JP2001073109A - Thermal spray powder, thermal spraying process, coated member and sprayed deposit - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermal spray coated member sprayed with aluminum- alloy-matrix thermal spraying material excellent in heat resistance, toughness, and wear resistance or a sprayed deposit and also to provide a thermal spray powder and a thermal spraying process for obtaining them. SOLUTION: The thermal spray powder has a composition consisting of, by weight, 0.5-3.5% Zr, 4-18% of one or more elements selected from the group consisting of La, Ce, Nd, and MM, 0.5-5% of one or more elements selected from the group consisting of Fe, Co, Ni, Ti, Mn, Cr, and Mo, and the balance essentially Al. The coated member and the sprayed deposit can be obtained by performing thermal spraying by the use of the thermal spray powder.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thermal spraying technique using an aluminum rapidly solidified powder, and more particularly, to a thermal spraying powder, a thermal spraying method, a coating member, and a thermal spray.

[0002]

2. Description of the Related Art A thermal spraying technique using an aluminum rapidly solidified powder is disclosed, for example, in Japanese Patent Application Laid-Open No. H11-172465. In this publication, Si (silicon) is 26
~ 80% by weight and optionally other additives,
It is shown that a wear resistant coating member having a composition consisting of Al (aluminum) and unavoidable impurities is formed by plasma spraying. By using such a composition with an increased amount of Si, a fine structure can be obtained, whereby the wear resistance and machinability are improved, and a wear-resistant coated member having a low friction coefficient (μ) can be obtained.

[0003]

In the above technique, Si
Although an attempt is made to increase the wear resistance by increasing the amount, this method has a limit in improving the wear resistance. Further, the thermal spray coating having this composition is very brittle. Also, the heat resistance of the sprayed coating is not sufficient. Further, when the cooling rate is high (〜１０10 ⁵ K / s) as in plasma spraying,
If manufactured by other spraying methods with slow cooling rate,
The above-mentioned improvement in wear resistance cannot be obtained.

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a spray-coated member or a sprayed product of an aluminum alloy matrix which is excellent in both heat resistance and toughness, and which is excellent in wear resistance. To provide a thermal spraying powder and a thermal spraying method for obtaining the same.

Another object of the present invention is to obtain a spray-coated member or a sprayed material having excellent heat resistance, toughness, and wear resistance even when a spraying method having a lower cooling rate than plasma spraying is used. .

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention did not contain Si or contained a small amount of Si, and also contained Zr (zirconium), a transition metal element and a rare earth element. It has been found that by performing thermal spraying using a thermal spray powder having a composition contained in a desired amount, a coated member or a thermal sprayed material having both excellent heat resistance and toughness and excellent wear resistance can be obtained.

Therefore, the thermal spraying powder according to one aspect of the present invention contains Zr in an amount of 0.5% by weight to 3.5% by weight, and contains La (lanthanum), Ce (cerium), Nd (neodymium) and MM. (Misch metal) containing at least one member selected from the group consisting of 4% by weight or more and 18% by weight or less,
e (iron), Co (cobalt), Ni (nickel), Ti
(Titanium), Mn (manganese), Cr (chromium), and Mo (molybdenum), containing at least one selected from the group consisting of 0.5% by weight or more and 5% by weight or less, with the balance being substantially A
l.

[0008] Further, the thermal spraying powder according to another aspect of the present invention is characterized in that the composition of the thermal spraying powder of the above one aspect further comprises one or more Si.
It has a composition containing from 0% by weight to 20% by weight.

The thermal spray powder according to one or another aspect of the present invention contains at least one of La, Ce, Nd and MM. These rare earth elements increase the viscosity of the molten metal to make the structure finer, and at the same time, increase the high-temperature strength by crystallizing Al-rare earth intermetallic compounds at crystal grain boundaries. 4% by weight of these rare earth elements
When the amount is less than the above, the effects of the above-mentioned structure refinement and improvement in high-temperature strength are not obtained. When the amount exceeds 18% by weight, those effects are saturated and the material becomes brittle.

Further, Fe, Co, Ni, Ti, Mn, C
The transition metal elements of r and Mo serve to further increase the viscosity of the molten metal, make the structure finer, and enhance the heat resistance by using the molten metal as an Al-rare earth-transition metal system. When the content of these transition metal elements is less than 0.5% by weight, the effect of refining the structure and improving the heat resistance is small, and when it exceeds 5% by weight, the toughness value is reduced.

Zr plays a role of reducing Al crystal grains by using Al ₃ Zr as a preferential nucleus of Al. Zr
When the content is less than 0.5% by weight, the above-mentioned effect of refining the crystal grains is small, and when the content exceeds 3.5% by weight, the melting point is increased, so that it is difficult to produce an atomized powder. .

In one aspect of the present invention, Si is not contained, and in another aspect, the content of Si is 10% by weight or more and 20% by weight or less, which is smaller than that of the conventional example. For this reason, there is no decrease in toughness caused when a large amount of Si is contained as in the conventional example. The particle size of the Si primary crystal is 2 to
4 μm. If the content of Si is less than 10% by weight, the effect of improving the wear resistance is small, and if it exceeds 20% by weight, the toughness is reduced.

[0013] The thermal spraying powder according to still another aspect of the present invention comprises the thermal spraying powder according to one or other aspects of the present invention described above, and Al ₂ O ₃ , SiC, AlN, Si ₃ N ₄ , ZrO ₂ ,
It is composed of a mixed powder containing at least one hard particle powder selected from the group consisting of TiC and SiO ₂ .

By mixing these hard particle powders, it is possible to obtain higher wear resistance than when Si is added. This is because these hard particles have higher heat resistance, higher hardness and higher toughness than Si. In addition, it is preferable that these hard particle powders are mixed in a range of 2% by weight or more and 10% by weight or less based on the mixed powder.

[0015] The thermal spraying method of the present invention is performed using the thermal spraying powder according to the above one or other aspects. By performing thermal spraying using the powder having the above composition, it is possible to produce a coated member or a sprayed material having both excellent heat resistance and toughness and excellent wear resistance.

The coating member according to one aspect of the present invention manufactured by the above method includes a base material and a film formed on the surface of the base material. The film has a Zr of 0.5
Fe, Co, Ni, Ti, M containing at least one selected from the group consisting of La, Ce, Nd and MM at 4 wt% to 18 wt%.
at least one selected from the group consisting of n, Cr and Mo in an amount of 0.5% by weight or more and 5% by weight or less, with the balance being substantially A
l.

A coating member according to another aspect of the present invention manufactured by the above method includes a base material and a film formed on the surface of the base material. The coating is made by adding 10% by weight of Si to the composition of the coating of the coating member of the above aspect.
The composition contains at least 20% by weight.

The coating member according to one and other aspects of the present invention has excellent heat resistance and toughness and excellent abrasion resistance, as described above, because the film has the above composition.

Preferably, in the covering member according to the above one and other aspects, the substrate is an Al alloy.

Although the Al alloy is light, it generally has poor sliding resistance and heat resistance. Therefore, by adding a film having excellent heat resistance, toughness and abrasion resistance to the above, the added value of the substrate can be increased. Further, since the film is made of an Al-based material, the difference in thermal expansion coefficient from the base material can be reduced, and peeling based on the difference in thermal expansion coefficient can be prevented.

In the coating member according to the above one and other aspects, preferably, the coating is a coating formed by thermal spraying.

By forming a coating by thermal spraying,
A surface film can be produced very easily. Atomized spraying is inferior in that the cooling rate is slower than plasma spraying. However, in forming a film having the above composition, atomization spraying can sufficiently achieve a finer structure.

The thermal spray according to one aspect of the present invention contains Zr in an amount of 0.5% by weight or more and 3.5% by weight or less, and La, Ce,
Containing at least one member selected from the group consisting of Nd and MM in an amount of 4% by weight or more and 18% by weight or less, Fe, Co, Ni, T
It contains at least one selected from the group consisting of i, Mn, Cr and Mo in an amount of 0.5% by weight or more and 5% by weight or less, with the balance being substantially composed of Al and formed of flat particles. .

A sprayed material according to another aspect of the present invention has a composition further containing 10% by weight or more and 20% by weight or less of Si in the composition of the sprayed material of the above one aspect, and is formed from flat particles. I have.

[0025] The sprayed material according to the above one and other aspects has the above composition, so that it has excellent heat resistance, toughness, and abrasion resistance, and has a relatively low cooling rate (10%) other than plasma spraying, such as atomizing spraying. ² to 10 ⁴ K /
Also in s), a fine structure can be obtained. Therefore, good characteristics can be obtained not only for the coating material but also for the bulk body.

The thermal sprayed material in the present application means a material formed by thermal spraying, and includes a form of a coating or a bulk body.

[0027]

EXAMPLES (Example 1) Compositions of Tables 1 to 3 (Nos. 1 to 3)
8) Air atomized powder of 80
200μm thick on one side of 5052 alloy of × 40 × 5mm
Was formed. Prior to thermal spraying, blasting was performed with # 60 alumina beads for the purpose of improving the adhesion of the coating. When hard particle powder is added to the sprayed powder, the average particle size of any hard particle powder is 2 μm.
A zirconia ball having a diameter of 10 mm was put into a V-type mixer, and the mixture was stirred for 1 hour and uniformly mixed. The surface of the thermal spray coating was polished flat at $ 800, and the wear resistance was examined by a pin-on-disk test.

The mating material is φ80 × 10 mm nitrided steel,
The test conditions were as follows: temperature: room temperature, load: 60 kg, friction speed:
4.4 m / s, friction length: 200 m, lubricant: SAE10
W30. Table 4 shows the length of the worn portion in mm.

From these results, it can be seen that the abrasion resistance equal to or higher than that of the comparative example containing a large amount of Si was obtained in the example of the present invention.

The hardness was measured by buffing the coated surface of the plate material and applying a load of 100 g with a Vickers hardness meter.
To evaluate the heat resistance, the hardness test piece was heated and annealed in a constant temperature bath in a nitrogen atmosphere for 24 hours, and then naturally cooled to room temperature, and the hardness was measured similarly. The results are also shown in Table 4.

From these results, in the example of the present invention, the hardness Hv is 150 or more at a temperature of 400 ° C. or less, the hardness Hv is 120 or more at a temperature of 450 ° C., and the hardness Hv is 60 or more at a temperature of 500 ° C. And heat resistance is very high.

Further, in order to measure the high-temperature fatigue strength of the film, an Ono-type rotating bending fatigue test piece was prepared at 5052, and its gauge (φ6) was shot blasted in the same manner as described above, and then subjected to plasma spraying at 200 μm. After forming a thermal sprayed coating having a thickness of 10 mm and lapping, a fatigue strength of 10 ⁷ was measured at 300 ° C. This is the number 1, 4, 20, 27, 2
Performed on 9, 35 samples. Table 4 shows the results.

From these results, it is not possible to maximize the wear resistance without adding hard particles. However, even when hard particles are not added, the high-temperature strength of the film is high in the present invention, so that high fatigue strength can be obtained. It can be seen that it is expressed.

Further, in order to evaluate the toughness of the film, 5
After performing shot blasting on the side surface of a φ30 × 40h disk of No. 052 in the same manner as described above, 200
A sprayed coating having a thickness of μm was formed, polished at $ 800, and upset at 450 ° C. by 80% using a 10-ton autograph to evaluate the presence or absence of cracks. Table 4 shows the results.

From these results, it can be seen that the coating of the present invention is excellent in toughness, so that hot plastic working after formation of the coating is possible.

Table 1 shows examples of the present invention having a composition not containing Si, and Table 3 shows examples of the present invention having a composition containing Si. Further, in Tables 1 to 3, the description of "remaining" in the column of Al means that it is the remaining part.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

[0040]

[Table 4]

Further, the cross-sectional structure of the base material and the sprayed coating in the sample of the present invention of sample No. 1 was observed. The results are shown in FIGS. 1 and 2 that the thermal spray coating of the present invention is formed of flat particles.

The transition metal elements Fe, Ni, Ti, M
It was confirmed that the same characteristics as those of the examples of the present invention were obtained when Co or Cr was added in the range of 0.5% by weight or more and 5% by weight or less instead of n and Mo. Rare earth element L
It was confirmed that the same characteristics as those of the examples of the present invention were obtained when Nd was added in the range of 4% by weight to 18% by weight instead of a, Ce, and MM. Hard particles Al ₂ O ₃ ,
SiC, ZrO ₂ , Ti instead of AlN, Si ₃ N ₄
It was confirmed that even when C and SiO ₂ were mixed in a range of 2% by weight or more and 10% by weight or less, characteristics similar to those of the present invention were obtained.

As hard particles, Al ₂ O ₃ is Hv2
500, ρ (density) 3.99, and SiC is H
v3500, ρ2.8, AlN is Hv14
00, ρ3.3, Si ₃ N ₄ is Hv180
0, ρ3.3, ZrO ₂ is Hv1300,
ρ6.0 is used, TiC is Hv3200, ρ4.
92, and SiO ₂ is Hv1250, ρ2.5
Was used.

From the results in Tables 1, 2 and 4, Z
r of not less than 0.5% by weight and not more than 3.5% by weight, La, C
e, Nd and MM containing at least one selected from the group consisting of 4% by weight or more and 18% by weight or less, Fe, Co, Ni,
1 selected from the group consisting of Ti, Mn, Cr and Mo
A coating excellent in both heat resistance and toughness and excellent in abrasion resistance by using a thermal spraying powder having a composition containing 0.5% by weight or more and 5% by weight or less and the balance substantially consisting of Al. It has been found that a component or a spray can be obtained.

The low toughness values in Comparative Examples Nos. 20 to 26 are considered to be due to the embrittlement of the thermal spray coating due to the large amount of Si. Also number 2
The low heat resistance of Samples 0 to 26 is considered to be due to the absence of rare earth elements.

The low heat resistance of Comparative Example No. 27 is considered to be due to the low Zr content.

In the comparative example of No. 28, the reason why the composition of the thermal sprayed coating did not meet the target is considered to be that the Zr content was large and atomization was difficult.

The reason why the heat resistance was low in Comparative Example No. 29 is probably because the content of the transition metal element was small.

The reason why the toughness value was low in Comparative Example No. 30 is considered to be that the content of the transition metal element was too large.

The reason why the heat resistance was low in the comparative example of No. 31 is probably because the content of the rare earth element was small.

The reason why the comparative examples of Nos. 32 and 33 exhibited low toughness values is considered to be that the content of the rare earth element was too large.

Further, from the results in Tables 3 and 4, Zr was contained in an amount of 0.5% by weight or more and 3.5% by weight or less, and La, Ce,
Containing at least one member selected from the group consisting of Nd and MM in an amount of 4% by weight or more and 18% by weight or less, Fe, Co, Ni, T
one or more selected from the group consisting of i, Mn, Cr and Mo, in an amount of 0.5% by weight or more and 5% by weight or less;
By using a thermal spraying powder having a composition containing at least 20% by weight and not more than 20% by weight, with the balance substantially consisting of Al, it is possible to obtain a coated member or a sprayed material having both excellent heat resistance and toughness and excellent wear resistance. Turned out to be.

In the comparative example of No. 34, the reason why the self-wear amount was large is considered to be that the Si content was small.

The reason why the low toughness value was obtained in Comparative Example No. 38 is considered to be that the Si content was too large.

Further, from the results of Tables 1 to 4, it was found that A was higher in both cases where Si was not contained and when Si was contained in a small amount.
l ₂ O ₃ , SiC, AlN, Si ₃ N ₄ , ZrO ₂ , TiC
It has been found that by using a mixed powder containing one or more hard particles selected from the group consisting of SiO ₂ and SiO _2, a coated member or a sprayed material having further excellent wear resistance can be obtained.

(Example 2) A molten metal having a composition of No. 1 (120
(0 ° C.), and subjected to Ar gas atomization in an Ar gas atmosphere. The diameter of the nozzle was 1 mm, and the pressure of the atomizing gas was 50 kg / cm ² . Lower side of nozzle 10c
m, 50 after blasting used in Example 1
By scanning the 52 plates, a sprayed coating having a thickness of 200 μm was formed. The hardness of this film was Hv200, and the amount of self-wear due to the pin-on-disk was 5.5 mm, showing the same characteristics as in the case of the plasma spraying of Example 1.

From these results, it was found that the thermal spray powder of the present composition was used.
Atomizing spraying (cooling rate 10 ^Three-10^FourK / s)
Even if a more thermal spray coating is made,
Plasma spraying (cooling rate 10^FiveK / s)
It was found to have similar properties.

(Example 3) The atomized thermal spraying of Example 2 was performed for 10 minutes to obtain a bulk body having a thickness of 30 mm. The hardness of this bulk body is still Hv200,
The amount of self-wear due to the pin-on-disk was 5.0 mm.

From these results, it was found that the thermal spraying powder of the present composition was used.
Atomizing spraying (cooling rate 10 ^Three-10^FourK / s)
When making a bulk body (so-called spray for
Mining: Cooling rate is 10^Two-10^ThreeK / s)
Is a plasma spray (cooling rate of 10^FiveK / s)
It was found that the film had the same characteristics as those of the film obtained in the above.

When the bulk body was observed, it was found that it was formed of flat particles as in Example 1.

The embodiments disclosed this time are to be considered in all respects as illustrative and not restrictive. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

[0062]

As described above, according to the present invention, as compared with the conventional example, the thermal spraying powder contains no or a small amount of Si and a desired amount of Zr, a rare earth element and a transition metal element. By using, it is possible to obtain a spray-coated member or a sprayed product of an aluminum alloy matrix having both excellent heat resistance and toughness and excellent wear resistance.

Further, even when a thermal spraying method having a lower cooling rate than the plasma thermal spraying is used, a thermal spray coated member or a thermal sprayed material having excellent heat resistance, toughness and wear resistance can be obtained.

[Brief description of the drawings]

FIG. 1 is a diagram showing a cross-sectional structure of a covering member of an example of the present invention.

FIG. 2 is an enlarged view of FIG. 1;

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Manabu Hashikura 1-1-1, Konokita, Itami City, Hyogo Prefecture Inside Itami Works, Sumitomo Electric Industries, Ltd. No. 1-1 F-term in Sumitomo Electric Industries, Ltd. Itami Works (reference) 4K031 AB08 CB01 CB37 CB43 CB45 CB46

Claims (11)

[Claims] (1) Zr is contained in an amount of 0.5 to 3.5% by weight, and one or more selected from the group consisting of La, Ce, Nd and MM is contained in an amount of 4 to 18% by weight;
e, containing at least one selected from the group consisting of Co, Ni, Ti, Mn, Cr and Mo in an amount of 0.5% by weight or more and 5% by weight or less, with the balance being substantially Al. Powder for thermal spraying. 2. A composition containing Zr in an amount of 0.5% by weight to 3.5% by weight, at least one selected from the group consisting of La, Ce, Nd and MM in an amount of 4% by weight to 18% by weight;
e, at least one selected from the group consisting of Co, Ni, Ti, Mn, Cr and Mo, in an amount of 0.5% by weight or more and 5% by weight or less, Si in an amount of 10% by weight or more and 20% by weight or less, and the balance substantially A powder for thermal spraying, characterized by having a composition consisting of Al. 3. A thermal spraying method using the thermal spraying powder according to claim 1. 4. A powder for thermal spraying according to claim 1 or 2, further comprising Al
_A thermal spray powder comprising a mixed powder containing at least one hard particle powder selected from the group consisting of ₂ O ₃ , SiC, AlN, Si ₃ N ₄ , ZrO ₂ , TiC and SiO ₂ . 5. A thermal spraying method using the thermal spray powder according to claim 4. 6. A base material, comprising: a film formed on the surface of the base material; wherein the film contains 0.5% by weight or more and 3.5% by weight or less of Zr; La, Ce, Nd and At least one selected from the group consisting of MM in an amount of 4% by weight or more and 18% by weight or less;
A coating member comprising at least one selected from the group consisting of e, Co, Ni, Ti, Mn, Cr and Mo in an amount of 0.5% by weight or more and 5% by weight or less, with the balance being substantially composed of Al. 7. A base material, comprising: a film formed on the surface of the base material; the film containing Zr in an amount of 0.5% by weight or more and 3.5% by weight or less, and La, Ce, Nd and At least one selected from the group consisting of MM in an amount of 4% by weight or more and 18% by weight or less;
e, at least one selected from the group consisting of Co, Ni, Ti, Mn, Cr and Mo, in an amount of 0.5% by weight or more and 5% by weight or less, Si in an amount of 10% by weight or more and 20% by weight or less, and the balance substantially A coating member having a composition consisting of Al. 8. The covering member according to claim 6, wherein said base material is an Al alloy. 9. The covering member according to claim 6, wherein the coating is a coating formed by thermal spraying. 10. Zr is added in an amount of 0.5% by weight to 3.5% by weight.
Containing at least one selected from the group consisting of La, Ce, Nd and MM in an amount of 4% by weight or more and 18% by weight or less;
At least one selected from the group consisting of Fe, Co, Ni, Ti, Mn, Cr and Mo in an amount of 0.5% by weight to 5% by weight;
A sprayed product having the following composition, the balance being substantially composed of Al, and formed from flat particles. 11. Zr is not less than 0.5% by weight to 3.5% by weight.
Containing at least one selected from the group consisting of La, Ce, Nd and MM in an amount of 4% by weight or more and 18% by weight or less;
At least one selected from the group consisting of Fe, Co, Ni, Ti, Mn, Cr and Mo in an amount of 0.5% by weight to 5% by weight;
Below, containing 10% by weight or more and 20% by weight or less of Si,
A sprayed material having a composition substantially consisting of Al, and formed from flat particles.