat's arrival divergent section, thereby forms supersonic airstream.
Present cold air power spraying and coating all is to adopt to have the Raoul nozzle and realize ultrasonic.The Raoul nozzle can have different geometric formats, its principal character parameter comprises: geometric profile (as, the cross section of divergent section is circle or rectangle), the ratio (abbreviation aspect ratio) of the length of divergent section and outlet cross-sectional area and the thinnest position (throat or neck) cross-sectional area.
Usually, powder particle to be sprayed is by the throat upstream of powder feeding pipe injection Raoul nozzle, the i.e. convergence section of nozzle.The pressure that this is regional and the input pressure of powder feeding pipe are approaching, reach as high as 3.5MPa, and this means that also employed powder feeder must be a kind of high pressure powder feed device here.Yet the conveying of powder particle can run into a lot of problems under so high pressure, and the turbulent flow that resembles the powder feeding pipe end is exactly one of weakness of said apparatus.If the method according to routine is delivered to nozzle upstream with powder, this weakness just makes that powder is inhomogeneous with mixing of working gas and is difficult to the convergence section of accurate concentrated area by nozzle and converges to part the narrowest in the runner (throat).
The most important parameter of cold air power spraying and coating is that powder particle arrives substrate speed before.For given material, there is a critical speed, the particle that has only speed to surpass this critical value just can be attached on and form coating on the substrate.In order to reach critical speed, it is unimpeded that the inwall of nozzle must keep, and sticking trowel used for plastering of no powder and plug are long-pending.Throat's cross-sectional diameter of Raoul nozzle has only 1.5-3.5mm, and this has not only strengthened the manufacture difficulty and the cost of nozzle, and is easy to cause powder particle to the wearing and tearing of runner especially throat, sticking trowel used for plastering and obstruction.Even if the long-pending spraying process that do not cause of sticking trowel used for plastering and plug interrupts, also can influence the inherent quality of spraying coating process and coating.Because the temperature and the jet velocity of working gas are restricted, the powder particle diameter that conventional cold air power spraying and coating method can spray limited (between 1-50 μ m), maximum can not surpass 50 μ m.
In order to solve the sticking trowel used for plastering and the blockage problem of Raoul nozzle, patent WO98/22639, US2002/0071906, US2003190414, EP1445033 and RU2229944 propose: from the side of Raoul nozzle diverging section powder particle to be sprayed is injected runner (downstream of throat), rather than resembling usually powder is delivered to the convergence section (upstream of throat) of Raoul nozzle.For this reason, need open powder feeding hole so that be connected at the sidewall of Raoul nozzle diverging section with powder feeding pipe.These inventions can solve the obstruction and the wear problem of nozzle effectively, help breaking through working gas temperature and jet velocity, but have increased the difficulty of processing of nozzle in the perforate of Raoul nozzle wall, make that also the powder feeding pipeline is complicated simultaneously.
Patent US2003190414 and EP1445033 adopt the method for directly powder particle to be sprayed being injected runner downstream divergent section, the temperature of working gas can be brought up to 600 ℃ to 700 ℃ and be unlikely to cause the powder smelting to be sprayed in downstream, thereby make can cold air power spraying and coating the maximum powder particle diameter reach 106 μ m[US2003190414], even reach 250 μ m[EP1445033].But, though this method helps breaking through the limitation of working gas temperature, jet velocity and powder particle diameter, but higher working gas temperature (patent US2003190414 even permission are brought up to 1650 ℃ with temperature) has not only increased the probability of powder oxidation to be sprayed or phase transformation, and bring a series of problems can for the preceding thorax of helix tube, gas piping, spray gun of high-pressure working gas heater and selection, manufacturing, the operation and maintenance of nozzle
Patent US2004166247 has also adopted the technical scheme of powder particle directly being sent to the nozzle diverging section, but need not open powder feeding hole at the sidewall of nozzle.Its method is: powder feeding pipe is passed throat along nozzle flow channel from the upstream convergence section directly be inserted into the downstream divergent section, powder particle is directly sent to the runner of divergent section by the axis, longshore current road, end of powder feeding pipe.This invention can effectively solve the obstruction and the wear problem of nozzle, and the processing of nozzle is also very easy.Its shortcoming is that the powder feeding pipe end is easy to produce turbulent flow.Usually, the internal diameter of powder feeding pipe is about 3mm, even if tube wall has only 0.5mm thick, the cross section outside diameter of end also has about 4mm.Like this, the effective cross section area in the nozzle diverging section of powder feeding pipe end correspondence has just had 12mm
2Above sudden change, this will cause turbulent flow or turbulent flow at this position.Because the speed at the divergent section working gas in nozzle downstream had reached supersonic speed already, above-mentioned turbulent flow or turbulent flow will have a negative impact to the steady acceleration of powder particle.This influence obviously than powder feeding pipe outlet serious many of the situation of nozzle upstream.In addition, the powder feeding pipe end is a dead angle of working gas velocity field, and its speed is far below the average speed of this position working gas, and the powder particle of sending at this position can't effectively be quickened.
(3) summary of the invention
The object of the present invention is to provide a kind of cold air power spraying and coating method and device, can effectively avoid sticking trowel used for plastering and the obstruction of powder to be sprayed to nozzle throat, thereby the external pipeline system that keeps conventional powder feeding mechanism is avoided the complicated of powder feeding pipeline, can also not only rely on the working gas temperature that improves nozzle entrance to spray larger-size powder particle, and the effect of nozzle and the equivalence of conventional Raoul nozzle, but the processing and manufacturing of being more convenient for.
The present invention is achieved in that a kind of cold air power spraying and coating method, it is characterized in that
With working gas heating and import in the convergence section with the nozzle flow channel upstream of Raoul type nozzle equivalence, working gas is through expanding and acceleration in the downstream divergent section behind the nozzle throat;
Metal powder granulates to be sprayed is directly sent into the downstream divergent section of nozzle and quicken by wherein working gas;
Wherein:
Powder particle to be sprayed is to send to nozzle downstream divergent section through the powder feeding duct in the water conservancy diversion terminal that connects the powder feeding pipe end;
The axis of powder feeding pipe end and water conservancy diversion terminal overlaps with the axis of nozzle flow channel, and the flow direction of working gas, i.e. injection direction are pointed in the tip of water conservancy diversion terminal;
The side of water conservancy diversion terminal has at least two uniform flour openings, and there is an angle axis of flour opening and the axis of nozzle, and the axis of flour opening outlet offset nozzle runner is positioned at the side of water conservancy diversion terminal and is in nozzle downstream divergent section.
Above-mentioned cold air power spraying and coating method, described working gas runner is formed by nozzle outer body inwall and inner water conservancy diversion terminal outer profile, the cross-sectional area in formed space equates with the cross-sectional area of conventional Raoul nozzle relevant position between nozzle downstream diffuser water conservancy diversion terminal and the nozzle outer body, i.e. A
1-a=A, wherein A
1, a and A be respectively the cross-sectional area of nozzle outer body inner chamber, water conservancy diversion terminal and conventional Raoul nozzle flow channel relevant position.
Above-mentioned cold air power spraying and coating method, cross section is minimum in the formed annular region between described nozzle throat corresponding nozzle outer body inwall and the inner water conservancy diversion terminal outer profile locates, i.e. A
1-a
*=A
*, a wherein
*And A
*It is respectively the cross-sectional area of water conservancy diversion terminal and conventional Raoul nozzle throat.
Above-mentioned cold air power spraying and coating method, the angle of the axis of flour opening and nozzle axis is 10 ° to 60 ° on the described water conservancy diversion terminal; To between the water conservancy diversion terminal tip, and the distance of nozzle throat is that nozzle throat is to 1/3rd to 1/2nd of distance between the water conservancy diversion terminal tip at nozzle throat for flour opening outlet on the water conservancy diversion terminal.
Above-mentioned cold air power spraying and coating method, the working gas temperature of described nozzle entrance is between 200 ℃ to 700 ℃.Metal powder granulates diameter to be sprayed is between 5 μ m to 250 μ m.
A kind of cold air driven spray painter, comprise heater, preceding thorax, current distribution device, powder feeder, pipeline, nozzle, gases at high pressure divide two the tunnel to enter heater and powder feeder, pipeline connects heater and preceding thorax, working gas enters current distribution device through preceding thorax, enter nozzle body by current distribution device, powder feeder enters nozzle through powder feeding pipe, it is characterized in that nozzle comprises nozzle outer body and inner water conservancy diversion terminal, the axis of water conservancy diversion terminal overlaps with the axis of nozzle flow channel, and the flow direction of working gas is pointed at the tip of water conservancy diversion terminal; Nozzle flow channel comprises upstream convergence section, throat, downstream divergent section; Have the powder feeding duct in the water conservancy diversion terminal, the powder feeding duct connects outside powder feeding pipe, the side of water conservancy diversion terminal has at least two uniform flour openings, there is an angle axis of flour opening and the axis of nozzle, the axis of flour opening outlet offset nozzle runner is positioned at the side of water conservancy diversion terminal and is in nozzle downstream divergent section; The working gas runner is formed by nozzle outer body inwall and inner water conservancy diversion terminal outer profile.
The cross-sectional area in formed space equates with the cross-sectional area of conventional Raoul nozzle relevant position between the above-mentioned cold air driven spray painter, described nozzle downstream diffuser water conservancy diversion terminal and nozzle outer body, i.e. A
1-a=A, wherein A
1, a and A be respectively the cross-sectional area of nozzle outer body inner chamber, water conservancy diversion terminal and conventional Raoul nozzle flow channel relevant position.
Above-mentioned cold air driven spray painter, the angle of the axis of flour opening and nozzle axis is 10 ° to 60 ° on the described water conservancy diversion terminal; The flour opening number is 2 to 6 on the water conservancy diversion terminal, and the flour opening outlet is positioned on the same cross section of water conservancy diversion terminal, and equidistantly evenly distributes along the periphery of this cross section.
Above-mentioned cold air driven spray painter, the inwall of described nozzle outer body is a surface that the axis with nozzle is first rotary body in axle center, the exterior contour of water conservancy diversion terminal is a smooth surface that the axis with nozzle is second rotary body in axle center, nozzle upstream before throat, first rotary body is a round platform, second rotary body is a cylinder, and within first rotary body and the space outside second rotary body has constituted the convergence section of equivalent Raoul nozzle; Nozzle downstream after throat is up to the tip of water conservancy diversion terminal, first rotary body is a cylinder, second rotary body is to be positioned at the curved surface cone that the curve rotation at water conservancy diversion terminal tip obtains by the summit, space within first rotary body, outside second rotary body has constituted the divergent section of equivalent Raoul nozzle, the second curved surface cone between throat to water conservancy diversion terminal tip apart from the radius of turn at throat x place
L wherein
0Be divergent section length, promptly nozzle throat is to distance between the water conservancy diversion terminal tip, R
1Be the radius of turn of cylinder I, i.e. the internal diameter of nozzle outer body is with the cross section radius R of the equivalent Raoul nozzle diverging of circle section port
2Equate R
*Be equivalent Raoul nozzle throat cross section radius.
Above-mentioned cold air driven spray painter, after the described nozzle diverging section, promptly after inner water conservancy diversion terminal tip, the length of outer body flat segments is 1/4th to 1/3rd of divergent section length.
Above-mentioned cold air driven spray painter, described water conservancy diversion terminal is made up of two assemblies, the interface corresponding nozzle throat of two assemblies or the effective range of throat and by being threaded togather, wherein the corresponding assembly of nozzle upstream part adopts external screw thread, and the assembly of downstream part correspondence adopts internal thread.Two assemblies of water conservancy diversion terminal adopt different material manufacturings, and the density that wherein is in the material of nozzle downstream components is equal to or less than the density of upstream component, and the heat resistance of the material of upstream component is identical with downstream components or be higher than downstream components.
The present invention is heated to 200 ℃ to 700 ℃ and import in the convergence section with the nozzle flow channel upstream of Raoul type nozzle equivalence with working gas, and gas expands and quickens in the downstream divergent section through nozzle throat (part that runner is the narrowest) back; The powder particle to be sprayed of particle diameter 5 μ m to 250 μ m is directly sent into the downstream of nozzle and accelerated to 300m/s to 1200m/s by wherein working gas.Powder particle wherein to be sprayed is a divergent section of directly sending to the nozzle downstream through a water conservancy diversion terminal of powder feeding pipe end; The axis of powder feeding pipe end and water conservancy diversion terminal overlaps with the axis of nozzle flow channel, and the flow direction (injection direction) of working gas is pointed at the tip of water conservancy diversion terminal; The side of water conservancy diversion terminal has two or more flour openings, the axis of flour opening and the axis of nozzle are 5 ° to 75 ° angles, with 10 ° to 60 ° preferable, the axis of the outlet offset nozzle runner of flour opening is positioned at the side of water conservancy diversion terminal and is in the divergent section in nozzle downstream.
The invention has the advantages that:
1. meal outlet is not opened at water conservancy diversion terminal tip, only the physical dimension of water conservancy diversion terminal downstream assembly exterior contour is had relatively high expectations, and therefore can be processed into the shape that requires near theoretical.The effective cross section of this position nozzle is continuous, smooth change, and sudden change can not cause the turbulent flow as patent US2004166247 powder feeding pipe end.
2. because the flour opening outlet is placed throat's divergent section afterwards, the temperature of working gas even can be higher than the fusing point of powder to be sprayed and can not cause the fusing of powder, because working gas is through after the throat, temperature reduces rapidly, temperature is far below its fusing point (sometimes even be lower than room temperature) when touching powder, thereby broken through the restriction of conventional cold air power spraying and coating to temperature.
3. the outlet of water conservancy diversion terminal side flour opening is positioned at the divergent section of nozzle, and working gas temperature herein is lower, can avoid powder to nozzle outer body inwall with and the sticking trowel used for plastering of inner water conservancy diversion terminal outer wall and plug long-pending.
4. the outlet of water conservancy diversion terminal side flour opening is positioned at the divergent section of nozzle, and working gas herein produces strong swabbing action owing to jet effect to the powder particle in the flour opening along the water conservancy diversion terminal outer surface flow at high speed of smooth gradual change.Only rely on respect to conventional method that carrier gas is to the effect of dragging of powder particle in the powder feeding pipe, this swabbing action not only helps powder feeding, but also can overcome sticking trowel used for plastering and the blockage problem of powder particle in powder feeding pipe and inside, powder feeding duct.
5. working gas has formed swiftly flowing " cold " air film between nozzle outer body inwall and inner water conservancy diversion terminal outer wall, this air film has following two effects: the powder particle in the narrow zone between nozzle outer body 8 inwalls and inner water conservancy diversion terminal 9 outer walls is had strong purging and scrubs effect, can effectively avoid powder long-pending to the sticking trowel used for plastering and the plug of nozzle outer body 8 inwalls and inner water conservancy diversion terminal 9 outer walls; If correctly spray operation, promptly earlier for powder feeding behind the working gas, there has been above-mentioned air film outward in the meal outlet of water conservancy diversion terminal 9 sides during powder feeding, and powder particle is the inwall of impulse nozzle outer body 8 directly, thereby can reduce nozzle abrasion.
6. because virtual " the Raoul nozzle " of water conservancy diversion terminal side flour opening effect: the one side powder particle can produce " spontaneous " by flour opening time the preaceleration, add the powder feeding duct and contain the swabbing action of the effect of dragging of gas and the outer working gas of flour opening, powder particle can obtain more effective acceleration, improves temperature and sprays larger-size powder particle thereby can not only rely on; On the other hand, the powder particle speed of being sent by flour opening to be sprayed improves, temperature reduces, pressure reduces, reduce with the speed of working gas, the difference of temperature and pressure, this not only can reduce the sticking trowel used for plastering of nozzle outer body inwall and plug long-pending, and can reduce the fluctuation in working gas velocity field and temperature field.
7. the effect of nozzle of the present invention is identical with conventional Raoul nozzle, but the divergent section of nozzle outer body can be made the cylinder that a cross-sectional diameter equals equivalent conventional Raoul nozzle diverging section maximum gauge---simple shape, the straight tube that internal diameter is very big, therefore process very conveniently, cost reduces.
(4) description of drawings
The invention will be further described below in conjunction with the drawings and specific embodiments.
Fig. 1 is a cold air driven spray painter schematic diagram of the present invention;
Fig. 2 is the nozzle and the fitting structural representation that is associated;
Fig. 3 is a nozzle sectional axonometric drawing of the present invention;
Fig. 4 is the exterior contour schematic diagram of the water conservancy diversion terminal of nozzle interior in nozzle downstream divergent section.
Among the figure: 1 gases at high pressure, 2 heaters, 3 pipelines, 4 powder feeders, 5 powder feeding pipe, thorax before 6,7 current distribution devices, 8 nozzle outer body, 9 water conservancy diversion terminals, 9-1 water conservancy diversion terminal Upstream section, 9-2 water conservancy diversion terminal tract, 9-3 water conservancy diversion terminal internal powder conveying duct, the flour opening of 9-4 water conservancy diversion terminal.
(5) specific embodiment
Referring to Fig. 1, a kind of cold air driven spray painter, thorax 6 before 1 minute two tunnel, one tunnel gas through heater 2 heating of its gases at high pressure enters by pipeline 3 as working gas, the temperature of working gas is between 200 ℃ to 700 ℃ in the preceding thorax 6.Next the working gas in the preceding thorax 6 enters nozzle outer body 8 by current distribution device 7.Meanwhile, another road small part gas enters powder feeder 4 as carrier gas and powder particle to be sprayed is taken out of, directly delivers to the divergent section in nozzle outer body 8 downstreams by powder feeding pipe 5 and nozzle interior water conservancy diversion terminal 9.Powder feeding pipe 5 had been passed preceding thorax 6 before linking with water conservancy diversion terminal 9, the mode of arranging of this pipeline and conventional cold air power spraying and coating system are about the same, therefore can avoid making because of " walk around preceding thorax 6 and open powder feeding hole (patent US2003190414 and EP1445033) at nozzle outer body 8 sidewalls " the complicated problem of powder feeding pipeline.Simultaneously, thorax 6 before powder feeding pipe 5 was passed before linking with nozzle interior water conservancy diversion terminal 9, can also make carrier gas within the powder feeding pipe 5 and powder to be sprayed obtain to a certain degree preheating and expansion (supercharging), this is extremely important to virtual " the Raoul nozzle " realizing below will describing.
Referring to Fig. 2, Fig. 3, nozzle is combined by outer body 8 and inner water conservancy diversion terminal 9, and the working gas runner of nozzle is that the exterior contour by the inwall of nozzle outer body 8 and nozzle interior water conservancy diversion terminal 9 forms.In order to make nozzle of the present invention and the equivalence of conventional Raoul nozzle, the cross-sectional area of counting up to formed space between divergent section terminal point nozzle outer body 8 and the nozzle interior water conservancy diversion terminal 9 from throat must be corresponding one by one with conventional Raoul nozzle, that is the cross-sectional area at nozzle downstream divergent section middle distance throat x place
A
1-a=A or a=A
1-A
A wherein
1, a and A be respectively nozzle outer body 8 inner chambers of the present invention, water conservancy diversion terminal 9 and the conventional Raoul nozzle flow channel cross-sectional area at the x place.
Following formula is exactly the fundamental equation that makes nozzle of the present invention and the equivalence of conventional Raoul nozzle.In other words, in order to make nozzle of the present invention and the equivalence of conventional Raoul nozzle, the water conservancy diversion terminal 9 of nozzle interior must be made like this: the cross-sectional area a of throat's downstream diffuser water conservancy diversion terminal 9 should equal the body 8 relevant position cross-sectional area A of nozzle of the present invention outside
1Poor with the cross-sectional area A of conventional Raoul nozzle flow channel relevant position.
At x=0 place, A
1-a
*=A
*Minimum, the throat of corresponding nozzle of the present invention, wherein a
*And A
*It is respectively the cross-sectional area of the conventional Raoul nozzle flow channel of water conservancy diversion terminal 9 throat.
The end of nozzle upstream convergence section can overlap with the top of downstream divergent section, also can not overlap.Distance between the two, i.e. the effective length of nozzle throat is between 0mm to 20mm.Unless stated otherwise, otherwise following so-called " throat " all refers to the top of downstream divergent section.In addition, for forced working gas is treated the acceleration effect of sprayed particle, after the tip of nozzle interior water conservancy diversion terminal 9, i.e. the end of nozzle diverging section, nozzle outer body 8 also has one section straight extension---" flat segments ".
If nozzle outer body 8 inner chambers of the present invention, inner water conservancy diversion terminal 9 and conventional Raoul nozzle flow channel cross section all are just round, in other words, the inwall of nozzle outer body 8 is the surfaces that the axis with nozzle is first rotary body in axle center, and the exterior contour of nozzle interior water conservancy diversion terminal 9 is the smooth surfaces that the axis with nozzle is second rotary body in axle center: as mentioned above, throat at nozzle, be the x=0 place, the annular cross section area A between nozzle outer body 8 and the inner water conservancy diversion terminal 9
1-a
*=A
*Minimum.Since the cross section of runner be the flow channel cross-section diameter of the conventional Raoul nozzle throat just justified usually between 1.5mm to 3.5mm, especially between 2mm to 3mm, the annular cross-sectional area A of above-mentioned minimum
1-a
*=A
*Just at 1mm
2To 10mm
2Between, better at 2mm
2To 7mm
2Between.Usually, the aspect ratio of conventional Raoul nozzle
Between 5 to 20.If make the cylindrical cross-sectional area A of nozzle outer body 8 of the present invention from throat to water conservancy diversion terminal tip
1Cross-sectional area A with conventional Raoul nozzle diverging segment endpoint runner
2Equate, i.e. A
1=A
2So:
The cylindrical cross-sectional area A at nozzle outer body 8 of the present invention tip to the water conservancy diversion terminal from throat
1The water conservancy diversion terminal cross-sectional area a corresponding with nozzle throat
*The ratio
Just between 1.05 to 1.25.
Though it should be noted that nozzle of the present invention and the equivalence of conventional Raoul nozzle, the difficulty and the cost of processing all significantly are lower than conventional Raoul nozzle.The difficulty of conventional Raoul nozzle processing is that long and narrow divergent section runner is the higher taper shape of dimension precision requirement, especially Guan Jian nozzle throat narrower (the flow channel cross-section diameter is between 1.5mm to 3.5mm), this is a cold air power spraying and coating with the very expensive main cause of conventional Raoul nozzle.Different therewith is, the divergent section of nozzle outer body 8 of the present invention can be made the cylinder that a cross-sectional diameter equals equivalent conventional Raoul nozzle diverging section flow channel cross-section maximum gauge---simple shape, the straight tube that internal diameter is very big, therefore process very conveniently, cost reduces.
Nozzle downstream after throat is R up to the tip of water conservancy diversion terminal 9 (divergent section of nozzle) if rotary body I is a radius
1Cylinder, then have
Or
Wherein r and R are respectively the radius of turn of the conventional Raoul nozzle of nozzle interior water conservancy diversion terminal 9 of the present invention and circular cross section at distance throat x place.
Cross section for runner is just round conventional Raoul nozzle, and the cross circular section radius of throat and divergent section terminal point is respectively R
*And R
2, the axial length of counting the divergent section terminal point from throat is (divergent section length) l
0, then the cross circular section radius R at divergent section middle distance throat x place is
Therefore, have:
If make the cylindrical radius R at outer body 8 tip to the water conservancy diversion terminal of nozzle of the present invention from throat
1Flow channel cross-section radius of circle R with conventional Raoul nozzle diverging segment endpoint
2Equate, i.e. R
1=R
2(be equivalent to A
1=A
2), then have
Following formula is exactly to describe the equation of the water conservancy diversion terminal 9 of nozzle interior of the present invention at how much patterns (second rotary body) of nozzle downstream divergent section or exterior contour, the wherein all parameter (R of following formula right-hand member
*, R
2And l
0) characteristic parameters of matching convention Raoul nozzle all.Therefore, as long as a given conventional Raoul nozzle just can produce the corresponding equivalent nozzle of the present invention according to above-mentioned equation.Fig. 4 shows the exterior contour of the water conservancy diversion terminal 9 of nozzle interior of the present invention in nozzle downstream divergent section, and wherein horizontal linear is the inner surface contour line of nozzle outer body 8.Fig. 4 is a longitudinal cross-section of crossing the nozzle flow channel axis, wherein only shows first cross section, axis.
Referring to Fig. 2, said nozzle outer body 8 is assembled together with preceding thorax 6, and in the thorax 6, water conservancy diversion terminal 9 was connected on the boss of current distribution device 7 before current distribution device 7 was fixed on.As shown in Figures 2 and 3, water conservancy diversion terminal 9 is made up of two parts again itself: Upstream section 9-1 and tract 9-2, the two is by being threaded.Wherein Upstream section 9-1 is that external screw thread, tract 9-2 are internal thread.Because the temperature of upstream is higher than the downstream, above-mentioned connected mode more helps to utilize the sealing of reinforcement to this interface of expanding with heat and contract with cold.Two assemblies of water conservancy diversion terminal 9 can adopt different material manufacturings.The density of material that wherein is in the assembly 9-2 in nozzle downstream is equal to or less than the density of upstream component 9-1 (to reduce the deflection of the water conservancy diversion terminal 9 that deadweight causes), and the heat resistance of the material of upstream component 9-1 is identical with downstream components 9-2 or be higher than downstream components 9-2 (temperature of upstream is higher).
The terminal water conservancy diversion terminal Upstream section 9-1 that directly inserts of powder feeding pipe 5, having one in the water conservancy diversion terminal 9 is the powder feeding duct 9-3 that axle center, diameter equate with powder feeding pipe 5 internal diameters with the nozzle flow channel axis.Duct in the Upstream section 9-1 is connected with powder feeding pipe 5, and the duct in the tract 9-2 is communicated with the flour opening 9-4 on the water conservancy diversion terminal.
Enter the convergence section that the HTHP working gas of nozzle outer body 8 at first enters nozzle outer body 8 throat upstreams, the divergent section that enters the downstream through throat's (slit between nozzle outer body 8 outer body and the nozzle interior water conservancy diversion terminal 9) of nozzle outer body 8 expands and quickens, working gas temperature and all sharply reductions of pressure of expanding and having quickened.Under with the situation of nitrogen: at the l of distance throat as the copper powders may of working gas sprayed particle diameter 25 μ m
0/ 5 places, the speed of working gas reaches v
085%; l
0/ 4 places, v
088%; l
0/ 3 places, v
092%; l
0/ 2 places, v
097%; 3l
0/ 4 places, v
099%---l wherein
0Be nozzle diverging segment length, v
0Be the speed of working gas at the divergent section destination county.
This shows, if the l of portion the distance marquis is opened in the outlet of the flour opening 9-4 on the water conservancy diversion terminal 9
0/ 4 to 3l
0/ 4 places, the speed of working gas has reached v
088% to 99%, help acceleration to powder particle.According to experiment, if the l of portion the distance marquis is opened in the outlet of the flour opening 9-4 on the water conservancy diversion terminal 9
0/ 3 to l
0/ 2 places, the speed of working gas has reached v
092% to 97%, the most favourable to the steady acceleration of powder particle.In addition, because working gas temperature herein is lower, can reduce from the powder of flour opening 9-4 long-pending to the sticking trowel used for plastering and the plug of nozzle outer body 8 inwalls and inner water conservancy diversion terminal 9 outer walls.
Should open two flour opening 9-4 at least symmetrically on the nozzle interior water conservancy diversion terminal 9 of the present invention, also can open three flour opening 9-4, but the outlet in these three holes should evenly distribute along water conservancy diversion terminal 9 cross section contours.Usually, the number of flour opening 9-4 is between 2 to 6, and the outlet in these holes should be positioned on the same cross section of water conservancy diversion terminal 9 and along the cross section contour and evenly distribute, and the size shape of each meal outlet 9-4 also should be identical.
The angle of the axis of flour opening 9-4 and nozzle flow channel axis is very important, and in theory, this angle can be between 0 ° to 90 °.But, angle is too little, and the outlet of flour opening 9-4 is near the tip of water conservancy diversion terminal 9, and not only the duct is long, processing difficulties, and its effect is similar to the terminal powder delivery pattern (patent US2004166247) that powder feeding pipe 5 is extended to the nozzle diverging section, can cause the turbulent flow or the turbulent flow in velocity field and temperature field.Therefore, this angle should be greater than 5 °, more preferably greater than 10 °.On the contrary, if this angle is excessive, the working gas that water conservancy diversion terminal 9 outer wall high velocity stream are crossed can not produce the swabbing action of jet to the fluid in the flour opening 9-4 (carrier gas and powder particle).For this reason, this angle should be greater than 75 °.Therefore, if the axis of flour opening 9-4 and the angle of nozzle flow channel axis are controlled at 5 ° to 75 °, especially be controlled at 10 ° to 60 °, not only be convenient to processing and manufacturing, and the working gas of low pressure will produce strong swabbing action to the powder particle in the flour opening 9-4 owing to jet effect along the flow at high speed of the outer surface of the water conservancy diversion terminal 9 of smooth gradual change.This swabbing action not only helps powder feeding, and can overcome sticking trowel used for plastering and the blockage problem of powder particle in powder feeding pipe 5 and even water conservancy diversion terminal 9 inside.
The size and dimension of flour opening 9-4 is equally very important.Usually adopt circular hole, the cross-sectional area sum of all flour opening 9-4 should be more preferably 0.5 to 0.75 times for 0.5 to 1 times of the powder feeding duct 9-3 cross-sectional area of water conservancy diversion terminal 9 inside.If the cross-sectional area sum of flour opening 9-4 is too small, as less than 0.5, the size of each flour opening 9-4 is just too thin so, and this promptly is unfavorable for processing and manufacturing, also is unfavorable for smooth powder feeding; Otherwise, if the cross-sectional area sum of flour opening 9-4 is excessive, as greater than 1, the size of each flour opening 9-4 is just too thick so, in the 9-3 of powder feeding duct, just can not keep certain pressure, be difficult to guarantee evenly powder feeding swimmingly, the working gas that temperature is lower outside the higher powder of simultaneous temperature and the water conservancy diversion terminal 9 mix also can the fail temperature field uniformity.If making the cross-sectional area sum of all flour opening 9-4 is 0.5 to 1 times of powder feeding duct 9-3 cross-sectional area, especially 0.5 to 0.75 times, then the nebulizer gas pressure among the 9-3 of powder feeding duct will increase in flour opening 9-4 forward position.The bulbs of pressure that the preheating that stands in powder feeding pipe 5 of the powder of carrier gas in addition (through preceding thorax 6 time) causes, carrier gas in the powder feeding duct 9-3 of flour opening 9-4 forward position and powder will be all higher than air pressure outside the water conservancy diversion terminal 9 and temperature.Like this, flour opening 9-4 upstream exists compression, downstream to have dilating effect, therefore flour opening 9-4 resembles the throat of a Raoul nozzle, (powder feeding duct 9-3) is convergence section in the upstream, downstream (zone between nozzle outer body 8 and the inner water conservancy diversion terminal 9) is a divergent section, thereby constitutes virtual " a Raoul nozzle ".Consequently: on the one hand, powder particle can produce the preaceleration effect of " spontaneous " by flour opening 9-4 the time, add the swabbing action and the effect of dragging of the outer working gas of meal outlet, powder particle can obtain more effective acceleration, improves temperature and sprays larger-size powder particle thereby can not only rely on; On the other hand, the powder particle speed of being sent by flour opening 9-4 to be sprayed improves, temperature reduces, pressure reduces, reduce with the speed of working gas, the difference of temperature and pressure, not only can avoid long-pending, and can reduce the fluctuation in working gas velocity field and temperature field the sticking trowel used for plastering and the plug of nozzle outer body 8 inwalls.
Embodiment 1:
Adopt nitrogen as working gas, copper powder particles diameter to be sprayed is at 10 μ m to 30 μ m, and matrix is an aluminium sheet.Nozzle inlet place air pressure is 2.5MPa, 250 ℃ of temperature.The form of nozzle as shown in Figure 3, the divergent section of outer body 8 and flat segments length are respectively 60mm and 20mm, corresponding inner flow passage is that diameter is straight tube (cylinder) shape of Φ 7.4mm.The effective length of nozzle throat is 5mm.Nozzle interior water conservancy diversion terminal 9 is Φ 6.7mm corresponding to throat's cross section diameter of a circle, and runner is 7.75mm at the annular cross section area of throat
2, the ratio of water conservancy diversion terminal 9 cross-sectional areas that outer body 8 cylindrical cross-sectional areas are corresponding with throat is 1.22.Water conservancy diversion terminal 9-1 and 9-2 adopt copper and polybenzimidazoles manufacturing respectively, the diameter of phi 2.5mm of inner powder feeding duct 9-3.The radius of turn of water conservancy diversion terminal 9-2 curved surface cone,
Wherein x is the distance to nozzle throat.4 diameters that have a symmetrical distribution apart from throat 20mm place on water conservancy diversion terminal 9 are the flour opening 9-4 of Φ 1.0mm, the axis of flour opening 9-4 and nozzle flow channel axis are 45, and all flour opening 9-4 cross-sectional area sums are 0.64 with the ratio of powder feeding duct 9-3 cross-sectional area.The spraying result is: deposition about 70%, coating is evenly good.
Embodiment 2:
Adopt nitrogen as working gas, copper powder particles diameter to be sprayed is at 20 μ m to 50 μ m, and matrix is an aluminium sheet.Nozzle inlet place air pressure is 2.5MPa, 380 ℃ of temperature.The form of nozzle as shown in Figure 3, the divergent section of outer body 8 and flat segments length are respectively 65mm and 20mm, corresponding inner flow passage is that diameter is straight tube (cylinder) shape of Φ 8.1mm.The effective length of nozzle throat is 10mm.Nozzle interior water conservancy diversion terminal 9 is Φ 7.6mm corresponding to throat's cross section diameter of a circle, and runner is 6.17mm at the annular cross section area of throat
2, the ratio of water conservancy diversion terminal 9 cross-sectional areas that outer body 8 cylindrical cross-sectional areas are corresponding with throat is 1.14.Water conservancy diversion terminal 9-1 and 9-2 all adopt copper production, the diameter of phi 3.0mm of inner powder feeding duct 9-3.The radius of turn of water conservancy diversion terminal 9-2 curved surface cone,
Wherein x is the distance to nozzle throat.2 diameters that have a symmetrical distribution apart from throat 25mm place on water conservancy diversion terminal 9 are the flour opening 9-4 of Φ 2.0mm, the axis of flour opening 9-4 and nozzle flow channel axis are 15 ° of angles, and all flour opening 9-4 cross-sectional area sums are 0.89 with the ratio of powder feeding duct 9-3 cross-sectional area.The spraying result is: deposition about 70%, coating is evenly good.
Embodiment 3:
Adopt nitrogen as working gas, copper powder particles diameter to be sprayed is at 80 μ m to 120 μ m, and matrix is an aluminium sheet.Nozzle inlet place air pressure is 3.0MPa, 600 ℃ of temperature.The form of nozzle as shown in Figure 3, the divergent section of outer body 8 and flat segments length are respectively 100mm and 40mm, corresponding inner flow passage is that diameter is straight tube (cylinder) shape of Φ 8.7mm.The effective length of nozzle throat is 10mm.Nozzle interior water conservancy diversion terminal 9 is Φ 8.3mm corresponding to throat's cross section diameter of a circle, and runner is 5.34mm at the annular cross section area of throat
2, the ratio of water conservancy diversion terminal 9 cross-sectional areas that outer body 8 cylindrical cross-sectional areas are corresponding with throat is 1.10.Water conservancy diversion terminal 9-1 and 9-2 adopt stainless steel and copper production respectively, the diameter of phi 3.0mm of inner powder feeding duct 9-3.The radius of turn of water conservancy diversion terminal 9-2 curved surface cone,
Wherein x is the distance to nozzle throat.2 diameters that have a symmetrical distribution apart from throat 50mm place on water conservancy diversion terminal 9 are the flour opening 9-4 of Φ 1.5mm, the axis of flour opening 9-4 and nozzle flow channel axis are 15 ° of angles, and all flour opening 9-4 cross-sectional area sums are 0.50 with the ratio of powder feeding duct 9-3 cross-sectional area.The spraying result is: deposition about 65%, coating is evenly good.
Embodiment 4:
Adopt nitrogen as working gas, copper powder particles diameter to be sprayed is at 160 μ m to 210 μ m, and matrix is an aluminium sheet.Nozzle inlet place air pressure is 3.0MPa, 650 ℃ of temperature.The form of nozzle as shown in Figure 3, the divergent section of outer body 8 and flat segments length are respectively 150mm and 50mm, corresponding inner flow passage is that diameter is straight tube (cylinder) shape of Φ 7.8mm.The effective length of nozzle throat is 15mm.Nozzle interior water conservancy diversion terminal 9 is Φ 7.5mm corresponding to throat's cross section diameter of a circle, and runner is 3.60mm at the annular cross section area of throat
2, the ratio of water conservancy diversion terminal 9 cross-sectional areas that outer body 8 cylindrical cross-sectional areas are corresponding with throat is 1.08.The radius of turn of water conservancy diversion terminal 9-2 curved surface cone,
Wherein x is the distance to nozzle throat.Water conservancy diversion terminal 9-1 and 9-2 all adopt the manufacturing of IN718 alloy, the diameter of phi 3.5mm of inner powder feeding duct 9-3.On water conservancy diversion terminal 9, have the flour opening 9-4 that equally distributed 3 diameters are Φ 1.5mm apart from throat 100mm place, the axis of flour opening 9-4 and nozzle flow channel axis are 30 ° of angles, and all flour opening 9-4 cross-sectional area sums are 0.55 with the ratio of powder feeding duct 9-3 cross-sectional area.The spraying result is: deposition is near 60%, and coating is evenly good.
Claims (15)
1. a cold air power spraying and coating method is characterized in that
With working gas heating and import in the convergence section with the nozzle flow channel upstream of Raoul type nozzle equivalence, working gas is through expanding and acceleration in the downstream divergent section behind the nozzle throat;
Metal powder granulates to be sprayed is directly sent into the downstream divergent section of nozzle and quicken by wherein working gas;
Wherein:
Powder particle to be sprayed is to send to nozzle downstream divergent section through the powder feeding duct in the water conservancy diversion terminal that connects the powder feeding pipe end;
The axis of powder feeding pipe end and water conservancy diversion terminal overlaps with the axis of nozzle flow channel, and the flow direction of working gas, i.e. injection direction are pointed in the tip of water conservancy diversion terminal;
The side of water conservancy diversion terminal has at least two uniform flour openings, and there is an angle axis of flour opening and the axis of nozzle, and the axis of flour opening outlet offset nozzle runner is positioned at the side of water conservancy diversion terminal and is in nozzle downstream divergent section.
2. cold air power spraying and coating method according to claim 1, it is characterized in that the working gas runner is formed by nozzle outer body inwall and inner water conservancy diversion terminal outer profile, the cross-sectional area in formed space equates with the cross-sectional area of conventional Raoul nozzle relevant position between nozzle downstream diffuser water conservancy diversion terminal and the nozzle outer body, i.e. A
1-a=A, wherein A
1, a and A be respectively the cross-sectional area of nozzle outer body inner chamber, water conservancy diversion terminal and conventional Raoul nozzle flow channel relevant position.
3. cold air power spraying and coating method according to claim 2 is characterized in that between nozzle throat corresponding nozzle outer body inwall and the inner water conservancy diversion terminal outer profile the minimum place of cross section, i.e. A in the formed annular region
1-a
*=A
*, a wherein
*And A
*It is respectively the cross-sectional area of water conservancy diversion terminal and conventional Raoul nozzle throat.
4. cold air power spraying and coating method according to claim 1 and 2 is characterized in that the axis of flour opening on the water conservancy diversion terminal and the angle of nozzle axis are 10 ° to 60 °.
5. cold air power spraying and coating method according to claim 4, it is characterized in that on the water conservancy diversion terminal flour opening outlet at nozzle throat between the water conservancy diversion terminal tip, and the distance of nozzle throat is that nozzle throat is to 1/3rd to 1/2nd of distance between the water conservancy diversion terminal tip.
6. cold air power spraying and coating method according to claim 1, the working gas temperature that it is characterized in that nozzle entrance is between 200 ℃ to 700 ℃.
7. cold air power spraying and coating method according to claim 1 is characterized in that metal powder granulates diameter to be sprayed is between 5 μ m to 250 μ m.
8. cold air driven spray painter, comprise heater, preceding thorax, current distribution device, powder feeder, pipeline, nozzle, gases at high pressure divide two the tunnel to enter heater and powder feeder, pipeline connects heater and preceding thorax, working gas enters current distribution device through preceding thorax, enter nozzle body by current distribution device, powder feeder enters nozzle through powder feeding pipe, it is characterized in that nozzle comprises nozzle outer body and inner water conservancy diversion terminal, the axis of water conservancy diversion terminal overlaps with the axis of nozzle flow channel, and the flow direction of working gas is pointed at the tip of water conservancy diversion terminal; Nozzle flow channel comprises upstream convergence section, throat, downstream divergent section; Have the powder feeding duct in the water conservancy diversion terminal, the powder feeding duct connects outside powder feeding pipe, the side of water conservancy diversion terminal has at least two uniform flour openings, there is an angle axis of flour opening and the axis of nozzle, the axis of flour opening outlet offset nozzle runner is positioned at the side of water conservancy diversion terminal and is in nozzle downstream divergent section; The working gas runner is formed by nozzle outer body inwall and inner water conservancy diversion terminal outer profile.
9. cold air driven spray painter according to claim 8 is characterized in that the cross-sectional area in formed space between nozzle downstream diffuser water conservancy diversion terminal and the nozzle outer body equates with the cross-sectional area of conventional Raoul nozzle relevant position, i.e. A
1-a=A, wherein A
1, a and A be respectively the cross-sectional area of nozzle outer body inner chamber, water conservancy diversion terminal and conventional Raoul nozzle flow channel relevant position.
10. according to Claim 8 or 9 described cold air driven spray painters, it is characterized in that the axis of flour opening on the water conservancy diversion terminal and the angle of nozzle axis are 10 ° to 60 °.
11. cold air driven spray painter according to claim 10 is characterized in that the flour opening number is 2 to 6 on the water conservancy diversion terminal, the flour opening outlet is positioned on the same cross section of water conservancy diversion terminal, and equidistantly evenly distributes along the periphery of this cross section.
12. according to Claim 8 or 9 described cold air driven spray painters, the inwall that it is characterized in that the nozzle outer body is a surface that the axis with nozzle is first rotary body in axle center, the exterior contour of water conservancy diversion terminal is a smooth surface that the axis with nozzle is second rotary body in axle center, nozzle upstream before throat, first rotary body is a round platform, second rotary body is a cylinder, and within first rotary body and the space outside second rotary body has constituted the convergence section of equivalent Raoul nozzle; Nozzle downstream after throat is up to the tip of water conservancy diversion terminal, first rotary body is a cylinder, second rotary body is to be positioned at the curved surface cone that the curve rotation at water conservancy diversion terminal tip obtains by the summit, space within first rotary body, outside second rotary body has constituted the divergent section of equivalent Raoul nozzle, the second curved surface cone between throat to water conservancy diversion terminal tip apart from the radius of turn at throat x place
L wherein
0Be divergent section length, promptly nozzle throat is to distance between the water conservancy diversion terminal tip, R
1Be the radius of turn of cylinder I, i.e. the internal diameter of nozzle outer body is with the cross section radius R of the equivalent Raoul nozzle diverging of circle section port
2Equate R
*Be equivalent Raoul nozzle throat cross section radius.
13. according to Claim 8 or 9 described cold air driven spray painters, it is characterized in that after the nozzle diverging section that promptly after inner water conservancy diversion terminal tip, the length of outer body flat segments is 1/4th to 1/3rd of divergent section length.
14. according to Claim 8 or 9 described cold air driven spray painters, it is characterized in that the water conservancy diversion terminal is made up of two assemblies, the interface corresponding nozzle throat of two assemblies or the effective range of throat and by being threaded togather, wherein the corresponding assembly of nozzle upstream part adopts external screw thread, and the assembly of downstream part correspondence adopts internal thread.
15. cold air driven spray painter according to claim 14, two assemblies that it is characterized in that the water conservancy diversion terminal adopt different material manufacturings, the density that wherein is in the material of nozzle downstream components is equal to or less than the density of upstream component, and the heat resistance of the material of upstream component is identical with downstream components or be higher than downstream components.
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| CNB2005100274303A CN100406130C (en) | 2005-06-30 | 2005-06-30 | Cold air powered spraying method and device |
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|---|---|---|---|
| CNB2005100274303A CN100406130C (en) | 2005-06-30 | 2005-06-30 | Cold air powered spraying method and device |
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| CN100406130C CN100406130C (en) | 2008-07-30 |
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| CN101755070B (en) * | 2007-07-05 | 2012-12-05 | Fib环球服务股份公司 | Method and device for spraying a pulverulent material into a carrier gas |
| CN102814248A (en) * | 2012-08-01 | 2012-12-12 | 中国船舶重工集团公司第七二五研究所 | Nozzle for axial siphon powder delivering type cold spray |
| CN104878343A (en) * | 2015-05-18 | 2015-09-02 | 广东省工业技术研究院(广州有色金属研究院) | Preparation method of pure copper coating on surface of diamond/copper composite material |
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| FR2575678B1 (en) * | 1985-01-04 | 1988-06-03 | Saint Gobain Vitrage | PNEUMATIC POWDER EJECTOR |
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| CN1148266C (en) * | 2000-08-16 | 2004-05-05 | 中国石化集团洛阳石油化工工程公司 | Atomizing feed nozzle for petroleum processing |
| DE10126100A1 (en) * | 2001-05-29 | 2002-12-05 | Linde Ag | Production of a coating or a molded part comprises injecting powdered particles in a gas stream only in the divergent section of a Laval nozzle, and applying the particles at a specified speed |
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| CN102814248A (en) * | 2012-08-01 | 2012-12-12 | 中国船舶重工集团公司第七二五研究所 | Nozzle for axial siphon powder delivering type cold spray |
| CN102814248B (en) * | 2012-08-01 | 2014-12-10 | 中国船舶重工集团公司第七二五研究所 | Nozzle for axial siphon powder delivering type cold spray |
| CN104878343A (en) * | 2015-05-18 | 2015-09-02 | 广东省工业技术研究院(广州有色金属研究院) | Preparation method of pure copper coating on surface of diamond/copper composite material |
| CN111433587A (en) * | 2018-01-23 | 2020-07-17 | Cbrn国际有限责任公司 | Biological aerosol particle detector |
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