CN1614072A - Titanium-nickel-carbon reacting spraying composite powder and preparation thereof - Google Patents
Titanium-nickel-carbon reacting spraying composite powder and preparation thereof Download PDFInfo
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- CN1614072A CN1614072A CNA2004100803196A CN200410080319A CN1614072A CN 1614072 A CN1614072 A CN 1614072A CN A2004100803196 A CNA2004100803196 A CN A2004100803196A CN 200410080319 A CN200410080319 A CN 200410080319A CN 1614072 A CN1614072 A CN 1614072A
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Abstract
The invention was involved in Ti-Ni-C alloys response spray coating complex powder and its preparation method, which belonged to the powder manufacturing craft of metal ceramic complex coating technology. Cane sugar was used as precursor of carbon and it was carbonized under definite temperature to form Ti-Ni-C alloys response spray coating complex powder, which was enclosed by material powder. The technology was: mixing the Ti and Ni power with mixture ratio ->wet grinding->drying the slurry ->carbonization step by step->breaking and screening. The method not only settled the separation of response component during the response spray powder but also the cane sugar was used as precursor of carbon so it had low carbonization temperature, high carbon purity, small pollution of process of carbonization and the high industrial feasibility. To select Ni as the metal base to reduce rather large grain TiC conglobation and increase the wear-resisting property of coating.
Description
Technical field
The invention belongs to the flouring technology in the cermet composite coating technology of preparing, specially refer to a kind of preparation that is used for reactive spray TiC/Ni alloyed metal-ceramic composite coating.
Background technology
The metal-ceramic compound coating, especially the metal-ceramic compound coating that with the carbide is wild phase is a kind of wear-resistant coating with very big prospects for commercial application, and utilization is widely all arranged in the manufacturing of its wear member in fields such as Aeronautics and Astronautics, metallurgy, mine, oil and chemical industry and the reparation.Be that the metal-ceramic compound coating of wild phase especially is concerned by people with the TiC particle in recent years, because TiC has low-friction coefficient, high rigidity, low density and good high-temperature stability, it will replace employed WC in the traditional technology, Cr gradually
3C
2At present, be that ceramic phase in the metal-ceramic compound coating of wild phase adopts usually and adds the compound mode in advance in spraying starting material (powder, silk material etc.) with the carbide, ceramic phase skewness in the coating, granularity is thicker, ceramic/metal bonding interface vulnerable to pollution, this will influence the performance of coating greatly.Produced a kind of novel method for preparing metal-ceramic---reaction thermal spraying in recent years, it combines SHS technology and thermospray, utilizes the thermopositive reaction between powder and the powder, finishes the synthetic and deposition of material in spraying process simultaneously.The reaction heat of emitting in the reaction in building-up process can improve spraying temperature, reduces the porosity of coating, improves coating and matrix bond; And original position synthetic hard is tiny circular granular mutually, is uniformly dispersed the bonding interface cleaning of hard and metallic matrix.Therefore reaction thermal spraying has overcome the shortcoming of conventional spray paint metal-ceramic technology, has incomparable advantage aspect the preparation metal-ceramic compound coating.
Existing suitable research aspect metal-ceramic compound coating reaction thermal spraying both at home and abroad in recent years is especially to the research of TiC as the compound coating of wild phase.In " the Titanium carbide-iron composite coatings by reactive plasmaof ilmenite " of the 287th volume 121-125 page or leaf of J Alloys and Compounds in 1999, introduced and utilized ilmenite (FeTiO
3) be spray material, methane is reactant gases, reaction and plasma spraying the technology of TiC/Fe compound coating.But its process characteristic has determined that there is very large randomness in the reaction between constituent element in the spraying process, and reaction process is restive, and coated component is difficult to adjust simultaneously.Therefore reactive spray adopts compound spraying powder as spray material more present stage, utilizes Reactive Flame to prepare the TiC/Fe compound coating as having narrated in " the Reaction Mechanism of Preparing TiC-Fecoating by Reactive flame spray synthesis " of the 3rd phase 227-230 page or leaf of J Uni SciTechnol Beijing in 2000; At 20 volumes of powder metallurgy technology in 2002, introduced in " the TiC/Fe-Al compound coating Study on Reactive Flame " of the 4th phase 219-222 page or leaf and utilized Reactive Flame to prepare the TiC/FeAl compound coating.But the reactive spray composite powder that it adopts all is simple mechanically mixing powder or reunion powder (adding a spot of binding agent granulates), reaction constituent element separate easily under the effect of high speed flame stream, quite a few constituent element powder can't fully react, cause residual harmful phase in the coating, the tissue odds of coating is even, the coating quality instability.Therefore, can guarantee that the reactive spray composite powder technology of preparing of fully reacting between the reaction constituent element in the spraying process has become the gordian technique of reactive spray technology in the engineering practical application.
At above problem, the 14th the 8th phase of volume the 1389th～1393 page " Study of TiC/Fe Metal Ceramic Composite coating by Reactive Flame Spray " at China YouSe Acta Metallurgica Sinica in 2004 proposes to utilize pitch to prepare the higher Ti-Fe-C reacting spraying composite powder of raw material powder bonding strength as the presoma of carbon, it can effectively solve the separation problem of raw material powder, Zhi Bei TiC/Fe compound coating has good abrasion resistance simultaneously, but the presoma of the carbon that it adopts is a pitch, because pitch complicated component, carbonization temperature higher (about 600 ℃), be unfavorable for the easily adding of the alloying element of oxidation under the hot conditions, be not suitable for preparing the more compound coating of alloying element, this will influence the composition design of coating and widening of product category.Simultaneously, in the prepared TiC/Fe base composite coating, matrix Fe and TiC wettability are relatively poor, TiC particle gathering is easily grown up, the bigger TiC aggregate and the coefficient of expansion gap of matrix are bigger, can cause the stress between TiC aggregate and the matrix excessive, some can form crackle in the TiC aggregate, and this can make coating wear resistance descend to some extent to a certain extent.Therefore select the presoma of more suitable carbon and selection and TiC to have the metallic matrix of good wettability more can effectively widen the application prospect of TiC/ metal composite coating.
Summary of the invention
The invention provides a kind of novel process of utilizing common sucrose to prepare the Ti-Ni-C reacting spraying composite powder as the presoma of carbon, adopt the presoma of sucrose as carbon, through the carbonization under the certain temperature, form the Ti-Ni-C reacting spraying composite powder that raw material powder is coated by carbon on every side.Reaction constituent element separation problem in reactive spray powder when it not only can solve reaction thermal spraying and prepares the carbide compound coating, and the carbonization temperature of sucrose is low, the carbon purity height of generation pollutes for a short time in the carbonization process, and the industrialization feasibility is higher.Select Ni can obviously reduce the appearance of larger particles TiC aggregate simultaneously, improve the abrasion property energy as metallic matrix.
The Ti-Ni-C reacting spraying composite powder is to be raw material with Ti powder, Ni powder among the present invention, the one-tenth of compound spraying powder is grouped into by mass percentage, Ti:28%～58%, Ni:21%～66%, C:6%～13%, alloying element mass percent are Cr:0～14%, Fe:0～10%, Mo:0～6%, Si:0～3%, B:0～2%.
Technological process of the present invention is: with Ti powder, Ni powder and sucrose by proportioning mix → cake mass of slurry oven dry → oven dry after wet-milling → mixing wet-milling carries out the cake mass crushing and screening after step carbonation → carbonization.Its concrete processing parameter is: earlier Ti powder, Ni powder and sucrose are mixed, the sucrose mass percent is 19%～32%; During wet-milling, mixture is mixed with 1: 1～1.5: 1 (volume ratio) with alcohol, used steel ball is 3: 1～6: 1 with the volume ratio ratio of mixture again, and the ball milling time is 24～72 hours; During ball milling, drum's speed of rotation is 100～150r.p.m; Mixed slurry is dried in 45～60 ℃ temperature range, and drying time is 12～24 hours; Cake mass after the oven dry is carried out step carbonation in the heat treatment furnace of nitrogen protection handle: be heated to 200～250 ℃ earlier, be incubated 1～1.5 hour, and then be warming up to 300～350 ℃, carried out carbonizing treatment 2～2.5 hours; To the block crushing and screening after the carbonization.
Characteristics of the present invention are sucrose just can carbonization in lower temperature, and form carbon and be coated on clad structure around the raw material powder, the cohesive strength height of raw material powder and carbon, not easily separated in spraying process, what help reacting finishes.Selecting Ni is because Ni is better to the wettability of TiC as metallic matrix, grows up so the TiC particle is difficult for reuniting, and can obviously reduce the appearance of larger particles TiC aggregate; Ball milling is in order to make the uniform distribution of raw material powder particle size reduction and raw material powder, to be beneficial to the reaction in the spraying process; Adopt wet-milling not only can make raw material powder not oxidized in mechanical milling process as ball milling method, and sucrose be melted into help in the alcohol sucrose be distributed to more uniformly raw material powder around; Adopt the step carbonation method to be because contain a large amount of protiums and oxygen element in the sucrose, the purpose of carbonization is exactly protium and oxygen element will be removed, the raw material powder activity is stronger under higher carbonization temperature, oxygen element generation oxidizing reaction in the gas that is easy to produce with carbonization, exothermic heat of reaction has caused the self-propagating reaction of raw material powder simultaneously.If when carbonization temperature is low, can prevent the generation of oxidizing reaction and self-propagating reaction, but hydrogen-oxygen content is higher in the prepared dusty spray, carbonization is incomplete.In order to address this problem, adopt the step carbonation method to carry out carbonization.(200～250 ℃) remove hydrogen-oxygen by insulation 1～1.5 hour at first at a lower temperature.Because raw material powder is active less at this moment, and the gaseous emission that carbonization produces is slower, can avoid taking place self-propagating reaction.Temperature rises to 300～350 ℃ of continuation carbonizing treatment 2～2.5 hours then.Though this stage raw material powder is active higher, by the hydrogen-oxygen that removes of fs, the gas volume that the carbonization of this moment produces is very little, can not produce oxidation and self-propagating reaction.Nitrogen protection in the carbonization process can prevent the oxidation or the scaling loss of raw material powder oxidation and alloying element in the carbonization process.
Compared with prior art, the invention has the advantages that:
1, the Ti-Ni-C reacting spraying composite powder of the present invention's preparation forms the carbon clad structure around raw material powder, makes the cohesive strength height of raw material powder and carbon, and not easily separated in spraying process, what help reacting finishes.
2, adopt sucrose as presoma, carbonization temperature is low, and the carbon purity height of generation pollutes for a short time in the carbonization process, and commercial viability is higher.
3, select Ni can reduce the appearance of larger particles TiC aggregate, improve coating performance as metallic matrix.
4, nothing is harmful mutually residual in Zhi Bei the TiC/Ni reactive spray compound coating, and homogeneous microstructure.Coatingsurface hardness (HRC) is more than 60, and wear resistance obviously is better than conventional Ni60 wear-resistant coating.
Description of drawings
Fig. 1 is a Ti-Ni-C reactive spray composite powder structure photo.
Fig. 2 is Ti-Ni-C reactive spray composite powder XRDP.
Fig. 3 is a compound coating back scattering pattern.
Fig. 4 is the XRDP of compound coating.
From Fig. 1 Ti-Ni-C reactive spray composite powder structure photo, can see in the Ti-Ni-C reactive spray composite powder of preparation, form carbon and be coated on tiny raw material powder clad structure on every side, the cohesive strength height of raw material powder and carbon, not easily separated in spraying process, what help reacting finishes; X-Ray result can see from Fig. 2 Ti-Ni-C reactive spray composite powder, does not contain any other impurity in the composite powder that adopts this method to prepare, and does not also form oxide compound and carbide simultaneously in carbonization process; Can see that from Fig. 3 compound coating back scattering pattern the coating that obtains has typical thermospray lamella pattern, and homogeneous microstructure, and volume particle size TiC aggregate is less in the coating; Fig. 4 is the SEM high power photo of the lamella in the coating, and tiny as we can see from the figure TiC uniform particles is distributed in the metallic matrix, and it is closely spherical that the TiC particle becomes, and granular size is below 0.5 μ m; Can see that from the XRD result of Fig. 5 compound coating institute's coated component that obtains is simple, only by TiC and Ni
3Ti two phase composites do not have other impurity and generate mutually.
Embodiment
Raw material of the present invention is Ni powder, o powder, alloying element powder and sucrose.Prepared Ti-Ni-C reacting spraying composite powder composition is as shown in table 1.
Its concrete technical process is:
1, raw material powder is mixed by composition proportion, wet-milling 24～72 hours on ball mill then, the volume ratio of used steel ball and raw mix is 3: 1, and drum's speed of rotation is 120r.p.m, and ball-milling medium is an alcohol;
2, the mixed slurry behind the ball milling is dried in drying baker, bake out temperature is 50 ℃, and drying time is 12 hours;
3, drying is good lumpy material is put into the burning boat, carries out carbonizing treatment then in the nitrogen protection heat treatment furnace.At first removed hydrogen-oxygen 1.5 hours at 250 ℃.Temperature rises to 350 ℃ of continuation carbonizing treatment 2 hours then;
4, the porous block solid that obtains after the carbonization is carried out fragmentation, the dusty spray that requires granularity is prepared in screening.
Table 1 has provided several preferred embodiments of the present invention:
Table 1 preferred embodiment
| Preferred embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | ||
| T i-N i-C powder is that last anti-Cheng Yingfen spraying is compound | Ti mass percent (%) | ??28.2 | ??28.2 | ??56.3 | ??56.3 | ??42.1 | ??42.1 | ??42.1 | |
| Ni mass percent (%) | ??65.1 | ??31.1 | ??31.4 | ??21.4 | ??47.5 | ??27.5 | ??33 | ||
| C mass percent (%) | ??6.7 | ??6.7 | ??12.3 | ??12.3 | ??10.5 | ??10.5 | ??10.5 | ||
| Alloying element quality percentage composition (%) | ????Fe | ??0 | ??10 | ??0 | ??5 | ??0 | ??7 | ??2.4 | |
| ????Cr | ??0 | ??13 | ??0 | ??3 | ??0 | ??8 | ??7.6 | ||
| ????Mo | ??0 | ??5 | ??0 | ??0 | ??0 | ??2 | ??0 | ||
| ????Si | ??0 | ??3 | ??0 | ??1 | ??0 | ??2 | ??2.4 | ||
| ????B | ??0 | ??2 | ??0 | ??1 | ??0 | ??1 | ??2 | ||
| The mass percent (%) that sucrose adds | ??21.3 | ??21.3 | ??31.4 | ??25.1 | ??28.7 | ??25.0 | ??19.1 | ||
| The ball milling time (h) | ??24 | ??36 | ??24 | ??36 | ??36 | ??48 | ??72 | ||
| Spraying method | The spraying of acetylene flame | The spraying of acetylene flame | Plasma spraying | Plasma spraying | The spraying of acetylene flame | The spraying of acetylene flame | Plasma spraying | ||
| Coatingsurface Rockwell hardness (HRC) | ??60.4 | ??61.7 | ??66.4 | ??67 | ??65.4 | ??67.8 | ??70.2 | ||
| Coating wear resistance (comparing) with conventional Ni60 coating | 6 times | 8 times | 5 times | 6 times | 8 times | 10 times | 15 times | ||
In sum, and from accompanying drawing as can be known, adopt the method for Ti-Ni-C reacting spraying composite powder, can prepare hardness and wear resistance good metal ceramic composite coating.
Claims (2)
1, a kind of titanium-nickel-carbon reacting spraying composite powder, utilize the presoma of carbon to be carbon source, it is characterized in that: with Ti powder, Ni powder is raw material, and the one-tenth of compound spraying powder is grouped into by mass percentage, Ti:28%～58%, Ni:21%～66%, C:6%～13%, alloying element mass percent are Cr:0～14%, Fe:0～10%, Mo:0～6%, Si:0～3%, B:0～2%.
2, a kind of technology for preparing titanium-iron-carbon reacting spraying composite powder comprises raw material powder by the proportioning mixing and ball milling, the mixed powder oven dry, and carbonizing treatment, crushing and screening is characterized in that:
1) utilize the presoma of sucrose as carbon, when Ti powder, Ni powder and sucrose mixed by proportioning, the mass percent of sucrose was 19%～32%;
2) during wet-milling, mixture is mixed with 1: 1～1.5: 1 (volume ratio) with alcohol, used steel ball is 3: 1～6: 1 with the volume ratio ratio of mixture, and the ball milling time is 24～72 hours;
3) slurry that mixes was dried 12～24 hours in 45～60 ℃ of scopes;
4) block with oven dry is heated to 200～250 ℃ earlier in the heat treatment furnace of nitrogen protection, is incubated 1～1.5 hour, and then is warming up under 300～350 ℃, carries out carbonizing treatment 2～2.5 hours.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255557B (en) * | 2008-03-11 | 2010-06-02 | 潍坊学院 | Synthetic reaction plasma cladding powder and preparation technique thereof |
| CN103614682A (en) * | 2013-11-18 | 2014-03-05 | 中国人民解放军92537部队 | Wear-resisting corrosion-resistant composite coating for ship water-jet propeller impeller and preparation method thereof |
| CN106591671A (en) * | 2016-12-12 | 2017-04-26 | 威海职业学院 | TiC-Ti-Ni porous ceramic material and preparation method thereof |
| CN110387517A (en) * | 2019-07-30 | 2019-10-29 | 北京科技大学 | A kind of titanium-silico-carbo reacting spraying composite powder and preparation method thereof |
| CN111334696A (en) * | 2020-04-13 | 2020-06-26 | 山东交通学院 | TiC-based porous composite material and preparation method thereof |
| CN113365765A (en) * | 2018-12-13 | 2021-09-07 | 欧瑞康美科（美国）公司 | Mechanically alloyed metallic thermal spray material and thermal spray method using said material |
-
2004
- 2004-09-29 CN CNB2004100803196A patent/CN1288272C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255557B (en) * | 2008-03-11 | 2010-06-02 | 潍坊学院 | Synthetic reaction plasma cladding powder and preparation technique thereof |
| CN103614682A (en) * | 2013-11-18 | 2014-03-05 | 中国人民解放军92537部队 | Wear-resisting corrosion-resistant composite coating for ship water-jet propeller impeller and preparation method thereof |
| CN103614682B (en) * | 2013-11-18 | 2016-01-06 | 中国人民解放军92537部队 | Water jet propeller of ship impeller wear-resistant corrosion-resistant composite coating and preparation method thereof |
| CN106591671A (en) * | 2016-12-12 | 2017-04-26 | 威海职业学院 | TiC-Ti-Ni porous ceramic material and preparation method thereof |
| CN113365765A (en) * | 2018-12-13 | 2021-09-07 | 欧瑞康美科（美国）公司 | Mechanically alloyed metallic thermal spray material and thermal spray method using said material |
| CN113365765B (en) * | 2018-12-13 | 2024-04-02 | 欧瑞康美科（美国）公司 | Mechanically alloyed metallic thermal spray material and thermal spray method using the same |
| CN110387517A (en) * | 2019-07-30 | 2019-10-29 | 北京科技大学 | A kind of titanium-silico-carbo reacting spraying composite powder and preparation method thereof |
| CN110387517B (en) * | 2019-07-30 | 2020-12-01 | 北京科技大学 | Titanium-silicon-carbon reaction spraying composite powder and preparation method thereof |
| CN111334696A (en) * | 2020-04-13 | 2020-06-26 | 山东交通学院 | TiC-based porous composite material and preparation method thereof |
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