CN1209215C - Aluminum-coated nickel composite powder coated with ultramicro or nanometer aluminum powder and preparation method thereof - Google Patents
Aluminum-coated nickel composite powder coated with ultramicro or nanometer aluminum powder and preparation method thereof Download PDFInfo
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- CN1209215C CN1209215C CN 02100588 CN02100588A CN1209215C CN 1209215 C CN1209215 C CN 1209215C CN 02100588 CN02100588 CN 02100588 CN 02100588 A CN02100588 A CN 02100588A CN 1209215 C CN1209215 C CN 1209215C
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Abstract
An aluminum-coated nickel composite powder coated with ultrafine or nano aluminum powder is characterized in that nickel powder particles are used as cores, the aluminum powder forms coating layers on the outer surfaces of the nickel powder particles, and the average particle size of the aluminum powder is 30-800 nm. The aluminum-clad nickel composite powder coated by the ultramicro or nanometer aluminum powder has the following characteristics: (1) the coating shape of the composite particles is uniform and complete, and no scattered aluminum powder exists, so that the uniformity of the composite powder is good; (2) the composite powder has good fluidity, and the typical fluidity is 19s/50 g; (3) the composite powder has excellent combustion characteristics, so that the heating intensity is proper in the spraying operation process.
Description
Technical field
The present invention relates to clad products of a kind of metal dust and preparation method thereof, particularly relate to a kind of aluminum metal powder and coat goods of nickel and preparation method thereof.
Background technology
Compound nickel aluminium coating material is the important thermal spraying material of a class, and its application has been penetrated into each industrial circle of national economy of military project and civilian aspect along with the development of plasma spray technology.The many forms with composite powder of nickel aluminium are used for the processing of coatings such as all kinds of wear-resisting, high temperature resistances.
Traditional Al contained Ni end is a kind of cladded type composite powder, and Fa Zhan aluminium nickel coat powder then is a kind of non-cladded type powder composite powder thereafter.By contrast, the latter demonstrates characteristic preferably, and, spraying coating process higher as anchoring strength of coating be (spraying smog is few, flame adfluxion in) better.After aluminium nickel coat powder is heated to uniform temperature, strong exothermic reaction taking place between constituent element, thereby workpiece substrate and sprayed on material molten drop are fully heated, make molten drop realize little metallurgical binding with the fusion thin layer of matrix surface, obtains higher adhesion; Spraying back coating outer surface is coarse simultaneously, and a desirable surface that can connect other sprayed on material is provided.Thereby nickel aluminium coating is used as the bond coating of many materials more not only as working lining.This makes it have wide application market and prospect in the thermal spraying industry.
Sprayed on material manufacturers such as internationally famous METCO, Castolin all have the aluminium nickel coat composite powder product of oneself.China passes through number of research projects the beginning of the eighties at the end of the seventies by the Beijing Mine and Metallurgy General Inst, has at first developed aluminium nickel coat composite powder, and obtains bigger application in production and relevant new material development.Relatively reach investigation by analysis, the aluminium nickel coat composite powder comprehensive technical performance of development is near like product levels such as U.S. METCO450 and Switzerland Castolin25000.However, the aluminium nickel coat composite powder of former development still exposes deficiency aspect further the requiring of spraying coating process and coating structure performance satisfying.This is mainly reflected in the inhomogeneities of powder composition, the adaptability deficiency of spraying coating process, and coating structure is inhomogeneous, defective is more etc. causes comprehensive serviceability to need to improve.Primary aluminum nickel coat powder is the primary raw material preparation with coarse grain footpath nickel powder and fine grain aluminium powder.With the nickel powder is core, and the about 45-102 μ of its particle diameter m, aluminium powder then form clad at the outer surface of nickel powder particle, in principle aluminium powder heal detailed rules and regulations more help clad evenly, and will improve the flowability of powder, finally help obtaining evenly, dense coating.
But the aluminium powder average grain diameter that adopts is usually about 3-5 μ m at present, because the aluminium powder particle diameter is bigger, the effect that coats is still undesirable, and the nickel particle surface exists not coat distinguishes the aluminium powder that existence freely is scattered or self reunites in the powder, therefore, the common compound powder uneven components of aluminium nickel coat is mobile poor at present, is used for the thermal spraying meeting and causes heat release degree discomfort, coating structure is inhomogeneous, and the comprehensive usability of the more grade of defective is poor.
The preparation method of relevant Nano metal powder is a lot, as polishing, application number CN00105672, and CN00209258 in done detailed introduction in the patent application specification.As laser method, done detailed introduction among the application number CN00212238 in the patent application specification.As arc process, done detailed introduction among the application number CN00261101 in the patent application specification.As blasting, done detailed introduction among the publication number RU2149735 in the patent application specification.But,, do not retrieve and adopt ultra micro or Nano metal powder to coat the technology of other metallic particles by retrieval.
Summary of the invention
The purpose of this invention is to provide a kind of coating form even, complete, do not have the aluminium powder that is scattered, the aluminium nickel coat composite powder that the ultra micro of good fluidity or nanometer aluminium powder coat, and its preparation method is provided.
For achieving the above object, the present invention takes following technical scheme: the aluminium nickel coat composite powder that this ultra micro or nanometer aluminium powder coat, be to be core with the nickel powder particle, aluminium powder forms clad at the outer surface of nickel powder particle, and the average grain diameter of described aluminium powder is 30-800nm.
In the aluminium nickel coat composite powder that ultra micro of the present invention or nanometer aluminium powder coat, the average grain diameter optimum range of described aluminium powder is 50-150nm.
In the aluminium nickel coat composite powder that ultra micro of the present invention or nanometer aluminium powder coat, the average grain diameter of described nickel powder particle is 20-120 μ m.
In the aluminium nickel coat composite powder that ultra micro of the present invention or nanometer aluminium powder coat, by weight percentage, wherein, Al is 1-20wt%, and binding agent is 1-8wt%, and surplus is a nickel powder.
In the aluminium nickel coat composite powder that ultra micro of the present invention or nanometer aluminium powder coat, described binding agent optimum range is 2-5wt%.
In the aluminium nickel coat composite powder that ultra micro of the present invention or nanometer aluminium powder coat, described aluminium powder is evenly to be bonded on the outer surface of nickel powder particle by binding agent to form clad.
The method for preparing the aluminium nickel coat composite powder of ultra micro of the present invention or nanometer aluminium powder coating comprises the steps:
Prepare ultra micro or nanometer aluminium powder according to conventional method;
Prepare burden according to following weight percentage: ultra micro or nanometer aluminium powder are 1-20wt%, and binding agent is 1-8wt%, and surplus is a nickel powder;
Adopt spiral reunion agitating device to coat stirring, the nickel powder of the above-mentioned weight of in this device, packing into, binding agent and≤ultra micro or the nanometer aluminium powder of the above-mentioned weight of 40wt% coat in advance, stir, the ultra micro or the nanometer aluminium powder that add residuals weight afterwards again, carry out multilayer and coat stirring, be cured simultaneously and stir drying;
Carry out discharging after solidifying drying, sieve then, promptly get the aluminium nickel coat composite powder that ultra micro or nanometer aluminium powder coat.
Prepare in the method for the aluminium nickel coat composite powder that ultra micro of the present invention or nanometer aluminium powder coat, described binding agent is made up of epoxy resin, diamines, no phenyl ring oxygen solvent or diluent, epoxy resin, diamines, no phenyl ring oxygen solvent or diluent ratio of weight and number are 7-10: 0.5-2: 18-22: or form by phenolic resins, NL curing agent, no benzene synthetic thinner, phenolic resins, NL curing agent, no benzene synthetic thinner ratio of weight and number are 8-10: 0.5-2: 18-22.
Prepare in the method for the aluminium nickel coat composite powder that ultra micro of the present invention or nanometer aluminium powder coat, total addition of described nickel powder, binding agent and ultra micro or nanometer aluminium powder is the 20-80 volume % of screw rod reunion agitating device volume.
Prepare in the method for the aluminium nickel coat composite powder that ultra micro of the present invention or nanometer aluminium powder coat, the mixing time of described spiral reunion agitating device is: 10-100min.
Prepare in the method for the aluminium nickel coat composite powder that ultra micro of the present invention or nanometer aluminium powder coat, moto-vibro screen is adopted in described screening, and its top sieve is: the 120-180 order, following sieve is: the 280-360 order.
Prepare in the method for the aluminium nickel coat composite powder that ultra micro of the present invention or nanometer aluminium powder coat, the screw speed of described spiral reunion agitating device is: 30-300rpm.
In the present invention, when not adopting bonding agent, be to adopt the high-energy ball milling method coating of reuniting.
Description of drawings
Fig. 1 is the aluminium nickel coat composite powder preparation technology flow chart that ultra micro of the present invention or nanometer aluminium powder coat
Fig. 2 is conventional aluminium nickel coat composite powder granule-morphology figure
Fig. 3 is the granule-morphology figure of the aluminium nickel coat composite powder of ultra micro of the present invention or nanometer aluminium powder coating
Fig. 4 (a) is the differential thermal analysis result diagram of conventional aluminium nickel coat composite powder under air conditions
Fig. 4 (b) is the differential thermal analysis result diagram of aluminium nickel coat composite powder under air conditions that ultra micro of the present invention or nanometer aluminium powder coat
Fig. 5 (a) is the metallographic structure figure of the nano aluminum nickel coat coating of plasma spraying
Fig. 5 (b) is the metallographic structure figure of the conventional aluminium nickel coat coating of plasma spraying
Fig. 5 (c) is the metallographic structure figure of isoionic METCO450 coating
The specific embodiment
The aluminium powder average grain diameter 30-800nm that the present invention adopts compares obvious refinement with common in the past average grain diameter 3-5 μ m.The specific area of aluminium powder enlarges markedly.Because the particle diameter of nanometer aluminium powder is thin, is difficult in reunion coating process, only just can reach the covering amount requirement, thereby needs to realize that uniform multilayer coats by one deck coating.By research, determined following process route, as shown in Figure 1.
1, the preparation of ultra micro or nanometer aluminium powder
Adopt known method to prepare ultra micro or nanometer aluminium powder.
2, selection of binder
The effect of binding agent is that ultra micro or nanometer aluminium powder evenly are bonded in hundreds of times big nickel powder particle surface of particle diameter, and realizes that uniform multilayer coats, and forms uniform nickel/aluminium complex.Require adhesion strength height, good dispersion, be easy to drying (solidifying or volatilization), and heat-resisting, moisture-proof.Described binding agent is made up of epoxy resin, diamines, no phenyl ring oxygen solvent or diluent, and epoxy resin, diamines, no phenyl ring oxygen solvent or diluent ratio of weight and number are 7-10: 0.5-2: 18-22; Or form by phenolic resins, NL curing agent, no benzene synthetic thinner, phenolic resins, NL curing agent, no benzene synthetic thinner ratio of weight and number are 8-10: 0.5-2: 18-22.
3, reunion cladding process
In fact reunion cladding process process steps comprises: adorn nickel powder material, adding additives, add a part of ultra micro or nano aluminum powder, pre-coating, stir, add remaining ultra micro or nano aluminum powder, coat stirring, solidify drying, discharging.The coating process spiral reunion agitating device on carry out, spiral reunion agitating device is formed by being provided with by the screw rod of drive force in the appearance body with charging and discharging mouth.
Nickel powder adopts the atomizing nickel powder (grain shape is subsphaeroidal) of Beijing Mine and Metallurgy General Inst's production as primary raw material, and its nickel content is greater than 99.0%; Particle diameter distributes and is controlled at the index that slightly is narrower than the ultimate size requirement.And the average grain diameter of ultra micro or nanometer aluminium powder usually can be in the 30-800nm range regulation.
For guaranteeing to coat the effect that stirs, charge should be controlled certain relative quantity, and experiment shows that the 20-80% that accounts for the agglomeration device volume with stocking volume is advisable.
Reunion of the present invention is stirred in the coating process, be to be undertaken by following step, first in spiral reunion agitating device, pack into nickel powder material, binding agent and part ultra micro or nano aluminum powder, start agitating device and give coating, stir, add remaining ultra micro more afterwards or the nano aluminum powder coats stirring.
Solidify dry the coating in the agitation phases and carry out simultaneously, after finishing the coating stage, still proceeding in reunion.Carry out discharging after solidifying drying, after discharging is detained, finally obtain the compound nickel aluminium lamination material that ultra micro of the present invention or nanometer aluminium powder coat through screening.Solidify dry temperature and be room temperature-150 ℃.
Aluminium nickel coat composite powder (hereinafter to be referred as aluminium nickel coat of the present invention) that ultra micro of the present invention or nanometer aluminium powder coat and the common aluminium nickel coat composite powder (hereinafter to be referred as the primary aluminum nickel coat) that coats than Grenaille compare, and wherein mobile, apparent density sees Table 1.
Table 1 aluminium nickel coat of the present invention and primary aluminum nickel coat composite powder part characteristic are relatively
| Product | Mobile (s/50g) | Apparent density (g/cm 3) |
| The primary aluminum nickel coat | 23 | 3.426 |
| Aluminium nickel coat of the present invention | 19 | 3.498 |
As seen from Table 1, aluminium nickel coat of the present invention is better than the primary aluminum nickel coat on mobile and apparent density performance.
The granule-morphology of aluminium nickel coat of the present invention is seen Fig. 3 photo, compares with the granule-morphology of primary aluminum nickel coat in Fig. 2 photo.Although adopt formerly to add bigger bonding dosage than Grenaille, still be difficult to obtain desirable adhesive effect, the nickel particle surface exists and coats the district, exists in the powder freely to be scattered or the aluminium powder of self reunion.The aluminum particle of greater particle size is difficult to realize strong bond because the contact-making surface of its unit mass and nickel particle is little.And the composite powder after employing ultra micro or the coating of nanometer aluminium powder new technology is obviously even, bond effect is good, and does not have the aluminium powder that freely is scattered.Simultaneously, also uniform " nickel/nano aluminum " composite particles of explanation coating presents configuration of surface preferably, and this is the good reason of its powder flowbility just.Aluminium nickel coat of the present invention is better than the primary aluminum nickel coat on combustion characteristics (differential thermal).Fig. 4 is differential thermal analysis result diagram, and Fig. 4 (a) is depicted as the primary aluminum nickel coat, aluminium nickel coat of the present invention shown in Fig. 4 (b).The exothermal effect of the aluminium nickel coat composite powder that aluminium powder of the present invention coats is the strong and broad than primary aluminum nickel coat composite powder exothermal effect obviously.
Test detects and shows the spraying coating process superior performance of aluminium nickel coat composite powder of the present invention.Be mainly reflected in that heating strength is more suitable, smog is few, flame banishes heat and concentrates, the powder deposition efficiency height.
Fig. 5 be primary aluminum nickel coat coatings 5 (a) with nano aluminum nickel coat coatings 5 (b) plasma spraying after the typical coating tissue morphology, give the Fig. 5 of typical organization (c) behind the METCO450 plasma spraying among the figure.Relatively as seen, the tissue morphology of Fig. 5 (a) is obviously more even, fine and close, tiny than Fig. 5 (b), slightly is better than Fig. 5 (c) simultaneously.Evenly, fine and close coating structure not only helps conventional mechanical property, and is of value to the raising of the thermal conductivity of non-oxidizability, coating, finally widen coating the use field, prolong the service life of coating.
Adopt the anchoring strength of coating after anchoring strength of coating after the spraying of ultra micro of the present invention or nano aluminum nickel coat is better than primary aluminum nickel coat spraying.
Table 2 has been listed the typical testing result of plasma spraying coating.The result shows that not only spraying coating process is good for the nickel aluminium composite powder that aluminium powder of the present invention coats, because composition is even, the improvement of spraying process thermal characteristics, has obtained even, fine and close, tiny coating structure, and has made Bond Strength of Coating increase simultaneously.By the raising of bond strength, the nickel aluminium composite powder product that makes nanometer aluminium powder of the present invention coat can satisfy the requirement of the bonding bottom spraying of military project department vitals.
The comparison of table 2 anchoring strength of coating
| Product | 0.6-0.9mm thick coating (MPa) | 0.06-0.15mm thick coating (MPa) |
| The nano aluminum nickel coat | 35.8 | 48.7-55.0 |
| The primary aluminum nickel coat | 32.2 | 44.0-51.5 |
Embodiment
Method according to routine prepares nanometer aluminium powder, and its average grain diameter is 50-150nm; And choose the nickel powder that average grain diameter is 20-120 μ m; And by following proportioning weighing, nanometer aluminium powder 6wt%, bonding agent are 4wt%, and surplus is a nickel powder.And with the mixture of epoxy resin, diamines, no phenyl ring oxygen solvent or diluent as binding agent, wherein, the weight ratio of epoxy resin, diamines, no phenyl ring oxygen solvent or diluent is 9: 1: 20.
Adopt screw rod reunion agitating device to coat stirring, and undertaken by following step, the nickel powder material of the above-mentioned weight of in spiral reunion agitating device, packing into earlier, and the sodium rice aluminium powder material of 1/3 amount, the binding agent that adds above-mentioned weight then, start agitating device and coat in advance, stir, the nanometer aluminium powder that adds residue 2/3 amount afterwards again coats, stirs.Wherein, feeding quantity is the 50 volume % that the cumulative volume of nickel powder, binding agent, nanometer aluminium powder accounts for the agitating device volume.The screw speed of agitating device is 150rpm.Mixing time is as the criterion with adhesive cures, and total time is 60min, and wherein pre-mixing time accounts for 1/3 of whole mixing time.
Solid drying carries out when the reunion coating is stirred simultaneously, and solidifying dry temperature is room temperature, after finishing the coating stirring, still can stop certain hour (about 15min) and proceed to solidify dry in agitating device.
Carry out discharging after solidifying drying, discharging is sieved by moto-vibro screen after being detained, requirement according to the final products particle diameter, adopting 150 orders is top sieve, and 300 orders obtain the aluminium nickel coat composite powder that ultra micro of the present invention or nanometer aluminium powder coat at last for sieving down.
The aluminium nickel coat composite powder that ultra micro of the present invention or nanometer aluminium powder coat has following characteristics:
(1) composite particles coating form is even, complete, does not have the aluminium powder that is scattered, thereby the composite powder good uniformity;
(2) composite powder good fluidity, typical case's flowability is 19s/50g;
(3) the composite powder combustion characteristics is superior, thereby calorific intensity is suitable in the spraying operating process.
The coating that the nickel aluminium composite powder that coats with ultra micro of the present invention or nanometer aluminium powder prepares has following characteristics:
(1) coating structure good uniformity, hole are few, obviously are better than the homemade nickel alclad composite powder coatings tissue that coats with the micron order aluminium powder, and slightly are better than the nickel alclad composite powder coatings tissue of external micron order aluminium powder coating;
(2) anchoring strength of coating is apparently higher than the aluminium nickel coat composite powder coatings that coats with the micron order aluminium powder, and can stably reach the adhesive strength requirement of external high-performance aero-engine used coating as primer, reaches more than the 48.3MPa.
Claims (10)
1, the aluminium nickel coat composite powder that coats of a kind of ultra micro or nanometer aluminium powder is to be core with the nickel powder particle, and aluminium powder forms clad at the outer surface of nickel powder particle, it is characterized in that the average grain diameter of described aluminium powder is 30-800nm.
2, the aluminium nickel coat composite powder of ultra micro according to claim 1 or nanometer aluminium powder coating is characterized in that the average grain diameter of described aluminium powder is 50-150nm.
3, the aluminium nickel coat composite powder of ultra micro according to claim 1 and 2 or nanometer aluminium powder coating is characterized in that the average grain diameter of described nickel powder particle is 20-120 μ m.
4, the aluminium nickel coat composite powder of ultra micro according to claim 3 or nanometer aluminium powder coating, it is characterized in that: by weight percentage, wherein, Al is 1-20wt%, and binding agent is 1-8wt%, and surplus is a nickel powder.
5, the aluminium nickel coat composite powder that coats of ultra micro according to claim 4 or nanometer aluminium powder is characterized in that, described aluminium powder is evenly to be bonded on the outer surface of nickel powder particle by binding agent to form clad.
6, a kind of method for preparing the aluminium nickel coat composite powder of described ultra micro of claim 1 or nanometer aluminium powder coating is characterized in that this method comprises the steps:
Prepare ultra micro or nanometer aluminium powder according to conventional method;
Prepare burden according to following weight percentage: ultra micro or nanometer aluminium powder are 1-20wt%, and binding agent is 1-8wt%, and surplus is a nickel powder;
Adopt spiral reunion agitating device to coat stirring, the nickel powder of the above-mentioned weight of in this device, packing into, binding agent and≤ultra micro or the nanometer aluminium powder of the above-mentioned weight of 40wt% coat in advance, stir, the ultra micro or the nanometer aluminium powder that add residuals weight afterwards again, carry out multilayer and coat stirring, be cured simultaneously and stir drying;
Carry out discharging after solidifying drying, sieve then, promptly get the aluminium nickel coat composite powder that ultra micro or nanometer aluminium powder coat.
7, the method for the aluminium nickel coat composite powder of preparation ultra micro according to claim 6 or nanometer aluminium powder coating, it is characterized in that, described binding agent is made up of epoxy resin, diamines, no phenyl ring oxygen solvent or diluent, and epoxy resin, diamines, no phenyl ring oxygen solvent or diluent ratio of weight and number are 7-10: 0.5-2: 18-22; Or form by phenolic resins, NL curing agent, no benzene synthetic thinner, phenolic resins, NL curing agent, no benzene synthetic thinner ratio of weight and number are 8-10: 0.5-2: 18-22.
8, the method for the aluminium nickel coat composite powder of preparation ultra micro according to claim 6 or nanometer aluminium powder coating is characterized in that the addition of described nickel powder, binding agent and ultra micro or nanometer aluminium powder is the 20-80 volume % of screw rod reunion agitating device volume.
9, the method for the aluminium nickel coat composite powder of preparation ultra micro according to claim 6 or nanometer aluminium powder coating is characterized in that the mixing time of described spiral reunion agitating device is: 10-100min.
10, the method for the aluminium nickel coat composite powder of preparation ultra micro according to claim 6 or nanometer aluminium powder coating is characterized in that, moto-vibro screen is adopted in described screening, and its top sieve is: the 120-180 order, following sieve is: the 280-360 order.
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| CN 02100588 CN1209215C (en) | 2002-02-06 | 2002-02-06 | Aluminum-coated nickel composite powder coated with ultramicro or nanometer aluminum powder and preparation method thereof |
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| CN 02100588 CN1209215C (en) | 2002-02-06 | 2002-02-06 | Aluminum-coated nickel composite powder coated with ultramicro or nanometer aluminum powder and preparation method thereof |
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| EP1928597B1 (en) * | 2005-09-27 | 2009-06-03 | ETH Zürich | Method for the attachment of nanoparticles to substrate particles |
| CN103084571B (en) * | 2012-12-30 | 2015-06-24 | 南京师范大学 | Nanometer Al/Ni/hydroxyl-terminatedpoly butadiene (HTPB) nucleus-shell structure energetic composite particle and preparation method thereof for solid propellant |
| CN103691938A (en) * | 2014-01-01 | 2014-04-02 | 北京矿冶研究总院 | Surface alloying method for metal coated powder |
| CN103817341B (en) * | 2014-03-04 | 2016-02-03 | 北矿新材科技有限公司 | A kind of preparation method of high heat release nickel-based composite pow-der |
| CN105970147B (en) * | 2016-06-06 | 2019-05-10 | 平高集团有限公司 | A kind of aluminium alloy based composites, preparation method and application |
| CN106270486B (en) * | 2016-08-30 | 2018-07-10 | 安徽克里斯特新材料有限公司 | A kind of preparation method of the bis- particle powders of Ni-Al |
| CN106623890B (en) * | 2016-09-14 | 2019-02-22 | 河南理工大学 | Graphene/nanometer aluminium powder composite granule, graphene/aluminum based composites comprising the composite granule and preparation method thereof |
| CN112063963A (en) * | 2020-09-17 | 2020-12-11 | 中国航发沈阳黎明航空发动机有限责任公司 | Aluminum-coated nickel composite powder and plasma spraying preparation method of coating thereof |
| CN112458391A (en) * | 2020-11-24 | 2021-03-09 | 安徽盈锐优材科技有限公司 | High-bonding-strength plasma spraying priming powder and preparation method thereof |
| CN113651659B (en) * | 2021-08-18 | 2022-05-24 | 北京理工大学 | Metal-based energetic fragment with impact reaction activity and preparation method thereof |
| CN115425236B (en) * | 2022-09-06 | 2023-06-02 | 浙江柔震科技有限公司 | Composite current collector and preparation method and device thereof |
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