CN105803380A - Preparation method for low-oxygen-content high-aluminum bronze coating - Google Patents
Preparation method for low-oxygen-content high-aluminum bronze coating Download PDFInfo
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- CN105803380A CN105803380A CN201610274373.7A CN201610274373A CN105803380A CN 105803380 A CN105803380 A CN 105803380A CN 201610274373 A CN201610274373 A CN 201610274373A CN 105803380 A CN105803380 A CN 105803380A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
- C23C4/08—Metallic material containing only metal elements
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Abstract
The invention discloses a preparation method for a low-oxygen-content high-aluminum bronze coating. A low-temperature supersonic spraying technology is adopted for spraying high-aluminum bronze powder on the surface of a copper alloy substrate to prepare the high-aluminum bronze coating. According to a spray gun adopted for spraying, the diameter of a combustion chamber of the spray gun is 6-10 cm, the length of a gun barrel of the spray gun is 20-25 cm, the ratio of the length of the gun barrel to the diameter of the combustion chamber is 2.0-3.5, the length of a powder injecting device of the spray gun is 4-8 cm, and the ratio of the diameter of the combustion chamber to the length of the powder injecting device is 1-2. The diameter of the combustion chamber, the length of the gun barrel and the length of the powder injecting device are optimized, and the temperature and speed of sprayed particles are regulated and controlled in a relatively independent mode, so that fuel is not fully combusted, powder particles are injected to the position with the highest pressure of flame flow, the heating and temperature rising time is shortened, and the low-oxygen-content high-aluminum bronze coating with the oxygen content being 0.8 wt% or lower is finally obtained.
Description
Technical field
The invention belongs to supersonic spray coating technical field, the preparation method being specifically related to a kind of low oxygen content Aluminum Bronze coating.
Background technology
Owing to copper alloy has the electric conductivity of brilliance, good anti-attrition, prominent ductility and sealing and excellent toughness, it is widely used in the parts such as the conductions such as manufacture axle sleeve, pump valve, pipe fitting, wear-resisting and sealing.But, in actual applications, owing to hardness of copper alloy is relatively low, corrosion resisting property is poor, under the Service Environment of ocean, some copper alloy parts such as tube shaft bearing lining, impeller etc. can produce the surface damages such as erosion corrosion, spot corrosion, local stress corrosion, had a strong impact on copper alloy application on naval vessel.
For solving the problems referred to above, adopting spraying technology is a kind of effective way in the corrosion-proof wear coating that copper alloy surface processability is excellent.On sprayed on material selects, Aluminum Bronze, owing to having the good characteristics such as intensity height, corrosion-proof wear excellent performance, fatigue performance be good, is solve the desirable protective material that copper alloy surface damages.And on spraying technology selects, the method preparing copper alloy coating at present mainly has the high temperature spraying technologies such as Ultrasonic Arc Sprayed, Supersonic Plasma Spraying, HVAF, prepared coating has the wear and corrosion behavior of excellence, but owing to spraying temperature is too high, be not suitable for the Aluminum Bronze alloy powder that spraying phase transformation is sensitive.
nullFor the problem that spraying temperature is too high，Chinese patent literature CN104962776A discloses a kind of low temperature supersonic spray coating technology，Adopting the propane that ignition temperature is low is combustion gas with compression air，The flame stream temperature stabilization in spray gun can be made to control within the scope of 600～900 DEG C，Temperature is significantly lower than Ultrasonic Arc Sprayed (more than 10000 DEG C) and Supersonic Plasma Spraying (more than 25000 DEG C)，Spray (3000～4000 DEG C) and supersonic air flame (HVAF) spraying (1000～1900 DEG C) also below supersonic oxygen flame (HVOF) simultaneously，The temperature making sprayed particle is consistently lower than the phase transition temperature (565 DEG C) of Aluminum Bronze material，Decrease the phase transformation of aerosolization Aluminum Bronze powder，Aerosolization Aluminum Bronze powder good characteristic ortho states is made to be implanted into coating，Thus ensureing the corrosion-proof wear performance that reparation is excellent.
But there is the problem that degree of oxidation is higher in the document, especially after propane pressure is more than 78PSI, coating oxygen content will more than 1wt%, higher oxygen content then can cause problems with: on the one hand, aluminium element etc. in Aluminum Bronze powder can take the lead in being combined formation oxide with oxygen element, and the chemical property of these oxides is incompatible with ambient components, can cause coating corrosion resistance degradation, and the segregation easily causing composition causes that stress is concentrated, thus form crackle；On the other hand, Al2O3High Deng the fusing point of oxide, wettability is poor, also results in the bond strength of coating, consistency decline, thus easily causing the problems such as disbonding.
Summary of the invention
It is an object of the invention to solve the problems referred to above, it is provided that the preparation method of the low oxygen content Aluminum Bronze coating of a kind of oxygen content≤0.8wt%.
Applicant finds through great many of experiments: spray gun structure is very big on the impact of Aluminum Bronze coating oxygen content, especially the chamber diameter in spray gun, barrel length and note powder device length.
Specifically, include the ratio of barrel length and chamber diameter of the spray gun of the prior art of Chinese patent literature CN104962776A more than 4, namely adopt the gun barrel that the combustor coupling of small diameter is longer.The combustor heating power that this design of prior art allows for minor diameter is relatively low, thus causing that the temperature of spray gun flame stream reduces, so can reduce the degree of sprayed particle oxidation；And longer gun barrel can increase the speed of flame stream, thus shortening the granule aerial flight time, so it also is able to reach the purpose of less oxidation.
But applicant finds through lot of experiments: the combustor of minor diameter coordinates the gun barrel of long length, deficiency due to heating power, can cause that sprayed particle dispersion phenomenon in high-speed flight process is very serious, specifically sprayed particle in Yan Liu edge flight speed well below at flame stream axis place, the temperature of such Yan Liu edge is then significantly larger than the temperature at flame stream axis place, thus is easier to cause oxidation.
The technical scheme realizing above-mentioned purpose of the present invention is: the preparation method of a kind of low oxygen content Aluminum Bronze coating, and it is to adopt low temperature supersonic spray coating technology in copper alloy matrix surface spraying Aluminum Bronze powder preparation Aluminum Bronze coating；The chamber diameter of spray gun that spraying adopts is 6～10cm, and the barrel length of spray gun is 20～25cm, and the ratio of barrel length and chamber diameter is 2.0～3.5；Oxygen content≤the 0.8wt% of the Aluminum Bronze coating prepared.
When the ratio of barrel length and chamber diameter is less than 2(such as barrel length < 20cm, chamber diameter > 10cm) time, the easy excessive temperature rise of sprayed particle is thus producing harmful phase transformation, oxygen content significantly improves, but also there will be the phenomenon of blocking gun barrel.
Note powder device length is equally very crucial, and different note powder device length determines powder and injects the position of combustor, so that it is guaranteed that powder particle injects the maximum pressure place of flame stream, shortens heating temperature rising-time, thus realizing the feature of dusty spray low-temperature and high-speed.Therefore, the note powder device length of the spray gun of the present invention is 4～8cm, and chamber diameter is 1～2 with note powder device length ratio.
The low temperature supersonic spray coating technology of the present invention be with propane be main combustion gas, compression air be combustion-supporting gas, hydrogen be reducing gas, nitrogen is for powder feeding carrier gas；Coating process parameter is: air pressure is 90～98PSI, and propane pressure is 78～82PSI, and hydrogen flowing quantity is 40～44L/min, and nitrogen flow is 38～42L/min, and spray distance is 120～160mm.
Spray gun (relative to copper alloy matrix laterally) translational speed is 900mm/s～1100mm/s, transverse reciprocating makes spray gun vertically move 1.5mm～2.0mm relative to copper alloy matrix after spraying one time again, until being coated with whole copper alloy surface, and repeat whole copper alloy matrix spraying 5～15 times according to required coating layer thickness.
The Aluminum Bronze powder that the present invention adopts is aerosolization Aluminum Bronze powder, and its particle diameter is 15 μm～45 μm, first dries 3h before using in 120 DEG C of baking ovens.This aerosolization Aluminum Bronze powder cooldown rate in preparation process reaches as high as 106K/s, can suppress γ2The generation of phase.The chemical composition of this aerosolization Aluminum Bronze powder is as follows: Al:13.30wt%, Fe:4.93wt%, Mn:1.62wt%, Zn:0.33wt%, Ni:0.31wt%, Co:5.49wt%, Cu surplus.
The low temperature supersonic spray coating technology of the present invention needs to use pressure-air jet pipe (by multi-direction pipe) that the copper alloy matrix back side is carried out air cooling in spraying process, ensure copper alloy matrix temperature≤150 DEG C, concrete control method is as follows: measure the temperature of copper alloy matrix in real time with digital surface thermometer (the real-time non-contact infrared thermometer of AR892), when the temperature measuring copper alloy matrix reaches 150 ± 2 DEG C, stop spraying line space of going forward side by side immediately cold, when the temperature of copper alloy matrix naturally cools to 100 ± 5 DEG C, be further continued for spraying.
The good effect that the present invention has: the method for (1) present invention is on spray gun structure designs, adopt split design philosophy, fuel chambers diameter, barrel length and note powder device length are optimized combination, realize the relatively independent regulation and control of sprayed particle temperature, speed, namely fuel burn in a combustion chamber with accelerate in gun barrel separate, so that fuel burn incompletely, powder particle is made to inject the maximum pressure place of flame stream, shorten heating temperature rising-time, finally prepare the oxygen content Aluminum Bronze coating lower than 0.8wt%.(2) method of the present invention does not result in the decline of coating corrosion resistance energy, without forming crackle, and can also keep higher bond strength and consistency, it is not easy to cause the problems such as disbonding.The Aluminum Bronze anchoring strength of coating of preparation is at more than 40Mpa, and average microhardness is at more than 280HV, and average deposition efficiency is more than 80%, but also has excellent decay resistance.
Accompanying drawing explanation
Fig. 1 is the tomograph of the spray gun critical piece that the present invention adopts.
Fig. 2 is the bond strength test results schematic diagram of the Aluminum Bronze coating prepared by each embodiment.
Fig. 3 is the micro-hardness testing result schematic diagram of the Aluminum Bronze coating prepared by each embodiment.
Fig. 4 is the XRD figure spectrum result schematic diagram of the Aluminum Bronze coating prepared by each embodiment and aerosolization Aluminum Bronze powder.
The section S EM figure of Fig. 5-1～Fig. 5-4 respectively Aluminum Bronze coating prepared by embodiment 1～embodiment 4.
Fig. 6 is the oxygen content test result schematic diagram of the Aluminum Bronze coating prepared by each embodiment.
Fig. 7 is the porosity test result schematic diagram of the Aluminum Bronze coating prepared by each embodiment.
The salt spray corrosion test result schematic diagram of Fig. 8-1～Fig. 8-4 respectively Aluminum Bronze coating prepared by embodiment 1～embodiment 4.
Detailed description of the invention
(embodiment 1)
The preparation method of the low oxygen content Aluminum Bronze coating of the present embodiment has steps of:
1. adopt particle diameter be the aerosolization Aluminum Bronze powder of 15 μm～45 μm as dusty spray, and be first placed in 120 DEG C of baking ovens drying 3h, stand-by.
The chemical composition of the aerosolization Aluminum Bronze powder that the present embodiment adopts is as follows: Al:13.30wt%, Fe:4.93wt%, Mn:1.62wt%, Zn:0.33wt%, Ni:0.31wt%, Co:5.49wt%, Cu surplus.
2. copper alloy matrix surface is carried out oil removing, rust cleaning and sandblasting alligatoring pretreatment, and cleans matrix surface with acetone.
The copper alloy matrix material that the present embodiment adopts is H62 pyrite.
Sandblasting roughening process is: sand material is Brown Alundum, and granularity is 1mm, and compressed air pressure is 0.7PSI, and sandblasting angle is 90 °, and distance is 100mm.
3. adopt low temperature supersonic spray coating technology in copper alloy matrix surface spraying step aerosolization Aluminum Bronze powder preparation Aluminum Bronze coating 1., spraying parameter is: air pressure is 90～94PSI, propane pressure is 78～80PSI, hydrogen flowing quantity is 40～44L/min, nitrogen flow is 38～42L/min, and spray distance is 140mm.
Detailed process is as follows: be arranged on fixed support by pretreated copper alloy matrix, being controlled spray gun by robot is 1000mm/s relative to copper alloy matrix transverse shifting speed, transverse reciprocating controls spray gun again after spraying one time and vertically moves 2.0mm, proceeding horizontal spraying, whole copper alloy matrix repeats spraying 4 times after all having sprayed 1 time.
The chamber diameter of spray gun is chosen as 6cm, and barrel length is chosen as 20cm, and note powder device length is chosen as 4cm.
Before spraying, copper alloy matrix is dried and the pre-heat treatment, keeps copper alloy matrix maximum temperature within the scope of 80～120 DEG C.
In spraying process, use pressure-air jet pipe that the copper alloy matrix back side is carried out air cooling, ensure copper alloy matrix temperature≤150 DEG C, concrete control method is as follows: measure the temperature of copper alloy matrix in real time with digital surface thermometer (the real-time non-contact infrared thermometer of AR892), when the temperature measuring copper alloy matrix reaches 150 ± 2 DEG C, stop spraying line space of going forward side by side immediately cold, when the temperature of copper alloy matrix naturally cools to 100 ± 5 DEG C, be further continued for spraying.
Aluminum Bronze coating prepared by the present embodiment is numbered A.
(test example 1)
Coating A is carried out bond strength test: carry out according to described in GB/T8642-2002 standard, bonding agent selects SHANGHAI RESEARCH INSTITUTE OF SYNTHETIC RESINS made E-7 type thermal structure glue, colloid proportioning provides according to description, and carries out bond strength test after 100 DEG C solidify 3h, and result is 45.7MPa.
(test example 2)
Coating A is carried out micro-hardness testing: adopting HXD-1000 type microhardness testers, load 100g, load time 15s, respectively in the microhardness value of the surface of coating A and 5 points of section gauge and average, result is 281HV.
(test example 3)
Aerosolization Aluminum Bronze powder and coating A are carried out x-ray diffraction experiment.
Adopting D8A diffractometer, test condition is: Cu-k α target, light tube voltage 40kV, electric current 30mA, scan pattern is scanning continuously, scanning step 0.02 °, time step 0.6s, and XRD figure spectrum result is shown in Fig. 4, wherein, curve e represents aerosolization Aluminum Bronze powder, and curve a represents coating A.
As seen from Figure 4: the thing of coating A and aerosolization Aluminum Bronze powder, mutually without significant change, does not observe obvious oxide peak, and coating well maintains aerosolization Aluminum Bronze powder good characteristic.
(test example 4)
Coating A is carried out degree of oxidation and porosity test.
Adopting Quanta200 type environmental scanning electron microscope that the cross section of coating A is observed, result is shown in Fig. 5-1, and utilizes subsidiary energy disperse spectroscopy that coating A microcell chemical element is analyzed, and the oxygen content recording coating A is 0.61%.
Meanwhile, adopting ImageJ image processing software that the section S EM figure of coating A is carried out porosity measurement, result is 0.34%.
(test example 5)
Coating A is deposited efficiency test (weight method): recording copper alloy matrix weight before spraying is 500g, weigh 100g powder and carry out spray test, after treating that powder sprays completely, weigh the overall weight of copper alloy matrix and coating, repeated measure 5 times respectively 582.3g, 583.2g, 582.8g, 581.9g, 582.1g, thus can calculating deposition efficiency respectively 82.3%, 83.2%, 82.8%, 81.9%, 82.1%, all more than 80%, average deposition efficiency is 82.5%.
(test example 6)
Coating A is carried out corrosion-resistant test: adopt Shanghai Mai Jie experimental facilities company YMX/Q-150 smog corrosion experiment case to test, corrosive environment adopts ISO0376-81976 specification, 5%NaCl solution is adopted to spray continuously, experimental box temperature constant keeps 35 ± 1 DEG C, in experimental box, pH value is maintained at about 7.5, viewing test pattern after 1000 hours, as shown in Fig. 8-1, coating A surface only occurs in that the homogeneous corrosion that local is slight.
(embodiment 2～embodiment 4)
The preparation method of the low oxygen content Aluminum Bronze coating of each embodiment is substantially the same manner as Example 1, is different in that chamber diameter, barrel length, note powder device length, air pressure and propane pressure, is specifically shown in table 1.
The coating according to the method for test example 1～test example 6 prepared by embodiment 2～embodiment 4 carries out correlated performance test, and result is shown in Fig. 2～Fig. 4, Fig. 5-1～Fig. 5-4, Fig. 6, Fig. 7, Fig. 8-1～Fig. 8-4 and table 1 respectively.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Coating is numbered | A | B | C | D |
| Chamber diameter | 6cm | 8cm | 10cm | 10cm |
| Barrel length | 20cm | 22cm | 20cm | 25cm |
| Note powder device length | 4cm | 6cm | 8cm | 8cm |
| Air pressure | 90～94PSI | 92～96PSI | 94～98PSI | 94～98PSI |
| Propane pressure | 78～80PSI | 78～80PSI | 78～80PSI | 80～82PSI |
| Bond strength | 45.7MPa | 47.6MPa | 41.3MPa | 43.6MPa |
| Average microhardness | 281HV | 302HV | 285HV | 314HV |
| Oxygen content | 0.61% | 0.74% | 0.68% | 0.79% |
| Porosity | 0.34% | 0.31% | 0.59% | 0.62% |
| Average deposition efficiency | 82.5% | 82.3% | 82.6% | 82.6% |
| Salt air corrosion surface topography | The homogeneous corrosion that local is slight | The homogeneous corrosion that local is slight | The homogeneous corrosion that local is slight | The homogeneous corrosion that local is slight |
(comparative example 1～comparative example 4)
The preparation method of the Aluminum Bronze coating of each comparative example is substantially the same manner as Example 1, is different in that chamber diameter, barrel length and note powder device length, is specifically shown in table 2.
Coating prepared by comparative example 1～comparative example 4 carries out the test of oxygen content, and result is in Table 2.
Table 2
| Embodiment 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Chamber diameter | 6cm | 6cm | 12cm | 5cm | 6cm |
| Barrel length | 20cm | 25cm | 18cm | 20cm | 15cm |
| Note powder device length | 4cm | 8cm | 8cm | 4cm | 8cm |
| Oxygen content | 0.61% | 0.92% | 1.24% | 0.98% | 1.09% |
Claims (5)
1. a preparation method for low oxygen content Aluminum Bronze coating, it is to adopt low temperature supersonic spray coating technology in copper alloy matrix surface spraying Aluminum Bronze powder preparation Aluminum Bronze coating；It is characterized in that: the chamber diameter of spray gun that spraying adopts is 6～10cm, and the barrel length of spray gun is 20～25cm, the ratio of barrel length and chamber diameter is 2.0～3.5；Oxygen content≤the 0.8wt% of the Aluminum Bronze coating prepared.
2. the preparation method of low oxygen content Aluminum Bronze coating according to claim 1, it is characterised in that: the note powder device length of spray gun is 4～8cm, and chamber diameter is 1～2 with note powder device length ratio.
3. the preparation method of low oxygen content Aluminum Bronze coating according to claim 1 and 2, it is characterized in that spraying parameter is: air pressure is 90～98PSI, propane pressure is 78～82PSI, hydrogen flowing quantity is 40～44L/min, nitrogen flow is 38～42L/min, and spray distance is 120～160mm.
4. the preparation method of the low oxygen content Aluminum Bronze coating according to claim 1 or 2 or 3, it is characterized in that: spray gun translational speed is 900mm/s～1100mm/s, transverse reciprocating makes spray gun vertically move 1.5mm～2.0mm relative to copper alloy matrix after spraying one time again, until being coated with whole copper alloy surface, and repeat whole copper alloy matrix spraying 5～15 times according to required coating layer thickness.
5. the preparation method of the low oxygen content Aluminum Bronze coating according to claim 1 or 2 or 3 or 4, it is characterised in that: spraying process controls copper alloy matrix temperature≤150 DEG C；Concrete grammar is as follows: measure the temperature of copper alloy matrix in real time with digital surface thermometer, when the temperature measuring copper alloy matrix reaches 150 ± 2 DEG C, stop spraying line space of going forward side by side immediately cold, when the temperature of copper alloy matrix naturally cools to 100 ± 5 DEG C, be further continued for spraying.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106167911A (en) * | 2016-07-31 | 2016-11-30 | 中国人民解放军装甲兵工程学院 | Photocopier roller low temperature remanufactures restorative procedure |
| CN107904543A (en) * | 2017-10-23 | 2018-04-13 | 中国人民解放军陆军装甲兵学院 | High densification copper alloy coating and preparation method thereof |
| CN110257753A (en) * | 2019-07-16 | 2019-09-20 | 中国科学院金属研究所 | A method of optimizing iron-based amorphous coating performance in supersonic flame spraying technology |
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| CN101187000A (en) * | 2007-12-06 | 2008-05-28 | 山东大学 | Process for spraying and coating bronze at steel and iron surface using oxygen-acetylene subsonic flame |
| CN104962776A (en) * | 2015-06-18 | 2015-10-07 | 中国人民解放军装甲兵工程学院 | High-alumina bronze coating for repairing volume damage and preparation method of high-alumina bronze coating |
| CN105117599A (en) * | 2015-08-25 | 2015-12-02 | 中国人民解放军装甲兵工程学院 | Establishment method for high aluminum bronze coating property forecasting model and optimization method for single property indicator of high aluminum bronze coating |
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| EP1550735A1 (en) * | 2002-10-09 | 2005-07-06 | National Institute for Materials Science | Method of forming metal coating with hvof spray gun and thermal spray apparatus |
| CN101187000A (en) * | 2007-12-06 | 2008-05-28 | 山东大学 | Process for spraying and coating bronze at steel and iron surface using oxygen-acetylene subsonic flame |
| CN104962776A (en) * | 2015-06-18 | 2015-10-07 | 中国人民解放军装甲兵工程学院 | High-alumina bronze coating for repairing volume damage and preparation method of high-alumina bronze coating |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106167911A (en) * | 2016-07-31 | 2016-11-30 | 中国人民解放军装甲兵工程学院 | Photocopier roller low temperature remanufactures restorative procedure |
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| CN107904543A (en) * | 2017-10-23 | 2018-04-13 | 中国人民解放军陆军装甲兵学院 | High densification copper alloy coating and preparation method thereof |
| CN107904543B (en) * | 2017-10-23 | 2020-04-14 | 中国人民解放军陆军装甲兵学院 | High-density copper alloy coating and preparation method thereof |
| CN110257753A (en) * | 2019-07-16 | 2019-09-20 | 中国科学院金属研究所 | A method of optimizing iron-based amorphous coating performance in supersonic flame spraying technology |
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| CN105803380B (en) | 2018-02-06 |
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