CN1940119A - Thermal spray powder and forming method of thermal spray coating - Google Patents
Thermal spray powder and forming method of thermal spray coating Download PDFInfo
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- CN1940119A CN1940119A CN 200610131877 CN200610131877A CN1940119A CN 1940119 A CN1940119 A CN 1940119A CN 200610131877 CN200610131877 CN 200610131877 CN 200610131877 A CN200610131877 A CN 200610131877A CN 1940119 A CN1940119 A CN 1940119A
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Abstract
A first thermal spray powder includes granulated and sintered yttria particles obtained by granulating and sintering a raw material powder in air or oxygen. The primary particles constituting the granulated and sintered yttria particles have an average particle size between 0.5 and 1.5 um inclusive, and 1.11 times or more as large as the raw material powder. A thermal spray layer with high plasma etching resistance which can resistant a plasma having 0.8 W/cm<2> output power toward the layer can be formed by using first thermal spray powder. A second thermal spray powder of this invention contains granulated and sintered yttria particles obtained by granulating and sintering a raw material powder in air or oxygen, and the primary particles have an average particle size between 3 and 8 um. A thermal spray layer with high plasma etching resistance which can resistant a plasma having no more than 0.8 W/cm<2> output power toward the layer can be formed by using second thermal spray powder.
Description
Technical field
The present invention relates to a kind of formation method that contains the thermal spray powder of yttrium oxide granulation-sintering particle and used the hot spray coating of this thermal spray powder.
Background technology
In the manufacturing field of semiconductor devices and liquid crystal apparatus, by used plasma (Japanese: dry etching (Dry Etching) プ ラ ズ マ), carry out the microfabrication of equipment.By at plasma flow process (Japanese: might be subjected to the semiconductor devices manufacturing installation of plasma etching damage and the part of liquid crystal apparatus manufacturing installation プ ラ ズ マ プ ロ セ ス) hot spray coating is set, improve the anti-plasma etching of this part with this, this technology is (for example with reference to a publication 2002-80954 communique) known to us.Like this,, can suppress dispersing of particulate, thereby improve the qualification rate of equipment by improving anti-plasma etching.
The hot spray coating that is used for this kind purposes for example can form by plasma thermal sprayed with the thermal spray powder that contains yttrium oxide granulation-sintering particle.Though carrying out for the exploitation of the thermal spray powder of various isoionic anti-plasma etchings such as height output plasma and low output plasma to improve hot spray coating, can't be met the yttrium oxide granulation-sintering particle of the performance that requires at present.
Summary of the invention
The 1st purpose of the present invention provides the plasma of unit surface hot spray coating is exported at 0.8W/cm
2More than (contain 0.8W/cm
2) plasma (this specification sheets hereinafter is called high output plasma.) the thermal spray powder that formation was suitable for of hot spray coating of anti-plasma etching excellence and the formation method of hot spray coating.The 2nd purpose of the present invention provides the plasma of unit surface hot spray coating is exported not enough 0.8W/cm
2Plasma (this specification sheets hereinafter is called low output plasma.) the hot spray powder that formation was suitable for of hot spray coating of anti-plasma etching excellence and the formation method of hot spray coating.
For reaching above-mentioned purpose, the invention provides following thermal spray powder.This thermal spray powder contains raw material powder granulation and sintering obtains in atmosphere or oxygen yttrium oxide granulation-sintering particle, and the median size that constitutes the primary particle of yttrium oxide granulation-sintering particle is 0.5～1.5 μ m and is more than 1.11 times of median size (containing 1.11 times) of raw material powder.
The present invention also provides following thermal spray powder.This thermal spray powder contains raw material powder granulation and sintering obtains in atmosphere or oxygen yttrium oxide granulation-sintering particle, and the median size that constitutes the primary particle of yttrium oxide granulation-sintering particle is 3～8 μ m.
The present invention also provides and contains the formation method that above-mentioned arbitrary thermal spray powder is formed the hot spray coating of hot spray coating operation through the atmos plasma thermospray.
Embodiment
The 1st example of the present invention below is described.
The thermal spray powder of the 1st example is made of yttrium oxide granulation-sintering particle in fact.Yttrium oxide granulation-sintering particle, promptly the thermal spray powder of the 1st example is by granulation-sintering process manufacturing.More specifically, be to make prilling powder from raw material powder, will pulverize behind this prilling powder sintering, further classification and making as required.
Raw material powder both can be a yttrium oxide powder, also can be the powder that can be converted to the material of yttrium oxide as the mixture of yttrium powder, yttrium hydroxide powder or these and yttrium oxide powder by granulation and sintering circuit.
Make prilling powder from raw material powder, both can carry out mist projection granulating, also can or compress granulation by the rolling granulation directly from raw material powder making prilling powder by the slurry that raw material powder and suitable dispersant are formed.
In order to obtain exporting for height the hot spray coating of isoionic anti-plasma etching excellence, the gas around during the sintering prilling powder is necessary for atmosphere or oxygen.Sintering prilling powder in the gas except that atmosphere and oxygen of argon gas and nitrogen etc. and the thermal spray powder that produces is difficult to form the isoionic anti-plasma etching excellence of hot spray coating export to(for) height.This be because, carry out agglomerating words with argon gas or nitrogen, the yttrium oxide that can occur in the prilling powder in sintering is reduced, the result can make the amount of the oxygen in the resulting thermal spray powder reduce.The hot spray coating that is formed by the few thermal spray powder of oxygen level contains the lattice imperfection that causes because of anoxic easily.Because the etching meeting of the hot spray coating that plasma carried out the preferentially defect part from hot spray coating begins to carry out, therefore, by the few formed hot spray coating of thermal spray powder of oxygen level to export isoionic anti-plasma etching for height relatively poor.
During 1500 ℃ of gas top temperature (sintering temperature) less thaies around during the sintering prilling powder, say 1550 ℃ of less thaies further, further say 1600 ℃ of less thaies, the exporting isoionic anti-plasma etching for height and may descend of hot spray coating.This is because along with the reduction of sintering temperature, it is insufficient to occur sintering easily.The inadequate words of sintering, the minimizing of the defect concentration that sintering produces is less, and what therefore obtain is the higher thermal spray powder of defect concentration.The hot spray coating that is formed by the higher thermal spray powder of defect concentration contains the defective that is caused by defective in the thermal spray powder easily.As mentioned above, because the etching meeting of the hot spray coating that plasma carried out the preferentially defect part from hot spray coating begins to carry out, therefore, by the higher formed hot spray coating of thermal spray powder of defect concentration that height is exported isoionic anti-plasma etching is relatively poor.In addition, the inadequate words of sintering, the powder feeding machine is to the course of conveying of thermal spraying machine, or in the thermospray flame, occurs the destruction of yttrium oxide granulation-sintering particle easily.Therefore, from improving inhibited oxidation yttrium granulation-sintering particle of destructive viewpoint export isoionic anti-plasma etching and to(for) height, sintering temperature is preferably and (is containing 1500 ℃) more than 1500 ℃, be more preferably and (containing 1550 ℃) more than 1550 ℃, best is (to contain 1600 ℃) more than 1600 ℃.
On the other hand, when sintering temperature surpasses 1800 ℃, says the exporting isoionic anti-plasma etching for height and may descend of hot spray coating further above 1750 ℃.This is because along with the rising of sintering temperature, it is excessive to occur sintering easily.Sintering over-drastic words are difficult to occur the softening or fusion of yttrium oxide granulation-sintering particle that thermospray flame brought.Therefore, fusion or not remollescent yttrium oxide granulation-sintering particle can not sneaked into hot spray coating, cause the density of hot spray coating to descend, make hot spray coating export isoionic anti-plasma etching decline for height.In addition, the softening or fusion of yttrium oxide granulation-sintering particle that thermospray flame is brought is difficult to carry out, and the deposit efficiency of thermal spray powder (thermospray qualification rate) also can descend.Therefore, from improving the viewpoint of exporting isoionic anti-plasma etching and improving the deposit efficiency of thermal spray powder for height of hot spray coating, sintering temperature is preferably and (is containing 1800 ℃) below 1800 ℃, is more preferably (containing 1750 ℃) below 1750 ℃.
The hold-time of the sintering temperature during the sintering prilling powder, (sintering time) less than was in the time of 12 minutes, said less than further 30 minutes, further said less than 1 hour, the particle growth that occurs primary particle easily is insufficient, occurs the destruction of yttrium oxide granulation-sintering particle easily.Therefore, for the destruction of inhibited oxidation yttrium granulation-sintering particle, sintering time is preferably and (is containing 12 minutes) more than 12 minutes, is more preferably (containing 30 minutes) more than 30 minutes, and best is (to contain 1 hour) more than 1 hour.
On the other hand, when sintering time surpasses 30 hours, say further to surpass 20 hours that further say to surpass 10 hours, the particle of primary particle is grown up and almost reached capacity, thereby does not have actual effect.Therefore, from the agglomerating actual effect, sintering time is preferably and (is containing 30 hours) below 30 hours, is more preferably (containing 20 hours) below 20 hours, and best is (to contain 10 hours) below 10 hours.
In order to obtain exporting for height the hot spray coating of isoionic anti-plasma etching excellence, the median size that constitutes the primary particle of yttrium oxide granulation-sintering particle must (contain 0.5 μ m) more than 0.5 μ m.Less than 0.5 μ m is difficult to form the isoionic anti-plasma etching excellence of hot spray coating export to(for) height by thermal spray powder.This is because along with reducing of the median size of the primary particle that constitutes yttrium oxide granulation-sintering particle, the ratio that is tabular zone in the hot spray coating of tabular single crystal structure will uprise.Owing to contain more crystal defect in tabular zone, the etching meeting of the hot spray coating that plasma carried out the preferentially defect part from hot spray coating begins to carry out, therefore, the hot spray coating that tabular regional percentage is high that height is exported isoionic anti-plasma etching is relatively poor.
But, constitute the median size less than 0.6 μ m of the primary particle of yttrium oxide granulation-sintering particle, even more than 0.5 μ m, (contain 0.5 μ m), the ratio in tabular zone in the hot spray coating may be higher slightly, and height is exported isoionic anti-plasma etching descending slightly of hot spray coating appears in the possibility of result.Therefore, export the viewpoint of isoionic anti-plasma etching from what improve hot spray coating for height, the median size that constitutes the primary particle of yttrium oxide granulation-sintering particle (contains 0.6 μ m) better more than 0.6 μ m.
In order to obtain exporting for height the hot spray coating of isoionic anti-plasma etching excellence, the median size that constitutes the primary particle of yttrium oxide granulation-sintering particle must (contain 1.5 μ m) below 1.5 μ m.Surpass 1.5 μ m, thermal spray powder also is difficult to form the isoionic anti-plasma etching excellence of hot spray coating export to(for) height.This is because along with the increase of the median size of the primary particle that constitutes yttrium oxide granulation-sintering particle, the width in tabular zone in the hot spray coating will become big.As mentioned above, owing to contain more crystal defect in tabular zone, the etching meeting of the hot spray coating that plasma carried out the preferentially defect part from hot spray coating begins to carry out, therefore, contain tabular bigger zone of width hot spray coating that height is exported isoionic anti-plasma etching is relatively poor.
But, the median size that constitutes the primary particle of yttrium oxide granulation-sintering particle surpasses the words of 1.4 μ m, even below 1.5 μ m, (contain 1.5 μ m), the width in tabular zone in the hot spray coating may be bigger than normal slightly, and the possibility of result hot spray coating occurs and height is exported isoionic anti-plasma etching descends slightly.Therefore, export the viewpoint of isoionic anti-plasma etching from what improve hot spray coating for height, the median size that constitutes the primary particle of yttrium oxide granulation-sintering particle (contains 1.4 μ m) better below 1.4 μ m.
In order to obtain exporting for height the hot spray coating of isoionic anti-plasma etching excellence, the median size that constitutes the primary particle of yttrium oxide granulation-sintering particle also is necessary for more than 1.11 times of median size (containing 1.11 times) of raw material powder.1.11 times of less thaies, thermal spray powder are difficult to form the isoionic anti-plasma etching excellence of hot spray coating export to(for) height.This be because, constitute 1.11 times of median size of the not enough raw material powder of median size of the primary particle of yttrium oxide granulation-sintering particle, sintering is with insufficient.Insufficient and the isoionic anti-plasma etching of the reason export to(for) height that can reduce hot spray coating of sintering as mentioned above.
But, 1.15 times words of the median size of the not enough raw material powder of median size of the primary particle of formation yttrium oxide granulation-sintering particle, even (containing 1.11 times) more than 1.11 times, it is insufficient that sintering also may show slightly, and height is exported isoionic anti-plasma etching descending slightly of hot spray coating appears in the possibility of result.Therefore, from improving the isoionic anti-plasma etching of viewpoint export to(for) height, the median size that constitutes the primary particle of yttrium oxide granulation-sintering particle is that more than 1.15 times of median size (containing 1.15 times) of raw material powder are better.
The median size less than 20 μ m of yttrium oxide granulation-sintering particle, say less than 22 μ m further, further say less than 25 μ m, say the words of less than 28 μ m more further, more thinner particle may be contained in yttrium oxide granulation-sintering particle, thereby the thermal spray powder of good fluidity may not be obtained.Therefore, in order to improve the flowability of thermal spray powder, the median size of yttrium oxide granulation-sintering particle is preferably more than 20 μ m and (contains 20 μ m), be more preferably more than 22 μ m and (contain 22 μ m), better is (to contain 25 μ m) more than 25 μ m, and best is (to contain 28 μ m) more than 28 μ m.In addition,, become unstable easily, occur the in uneven thickness of hot spray coating easily, or the anti-plasma etching of hot spray coating is inhomogeneous for the supply of the thermal spray powder of thermospray flame along with the flowability of thermal spray powder descends.
On the other hand, the median size of yttrium oxide granulation-sintering particle surpasses 60 μ m, say further and surpass 57 μ m, further say and surpass 55 μ m, say the words that surpass 52 μ m more further, fully softening or fusion may be difficult to by thermospray flame oxidation yttrium granulation-sintering particle, thereby the deposit efficiency of thermal spray powder may be reduced.Therefore, in order to improve deposit efficiency, the median size of yttrium oxide granulation-sintering particle is preferably below 60 μ m and (contains 60 μ m), is more preferably below 57 μ m (to contain 57 μ m), better is (to contain 55 μ m) below 55 μ m, and best is (to contain 52 μ m) below 52 μ m.
The cumulative volume of the pore that the diameter 3 μ m in yttrium oxide granulation-sintering particle are following surpasses 0.2cm
3/ g says to surpass 0.17cm further
3/ g further says to surpass 0.15cm
3/ g, the density of yttrium oxide granulation-sintering particle may descend, thereby may cause the density of the hot spray coating that is formed by thermal spray powder also to descend.Therefore, in order to improve the density of hot spray coating, the cumulative volume of the pore that the diameter 3 μ m in yttrium oxide granulation-sintering particle are following is preferably at 0.2cm
3/ g is following (to contain 0.2cm
3/ g), be more preferably at 0.17cm
3/ g is following (to contain 0.17cm
3/ g), best is at 0.15cm
3/ g is following (to contain 0.15cm
3/ g).In addition, the void content height of the hot spray coating that density is low, and since the etching of the hot spray coating that plasma carried out preferentially the pore periphery from hot spray coating begin to carry out, so the high hot spray coating of void content to export isoionic anti-plasma etching for height relatively poor.
Peak less than 0.06 μ m in the diameter Distribution of the pore in yttrium oxide granulation-sintering particle, say less than 0.07 μ m further, further say less than 0.08 μ m, the exporting isoionic anti-plasma etching for height and may descend slightly of hot spray coating.Therefore, export the viewpoint of isoionic anti-plasma etching for height from improving hot spray coating, peak in the diameter Distribution of the pore in yttrium oxide granulation-sintering particle is preferably more than 0.06 μ m and (contains 0.06 μ m), be more preferably more than 0.07 μ m and (contain 0.07 μ m), best is (to contain 0.08 μ m) more than 0.08 μ m.In addition, along with the step-down of the peak in the diameter Distribution of the pore in yttrium oxide granulation-sintering particle, the ratio regular meeting in tabular zone in the hot spray coating uprises.As mentioned above, owing to contain more crystal defect in tabular zone, and the etching meeting of the hot spray coating that plasma carried out preferentially the defect part from hot spray coating begin to carry out, therefore, that height is exported isoionic anti-plasma etching is relatively poor for the higher hot spray coating of the ratio in tabular zone.
On the other hand, peak in the diameter Distribution of the pore in yttrium oxide granulation-sintering particle surpasses 2 μ m, say further to surpass 1.9 μ m, further says, the exporting isoionic anti-plasma etching for height and may descend slightly of hot spray coating above 1.8 μ m.Therefore, export the viewpoint of isoionic anti-plasma etching from what improve hot spray coating for height, peak in the diameter Distribution of the pore in yttrium oxide granulation-sintering particle is preferably below 2 μ m and (contains 2 μ m), be more preferably below 1.9 μ m and (contain 1.9 μ m), best is (to contain 1.8 μ m) in addition below 1.8 μ m, along with uprising of the peak in the diameter Distribution of the pore in yttrium oxide granulation-sintering particle, the width in tabular zone in the hot spray coating can become big.As mentioned above, contain more crystal defect in tabular the zone, because the etching meeting of the hot spray coating that plasma carried out the preferentially defect part from hot spray coating begins to carry out, therefore, that height is exported isoionic anti-plasma etching is relatively poor for the hot spray coating that contains tabular zone of big width.
During the Bulk Specific Gravity less than 1.2 of yttrium oxide granulation-sintering particle, the density of yttrium oxide granulation-sintering particle may descend, thereby may cause the density of the hot spray coating that is formed by thermal spray powder also to descend.Therefore, in order to improve the density of hot spray coating, the Bulk Specific Gravity of yttrium oxide granulation-sintering particle (is containing 1.2) more than 1.2 better.In addition, as mentioned above, the void content height of the hot spray coating that density is low and since the etching of the hot spray coating that plasma carried out preferentially the pore periphery from hot spray coating begin to carry out, so the high hot spray coating of void content to export isoionic anti-plasma etching for height relatively poor.
On the other hand, though the Bulk Specific Gravity upper limit of yttrium oxide granulation-sintering particle is not particularly limited, the Bulk Specific Gravity of yttrium oxide granulation-sintering particle is preferably and (is containing 3.0) below 3.0.
The angle of repose of yttrium oxide granulation-sintering particle surpasses 48 degree, says further to surpass 44 degree, further says to surpass 40 degree, may not obtain the thermal spray powder of good fluidity.Therefore, in order to improve the flowability of thermal spray powder, the angle of repose of yttrium oxide granulation-sintering particle is preferably below 48 degree and (contains 48 degree), is more preferably below 44 degree (to contain 44 degree), and best is (to contain 40 degree) below 40 degree.In addition, as mentioned above, along with the flowability of thermal spray powder descends, become unstable easily for the supply of the thermal spray powder of thermospray flame, occur the in uneven thickness of hot spray coating easily, or the anti-plasma etching of hot spray coating is inhomogeneous.
The thermal spray powder of the 1st example is used to the formation of the hot spray coating that plasma thermal sprayed or other hot spray processs carry out.Gaseous tension around when thermal spray powder is carried out plasma thermal sprayed is preferably normal atmosphere.In other words, it is better that thermal spray powder is used for the atmos plasma thermospray.When the surrounding gas pressure during plasma thermal sprayed is not normal atmosphere, particularly under the situation of decompression, the exporting isoionic anti-plasma etching for height and may descend slightly of resulting hot spray coating.With the thermal spray powder plasma thermal sprayed that reduces pressure, the reduction of the yttrium oxide in the prilling powder may appear in thermospray, and the lattice imperfection that causes anoxic appears and in result easily in hot spray coating.As mentioned above, because the etching meeting of the hot spray coating that plasma carried out the preferentially defect part from hot spray coating begins to carry out, therefore, compare with the formed hot spray coating of atmos plasma thermospray, it is relatively poor that the formed hot spray coating of decompression plasma thermal sprayed is exported isoionic anti-plasma etching to height.
For by the formed hot spray coating of the thermal spray powder of the 1st example, the void content less than 1% of hot spray coating, say less than 2% further, further say the words of less than 3%, because hot spray coating is too fine and close, by the unrelieved stress in the hot spray coating, hot spray coating may be stripped from easily.Therefore, the void content of hot spray coating is preferably and (is containing 1%) more than 1%, is more preferably (containing 2%) more than 2%, and best is (to contain 3%) more than 3%.
On the other hand, the void content of hot spray coating surpasses 15%, says further to surpass 12%, further says above 10%, height is exported isoionic anti-plasma etching descending slightly of hot spray coating may occur.This is because as implied above, the etching of the hot spray coating that plasma carried out the preferentially pore periphery from hot spray coating begins to carry out.In addition, the void content of hot spray coating may contain the perforation pore in the hot spray coating in the above range the time, therefore possibly can't fully prevent the etch damage of plasma to base material.Therefore, from improving the viewpoint that height is exported isoionic anti-plasma etching and prevented to connect pore of hot spray coating, the void content of hot spray coating is preferably and (is containing 15%) below 15%, be more preferably and (containing 12%) below 12%, best is (to contain 10%) below 10%.
According to the 1st example, can obtain following advantage.
The thermal spray powder of the 1st example is set at: the sintering of the prilling powder of making from raw material powder carries out atmosphere or oxygen, simultaneously, the median size that constitutes the primary particle of this yttrium oxide granulation-sintering particle is 0.5～1.5 μ m and is more than 1.11 times of median size (containing 1.11 times) of raw material powder.Therefore, the formed hot spray coating of the thermal spray powder of the 1st example is exported isoionic anti-plasma etching excellence to height.In other words, the suitable hot spray coating of height being exported isoionic anti-plasma etching excellence that forms of the thermal spray powder of the 1st example.
The 2nd example of the present invention below is described.
The thermal spray powder of the 2nd example is made of yttrium oxide granulation-sintering particle in fact.Yttrium oxide granulation-sintering particle, promptly the thermal spray powder of the 2nd example is by granulation-sintering process manufacturing.More specifically, be to make prilling powder from raw material powder, will pulverize behind this prilling powder sintering, further classification and making as required.
Raw material powder both can be a yttrium oxide powder, also can be the powder that can be converted to the material of yttrium oxide as the mixture of yttrium powder, yttrium hydroxide powder or these and yttrium oxide powder by granulation and sintering circuit.
The median size less than 2 μ m of raw material powder say less than 3 μ m further, and the hot spray coating that is obtained by thermal spray powder may descend slightly for the isoionic anti-plasma etching of low output.Therefore, from improving the viewpoint of hot spray coating for the isoionic anti-plasma etching of low high output, the median size of raw material powder (contains 2 μ m) better more than 2 μ m, be more preferably more than 3 μ m (to contain 3 μ m).In addition, along with reducing of the median size of raw material powder, the ratio that is tabular zone in the hot spray coating of tabular single crystal structure will uprise.Owing to contain more crystal defect in tabular zone, the etching meeting of the hot spray coating that plasma carried out the preferentially defect part from hot spray coating begins to carry out, therefore, the hot spray coating that tabular regional percentage is high is relatively poor to the isoionic anti-plasma etching of low output.
On the other hand, the median size of raw material powder surpasses 8 μ m, says further to surpass 7 μ m, hot spray coating may occur and descend slightly for the isoionic anti-plasma etching of low output.Therefore, from improving the viewpoint of hot spray coating for the isoionic anti-plasma etching of low output, the median size of raw material powder is preferably below 8 μ m and (contains 8 μ m), is more preferably below 7 μ m (to contain 7 μ m).In addition, along with the change of the median size of raw material powder is big, the width that tabular zone in the hot spray coating can occur becomes big.As mentioned above, owing to contain more crystal defect in tabular zone, the etching meeting of the hot spray coating that plasma carried out the preferentially defect part from hot spray coating begins to carry out, therefore, it is relatively poor to the isoionic anti-plasma etching of low output to contain the hot spray coating in tabular zone of big width.
Raw material powder is made as prilling powder, both can carries out mist projection granulating, also can directly raw material powder be made into prilling powder by rolling granulation or compression granulation by the slurry that raw material powder and suitable dispersant are formed.
In order to obtain the hot spray coating for the isoionic anti-plasma etching excellence of low output, the gas around during the sintering prilling powder is necessary for atmosphere or oxygen.Sintering prilling powder in the gas except that atmosphere and oxygen of argon gas and nitrogen etc. and the thermal spray powder that produces is difficult to form the hot spray coating for the isoionic anti-plasma etching excellence of low output.This be because, carry out agglomerating words with argon gas or nitrogen, the yttrium oxide that can occur in the prilling powder in sintering is reduced, the result can make the amount of the oxygen in the resulting thermal spray powder reduce.The lattice imperfection that the easy appearance of hot spray coating that is formed by the few thermal spray powder of oxygen level causes because of anoxic.Because the etching meeting of the hot spray coating that plasma carried out the preferentially defect part from hot spray coating begins to carry out, therefore, relatively poor by the few formed hot spray coating of thermal spray powder of oxygen level for the isoionic anti-plasma etching of low output.
During 1600 ℃ of gas top temperature (sintering temperature) less thaies around during the sintering prilling powder, say 1620 ℃ of less thaies further, further say 1650 ℃ of less thaies, hot spray coating may descend for the isoionic anti-plasma etching of low output.This is because along with the reduction of sintering temperature, it is insufficient to occur sintering easily.The inadequate words of sintering, the minimizing of the defect concentration that sintering produces is less, and what therefore obtain is the higher thermal spray powder of defect concentration.The hot spray coating that is formed by the higher thermal spray powder of defect concentration contains the defective that is caused by defective in the thermal spray powder easily.As mentioned above, because the etching meeting of the hot spray coating that plasma carried out the preferentially defect part from hot spray coating begins to carry out, therefore, relatively poor by the formed hot spray coating of the higher thermal spray powder of defect concentration to the isoionic anti-plasma etching of low output.In addition, the inadequate words of sintering, the powder feeding machine is to the course of conveying of thermal spraying machine, or in the thermospray flame, occurs the destruction of yttrium oxide granulation-sintering particle easily.Therefore, from improving the destructive viewpoint of hot spray coating for the low isoionic anti-plasma etching of output and inhibited oxidation yttrium granulation-sintering particle, sintering temperature is preferably and (is containing 1600 ℃) more than 1600 ℃, be more preferably and (containing 1620 ℃) more than 1620 ℃, best is (to contain 1650 ℃) more than 1650 ℃.
In addition, when sintering temperature surpasses 1800 ℃, say further to surpass 1770 ℃ that further say to surpass 1750 ℃, hot spray coating may descend for the isoionic anti-plasma etching of low output.This is because along with the rising of sintering temperature, it is excessive to occur sintering easily.Sintering over-drastic words are difficult to occur the softening or fusion of yttrium oxide granulation-sintering particle that thermospray flame brought.Therefore, fusion or not remollescent yttrium oxide granulation-sintering particle can not sneaked into hot spray coating, cause the density of hot spray coating to descend, make hot spray coating for the isoionic anti-plasma etching decline of low output.In addition, the softening or fusion of yttrium oxide granulation-sintering particle that thermospray flame is brought is difficult to carry out, and the deposit efficiency of thermal spray powder (thermospray qualification rate) also can descend.Therefore, from improving the viewpoint of hot spray coating for the deposit efficiency of low isoionic anti-plasma etching of output and raising thermal spray powder, sintering temperature is preferably and (is containing 1800 ℃) below 1800 ℃, be more preferably and (containing 1770 ℃) below 1770 ℃, best is (to contain 1750 ℃) below 1750 ℃.
The hold-time of the sintering temperature during the sintering prilling powder, (sintering time) less than was in the time of 12 minutes, said less than further 30 minutes, further said less than 1 hour, the particle growth that occurs primary particle easily is insufficient, occurs the destruction of yttrium oxide granulation-sintering particle easily.Therefore, for the destruction of inhibited oxidation yttrium granulation-sintering particle, sintering time is preferably and (is containing 12 minutes) more than 12 minutes, is more preferably (containing 30 minutes) more than 30 minutes, and best is (to contain 1 hour) more than 1 hour.
On the other hand, sintering time surpasses 30 hours, says further to surpass 20 hours, further says to surpass 10 hours, and the particle of primary particle is grown up and almost reached capacity, thereby does not have actual effect.Therefore, from the agglomerating actual effect, sintering time is preferably and (is containing 30 hours) below 30 hours, is more preferably (containing 20 hours) below 20 hours, and best is (to contain 10 hours) below 10 hours.
In order to obtain the hot spray coating for the isoionic anti-plasma etching excellence of low output, the median size that constitutes the primary particle of yttrium oxide granulation-sintering particle must (contain 3 μ m) more than 3 μ m.Less than 3 μ m are difficult to form the hot spray coating of exporting isoionic anti-plasma etching excellence for low by thermal spray powder.This is because along with reducing of the median size of the primary particle that constitutes yttrium oxide granulation-sintering particle, the ratio in tabular zone in the hot spray coating will uprise.As mentioned above, owing to contain more crystal defect in tabular zone, the etching meeting of the hot spray coating that plasma carried out the preferentially defect part from hot spray coating begins to carry out, therefore, the hot spray coating that tabular regional percentage is high is relatively poor to the isoionic anti-plasma etching of low output.
But, constitute the median size less than 4 μ m of the primary particle of yttrium oxide granulation-sintering particle, even more than 3 μ m, (contain 3 μ m), the ratio in tabular zone in the hot spray coating may be higher slightly, and hot spray coating the isoionic anti-plasma etching of low output is descended slightly appears in the possibility of result.Therefore, from improving the viewpoint for the isoionic anti-plasma etching of low output of hot spray coating, the median size that constitutes the primary particle of yttrium oxide granulation-sintering particle (contains 4 μ m) better more than 4 μ m.
In order to obtain the hot spray coating for the isoionic anti-plasma etching excellence of low output, the median size that constitutes the primary particle of yttrium oxide granulation-sintering particle must (contain 8 μ m) below 8 μ m.Surpass 8 μ m, thermal spray powder also is difficult to form the hot spray coating for the isoionic anti-plasma etching excellence of low output.This is because along with the increase of the median size of the primary particle that constitutes yttrium oxide granulation-sintering particle, the width in tabular zone in the hot spray coating will become big.As mentioned above, owing to contain more crystal defect in tabular zone, the etching meeting of the hot spray coating that plasma carried out the preferentially defect part from hot spray coating begins to carry out, therefore, the hot spray coating that contains tabular bigger zone of width is relatively poor to the isoionic anti-plasma etching of low output.
But, the median size that constitutes the primary particle of yttrium oxide granulation-sintering particle surpasses 7 μ m, even below 8 μ m, (contain 8 μ m), the width in tabular zone in the hot spray coating may be bigger than normal slightly, and the possibility of result hot spray coating occurs the isoionic anti-plasma etching of low output is descended slightly.Therefore, from improving the viewpoint for the isoionic anti-plasma etching of low output of hot spray coating, the median size that constitutes the primary particle of yttrium oxide granulation-sintering particle (contains 7 μ m) better below 7 μ m.
The median size less than 20 μ m of yttrium oxide granulation-sintering particle, say less than 22 μ m further, further say less than 25 μ m, say the words of less than 28 μ m more further, more thinner particle may be contained in yttrium oxide granulation-sintering particle, thereby the thermal spray powder of good fluidity may not be obtained.Therefore, in order to improve the flowability of thermal spray powder, the median size of yttrium oxide granulation-sintering particle is preferably more than 20 μ m and (contains 20 μ m), be more preferably more than 22 μ m and (contain 22 μ m), better is (to contain 25 μ m) more than 25 μ m, and best is (to contain 28 μ m) more than 28 μ m.In addition,, become unstable easily, occur the in uneven thickness of hot spray coating easily, or the anti-plasma etching of hot spray coating is inhomogeneous for the supply of the thermal spray powder of thermospray flame along with the flowability of thermal spray powder descends.
On the other hand, the median size of yttrium oxide granulation-sintering particle surpasses 60 μ m, say further and surpass 57 μ m, further say and surpass 55 μ m, say the words that surpass 52 μ m more further, yttrium oxide granulation-sintering particle that thermospray flame is brought may be difficult to fully softening or fusion, thereby may reduce the deposit efficiency of thermal spray powder.Therefore, in order to improve deposit efficiency, the median size of yttrium oxide granulation-sintering particle is preferably below 60 μ m and (contains 60 μ m), is more preferably below 57 μ m (to contain 57 μ m), better is (to contain 55 μ m) below 55 μ m, and best is (to contain 52 μ m) below 52 μ m.
The not enough 0.1cm of the cumulative volume of the pore that the diameter 6 μ m in yttrium oxide granulation-sintering particle are following
3/ g says not enough 0.11cm further
3/ g further says not enough 0.12cm
3/ g hot spray coating may occur and descend slightly for the isoionic anti-plasma etching of low output.Therefore, from improving the viewpoint for the isoionic anti-plasma etching of low output of hot spray coating, the cumulative volume of the pore that the diameter 6 μ m in yttrium oxide granulation-sintering particle are following is preferably at 0.1cm
3/ g is above (to contain 0.1cm
3/ g), be more preferably at 0.11cm
3/ g is above (to contain 0.11cm
3/ g), best is at 0.12cm
3/ g is above (to contain 0.12cm
3/ g).In addition, along with diminishing of the cumulative volume of the pore below the 6 μ m of the diameter in yttrium oxide granulation-sintering particle, the ratio that tabular zone in the hot spray coating can occur uprises.As mentioned above, owing to contain more crystal defect in tabular zone, the etching meeting of the hot spray coating that plasma carried out the preferentially defect part from hot spray coating begins to carry out, therefore, the higher hot spray coating of the ratio in tabular zone is relatively poor to the isoionic anti-plasma etching of low output.
The cumulative volume of the pore that the diameter 6 μ m in yttrium oxide granulation on the other hand ,-sintering particle are following surpasses 0.3cm
3/ g says to surpass 0.28cm further
3/ g further says to surpass 0.27cm
3/ g, the density of yttrium oxide granulation-sintering particle may descend, thereby may cause the density of the hot spray coating that is formed by thermal spray powder also to descend.Therefore, in order to improve the density of hot spray coating, the cumulative volume of the pore that the diameter 6 μ m in yttrium oxide granulation-sintering particle are following is preferably at 0.3cm
3/ g is following (to contain 0.3cm
3/ g), be more preferably at 0.28cm
3/ g is following (to contain 0.28cm
3/ g), best is at 0.27cm
3/ g is following (to contain 0.27cm
3/ g).In addition, because the void content height of the hot spray coating that density is low, the etching of the hot spray coating that plasma carried out the preferentially pore periphery from hot spray coating begins to carry out, so the high hot spray coating of void content is relatively poor for the isoionic anti-plasma etching of low output.
Peak less than 0.4 μ m in the diameter Distribution of the pore in yttrium oxide granulation-sintering particle, say less than 0.43 μ m further, further say less than 0.45 μ m, may the descending slightly of hot spray coating for the isoionic anti-plasma etching of low output.Therefore, from improving the viewpoint of hot spray coating for the isoionic anti-plasma etching of low output, peak in the diameter Distribution of the pore in yttrium oxide granulation-sintering particle is preferably more than 0.4 μ m and (contains 0.4 μ m), be more preferably more than 0.43 μ m and (contain 0.43 μ m), best is (to contain 0.45 μ m) more than 0.45 μ m.In addition, along with the step-down of the peak in the diameter Distribution of the pore in yttrium oxide granulation-sintering particle, the ratio regular meeting in tabular zone in the hot spray coating uprises.As mentioned above, owing to contain more crystal defect in tabular zone, and the etching meeting of the hot spray coating that plasma carried out preferentially the defect part from hot spray coating begin to carry out, therefore, the higher hot spray coating of the ratio in tabular zone is relatively poor to the isoionic anti-plasma etching of low output.
On the other hand, peak in the diameter Distribution of the pore in yttrium oxide granulation-sintering particle surpasses 4 μ m, say further and surpass 3.8 μ m, further say the words that surpass 3.7 μ m, the density that yttrium oxide granulation-sintering particle may occur descends, thereby causes the density by the formed hot spray coating of thermal spray powder also to descend.Therefore, in order to improve the density of hot spray coating, peak in the diameter Distribution of the pore in yttrium oxide granulation-sintering particle is preferably below 4 μ m and (contains 4 μ m), is more preferably below 3.8 μ m (to contain 3.8 μ m), and best is (to contain 3.7 μ m) below 3.7 μ m.In addition, as mentioned above, because the void content height of the hot spray coating that density is low, the etching of the hot spray coating that plasma carried out the preferentially pore periphery from hot spray coating begins to carry out, so the high hot spray coating of void content is relatively poor for the isoionic anti-plasma etching of low output.
The Bulk Specific Gravity of yttrium oxide granulation-sintering particle is better 0.8～1.4.Bulk Specific Gravity the phenomenon of splash (spitting) occurred being called as easily less than 0.8 o'clock when the thermal spray powder thermospray.So-called splash, be excessive fused thermal spray powder stores from the nozzle inner walls of thermal spraying machine come off, to the phenomenon of thermospray object ejection.Occur splash during thermospray, the film uniformity in the coat side of resulting hot spray coating and the homogeneity of tabular single crystal structure can descend, and the uniformity coefficient of anti-plasma etching also can descend.Why splash appears during the Bulk Specific Gravity less than 0.8 of yttrium oxide granulation-sintering particle easily, be because reducing along with the Bulk Specific Gravity of yttrium oxide granulation-sintering particle, because the effect of thermospray flame, the destruction of yttrium oxide granulation-sintering particle are easy to generate excessively fused micropartical.On the other hand, the Bulk Specific Gravity of yttrium oxide granulation-sintering particle surpasses 1.4, and the abundant of yttrium oxide granulation-sintering particle that may be difficult to occur being brought by thermospray flame softens or fusion, thereby may reduce the deposit efficiency of thermal spray powder.
The crushing strength of yttrium oxide granulation-sintering particle is preferably at 8～15MPa.Crushing strength is easy to generate splash less than 8MPa during the thermal spray powder thermospray.Why crushing strength is easy to generate splash less than the words of 8MPa, be because diminishing along with the crushing strength of yttrium oxide granulation-sintering particle, because the effect of thermospray flame, the destruction of yttrium oxide granulation-sintering particle are easy to generate excessively fused micropartical.On the other hand, the crushing strength of yttrium oxide granulation-sintering particle is greater than 15MPa, may be difficult to occur the fully softening or fusion of yttrium oxide granulation-sintering particle that thermospray flame brought, thereby may reduce the deposit efficiency of thermal spray powder.
The thermal spray powder of the 2nd example is used to the formation of the hot spray coating that plasma thermal sprayed or other hot spray processs carry out.Gaseous tension around when thermal spray powder is carried out plasma thermal sprayed is preferably normal atmosphere.In other words, it is better that thermal spray powder is used for the atmos plasma thermospray.When the gaseous tension around during plasma thermal sprayed is not normal atmosphere, particularly under the situation of decompression, may the descending slightly of resulting hot spray coating for the isoionic anti-plasma etching of low output.With the thermal spray powder plasma thermal sprayed that reduces pressure, the reduction of the yttrium oxide in the prilling powder may appear in thermospray, and the lattice imperfection that causes anoxic appears and in result easily in hot spray coating.As mentioned above, because the etching meeting of the hot spray coating that plasma carried out the preferentially defect part from hot spray coating begins to carry out, therefore, compare with the formed hot spray coating of atmos plasma thermospray, the formed hot spray coating of decompression plasma thermal sprayed is relatively poor to the isoionic anti-plasma etching of low output.
For by the formed hot spray coating of the thermal spray powder of the 2nd example, the void content less than 2% of hot spray coating, say less than 3% further, further say the words of less than 5%, because hot spray coating is too fine and close, by the unrelieved stress in the hot spray coating, hot spray coating may be stripped from easily.Therefore, the void content of hot spray coating is preferably and (is containing 2%) more than 2%, is more preferably (containing 3%) more than 3%, and best is (to contain 5%) more than 5%.
On the other hand, the void content of hot spray coating surpasses 17%, says further to surpass 15%, further says to surpass 10%, hot spray coating may occur the isoionic anti-plasma etching of low output is descended slightly.This is because as implied above, the etching of the hot spray coating that plasma carried out the preferentially pore periphery from hot spray coating begins to carry out.In addition, the void content of hot spray coating may contain the perforation pore in the hot spray coating in the above range the time, therefore possibly can't fully prevent the etch damage of plasma to base material.Therefore, from improving hot spray coating to the low viewpoint of exporting isoionic anti-plasma etching and preventing to connect pore, the void content of hot spray coating is preferably and (is containing 17%) below 17%, be more preferably and (containing 15%) below 15%, best is (to contain 10%) below 10%.
According to the 2nd example, can obtain following advantage.
The thermal spray powder of the 2nd example is set at: the sintering of the prilling powder that raw material powder is made carries out in atmosphere or oxygen, and simultaneously, the median size that constitutes the primary particle of this yttrium oxide granulation-sintering particle is in 3～8 mu m ranges.Therefore, the formed hot spray coating of the thermal spray powder of the 2nd example is to the isoionic anti-plasma etching excellence of low output.In other words, the suitable hot spray coating that forms the isoionic anti-plasma etching excellence of low output of the thermal spray powder of the 2nd example.
The the 1st and the 2nd example is also variable as follows.
Thermal spray powder also can contain the composition beyond yttrium oxide granulation-sintering particle.But the least possible words of the composition in the thermal spray powder beyond contained yttrium oxide granulation-sintering particle are better.
Yttrium oxide granulation-sintering particle also can contain the composition beyond the yttrium oxide.But the content of the yttrium oxide in yttrium oxide granulation-sintering particle is preferably and (is containing 90%) more than 90%, is more preferably (containing 95%) more than 95%, and best is (to contain 99%) more than 99%.There is no particular restriction for composition beyond the yttrium oxide in yttrium oxide granulation-sintering particle, but be preferably rare earth oxide.
Then embodiment and the comparative example to the 1st example describes.
Make the thermal spray powder of embodiment 1～11 and comparative example 1～4, yttrium oxide granulation-sintering particle that they form after by yttrium oxide powder (raw material powder) granulation and sintering constitutes.In addition, the hold-time of the top temperature during sintering is 2 hours.By being carried out plasma thermal sprayed, each thermal spray powder forms hot spray coating then.The details of thermal spray powder and hot spray coating is as shown in table 1, and the thermospray condition when forming hot spray coating (atmos plasma thermospray condition and decompression plasma thermal sprayed condition) is as shown in table 2.
In " the median size A of raw material powder " hurdle of table 1, the median size of the raw material powder of shown laser diffraction/each thermal spray powder that diffuse transmission type fineness mensuration machine " LA-300 " is measured that is to use hole field stock company of making institute.
In " constituting the median size B of the primary particle of granulation-sintering particle " hurdle of table 1, the median size of the primary particle of the formation yttrium oxide granulation-sintering particle of shown each thermal spray powder that is to use field emission scanning electronic microscope (FE-SEM) mensuration.Specifically be, from each thermal spray powder, select 10 yttrium oxide granulation-sintering particles arbitrarily, from 10 yttrium oxide granulation-sintering particles selecting, select 50 primary particles separately arbitrarily, for each thermal spray powder, measure to add up to 500 primary particle, the green diameter (Feret footpath) that shown is measures average.Green diameter is the distance of clamping between 2 imaginary lines that extend in parallel of particle.
In " B/A " hurdle of table 1, shown is constitutes the median size of primary particle of yttrium oxide granulation-sintering particle of this hot spray powder with respect to the ratio of the median size of the raw material powder of each thermal spray powder.
In " sintering gas " hurdle of table 1, shown is when being used to make each thermal spray powder, the kind of surrounding gas during raw material powder sintering after the granulation.
In " sintering temperature " hurdle of table 1, shown is when being used to make each thermal spray powder, the highest gas temperature in the sintering circuit of the raw material powder after the sintering granulation.
In " median size of granulation-sintering particle " hurdle of table 1, the median size of the yttrium oxide granulation-sintering particle of shown laser diffraction/each thermal spray powder that diffuse transmission type fineness mensuration machine " LA-300 " is measured that is to use hole field stock company of making institute.
In " cumulative volume of the pore that diameter 3 μ m are following " hurdle of table 1, the cumulative volume of the pore in the yttrium oxide granulation-sintering particle of each thermal spray powder that the shown forced porosity meter of the mercury that is to use stock company of Shimadzu Seisakusho Ltd. " Porosizer-9320 " is measured below the diameter 3 μ m (in per 1 gram yttrium oxide granulation-sintering particle).
In " peak in the pore diameter distribution " hurdle of table 1, the peak during pore diameter distributes in the yttrium oxide granulation-sintering particle of each thermal spray powder that shown being to use " Porosizer-9320 " measured.The pore diameter of measuring in yttrium oxide granulation-sintering particle distributes, and generally can obtain 2 peak values.Wherein the peak value that occurs of major diameter one side (for example about 10 μ m) stems from slit between yttrium oxide granulation-sintering particle rather than the pore in yttrium oxide granulation-sintering particle, and the peak value that minor axis one side occurs stems from the pore in yttrium oxide granulation-sintering particle.
In " Bulk Specific Gravity " hurdle of table 1, the Bulk Specific Gravity of the yttrium oxide granulation-sintering particle of each thermal spray powder that shown is measures according to JIS Z2504.
In " angle of repose " hurdle of table 1, the angle of repose of the yttrium oxide granulation-sintering particle of each thermal spray powder that the shown A.B.D powder characteristics mensuration machine " A.B.D-72 type " that is to use a well physics and chemistry to learn apparatus stock company is measured.
In " thermospray gas " hurdle of table 1, shown is be used to form hot spray coating each thermal spray powder is carried out plasma thermal sprayed the time gaseous tension.
Shown in " deposit efficiency " hurdle of table 1 is that the weight of the hot spray coating that forms behind each thermal spray powder of thermospray is with respect to ratio---the evaluation result of deposit efficiency of the weight of the thermal spray powder of thermospray use.In this hurdle, ◎ (excellent) expression deposit efficiency (is containing 50%) more than 50%, less than 50% that zero (very) expression (contains 40%) more than 40%, * (poor) expression less than 40%.
Shown in " density " hurdle of table 1 is evaluation result to the density of the hot spray coating that forms behind each thermal spray powder of thermospray.Particularly, at first each hot spray coating is used and orthogonal cut-out of its upper surface, this section is carried out mirror ultrafinish with the colloid silica of median size 6nm.Use the image analysis treatment unit " NSFJ1-A " of N-support company to measure void content then at the section of hot spray coating.In " density " hurdle, ◎ (excellent) expression void content less than 6%, zero (very) is illustrated in the less than 12% that (contains 6%) more than 6%, and * (poor) represented (to contain 12%) more than 12%.
Shown in " anti-plasma etching " hurdle of table 1 is evaluation result to the anti-plasma etching of the hot spray coating that forms behind each thermal spray powder of thermospray.Particularly, at first the colloid silica with median size 0.06 μ m carries out mirror ultrafinish to the surface of each hot spray coating, hot spray coating surface after covering part and grind with Kapton Tape is carried out plasma etching with the condition shown in the table 3 to the whole surface of hot spray coating afterwards.Use the difference of height determinator " Alpha-Step " of KLA-Tencor company to measure the part be covered and the difference of height between the part of not being covered then.In " anti-plasma etching " hurdle, above (containing 12nm/min) the not enough 14nm/min of ◎ (excellent) the expression not enough 12nm/min zero of difference of height (very) expression 12nm/min, * (poor) expression 14nm/min above (containing 14nm/min).
Table 1
Table 2
| ： ( A#40 ) Al ( A6061 ) ( 50mm×75m×5mm ) ：Paxair“SG-100” ：Paxair“Model 1264” ：50psi ( 0.34MPa ) ：50psi ( 0.34MPa ) ：37.0V ：900A ：120mm ：20g ： ( A#40 ) Al ( A6061 ) ( 50mm×75m×5mm ) ：Sulzer-Metco“F4” ：Sulzer-Metco“Twin10” ：42L/min ：10L/min ：43.0V ：620A ：200mm ：20g |
Table 3
| Etching system: Reactive Ion Etching device " NLD-800 " etching gas: the CF of ULVAC stock company 4Etchant gas flow: 0.054L/min combustion chamber pressure: 1Pa plasma output: 400W plasma irradiation area: diameter 200mm is for the plasma output of unit surface hot spray coating: 1.3W/cm 2Etching period: 1 hour |
As shown in table 1, in the hot spray coating of embodiment 1～11, be output as 1.3W/cm for the plasma of unit surface hot spray coating
2The isoionic anti-plasma etching of high-output power aspect, can obtain satisfying the actual result who uses.Relative therewith, the meltallizing epithelium of comparative example 1～4 then can not obtain the result that identical anti-plasma etching aspect can satisfy actual use.
Then embodiment and the comparative example to the 2nd example describes.
Make the thermal spray powder of embodiment 101～111 and comparative example 101～106, yttrium oxide granulation-sintering particle that they form after by yttrium oxide powder (raw material powder) granulation and sintering constitutes.In addition, the hold-time of the top temperature during sintering is 2 hours.By being carried out plasma thermal sprayed, each thermal spray powder forms hot spray coating then.The details of thermal spray powder and hot spray coating is as shown in table 4, and the thermospray condition when forming hot spray coating (atmos plasma thermospray condition and decompression plasma thermal sprayed condition) is as shown in table 5.
In " median size of raw material powder " hurdle of table 4, the median size of the raw material powder of shown laser diffraction/each thermal spray powder that diffuse transmission type fineness mensuration machine " LA-300 " is measured that is to use hole field stock company of making institute.
In " constituting the median size of the primary particle of granulation-sintering particle " hurdle of table 4, the median size of the primary particle of the formation yttrium oxide granulation-sintering particle of shown each thermal spray powder that is to use field emission scanning electronic microscope (FE-SEM) mensuration.Specifically be, from each thermal spray powder, select 10 yttrium oxide granulation-sintering particles arbitrarily, from 10 yttrium oxide granulation-sintering particles selecting, select 50 primary particles separately arbitrarily, for each thermal spray powder, measure to add up to 500 primary particle, the green diameter (Feret footpath) that shown is measures average.Green diameter is the distance of clamping between 2 imaginary lines that extend in parallel of particle.
In " sintering gas " hurdle of table 4, shown is when being used to make each thermal spray powder, the kind of the surrounding gas during raw material powder sintering after the granulation.
In " sintering temperature " hurdle of table 4, shown is when being used to make each thermal spray powder, upper air temperature degree in the sintering circuit of the raw material powder after the sintering granulation.
In " median size of granulation-sintering particle " hurdle of table 4, the median size of the yttrium oxide granulation-sintering particle of shown laser diffraction/each thermal spray powder that diffuse transmission type fineness mensuration machine " LA-300 " is measured that is to use hole field stock company of making institute.
In " cumulative volume of the pore that diameter 6 μ m are following " hurdle of table 4, the cumulative volume of the pore in the yttrium oxide granulation-sintering particle of each thermal spray powder that the shown forced porosity meter of the mercury that is to use stock company of Shimadzu Seisakusho Ltd. " Porosizer-9320 " is measured below the diameter 6 μ m (in per 1 gram yttrium oxide granulation-sintering particle).
In " peak in the pore diameter distribution " hurdle of table 4, the peak during pore diameter distributes in the yttrium oxide granulation-sintering particle of each thermal spray powder that shown being to use " Porosizer-9320 " measured.The pore diameter of measuring in yttrium oxide granulation-sintering particle distributes, and generally can obtain 2 peak values.Wherein the peak value that occurs of major diameter one side (for example about 10 μ m) stems from slit between yttrium oxide granulation-sintering particle rather than the pore in yttrium oxide granulation-sintering particle, and the peak value that minor axis one side occurs stems from the pore in yttrium oxide granulation-sintering particle.
In " Bulk Specific Gravity " hurdle of table 4, the Bulk Specific Gravity of the yttrium oxide granulation-sintering particle of each thermal spray powder that shown is measures according to JIS Z2504.
In " crushing strength " hurdle of table 4, the crushing strength σ [MPa] that shown is according to the yttrium oxide granulation-sintering particle of σ=each thermal spray powder that 2.8 * L/ π/d2 calculates.In the following formula, L represents critical load [N], and d represents the median size [mm] of the yttrium oxide granulation-sintering particle of each thermal spray powder.Critical load refers to, and when the compressive load that will increase with certain speed was applied to yttrium oxide granulation-sintering particle with pressure head, the displacement of pressure head was applied to the size of the compressive load on yttrium oxide granulation-sintering particle when increasing rapidly.What the mensuration of this critical load was used is the slight compression experimental installation " MCTE-500 " of stock company of Shimadzu Seisakusho Ltd..
In " thermospray gas " hurdle of table 4, shown is be used to form hot spray coating each thermal spray powder is carried out plasma thermal sprayed the time gaseous tension.
Shown in " deposit efficiency " hurdle of table 4 is that the weight of the hot spray coating that forms behind each thermal spray powder of thermospray is with respect to the ratio of the weight of the thermal spray powder that is used for thermospray---the evaluation result of deposit efficiency.In this hurdle, ◎ (excellent) expression deposit efficiency (is containing 50%) more than 50%, less than 50% that zero (very) expression (contains 40%) more than 40%, * (poor) expression less than 40%.
Shown in " density " hurdle of table 4 is evaluation result to the density of the hot spray coating that forms behind each thermal spray powder of thermospray.Particularly, at first each hot spray coating is used and orthogonal cut-out of its upper surface, this section is carried out mirror ultrafinish with the colloid silica of median size 6nm.Use the image analysis treatment unit " NSFJ1-A " of N-support company to measure void content then at the section of hot spray coating.In " density " hurdle, less than 12% that the expression of ◎ (excellent) expression void content less than 6%, zero (very) (contains 6%) more than 6%, * (poor) expression (contains 12%) more than 12%.
Shown in " anti-plasma etching " hurdle of table 4 is evaluation result to the anti-plasma etching of the hot spray coating that forms behind each thermal spray powder of thermospray.Particularly, at first the colloid silica with median size 0.06 μ m carries out mirror ultrafinish to the surface of each hot spray coating, hot spray coating surface after covering part and grind with Kapton Tape is carried out plasma etching with the condition shown in the table 6 to the whole surface of hot spray coating afterwards.Use the difference of height determinator " Alpha-Step " of KLA-Tencor company to measure the part be covered and the difference of height between the part of not being covered then.In " anti-plasma etching " hurdle, the not enough 280nm of ◎ (excellent) expression difference of height, above (containing 280nm) the not enough 320nm of zero (very) expression 280nm, * (poor) expression 320nm above (containing 320nm).
Table 4
Table 5
| ： ( A#40 ) Al ( A6061 ) ( 50mm×75m×5mm ) ：Paxair“SG-100” ：Paxair“Model 1264” ：50psi ( 0.34MPa ) ：50psi ( 0.34MPa ) ：37.0V ：900A ：120mm ：20g ： ( A#40 ) Al ( A6061 ) ( 50mm×75m×5mm ) ：Sulzer-Metco“F4” ：Sulzer-Metco“Twin10” ：42L/min ：10L/min ：43.0V ：620A ：200mm ：20g |
Table 6
| Etching system: Reactive Ion Etching device " RIE-200 " etching gas: the CF of Samco stock company 4Etchant gas flow: 0.054L/min combustion chamber pressure: 5Pa plasma output: 100W plasma irradiation area: diameter 200mm is for the plasma output of unit surface hot spray coating: 0.3W/cm 2Etching period: 8 hours |
As shown in table 4, in the hot spray coating of embodiment 101～111, be output as 0.3W/cm for the plasma of unit surface hot spray coating
2The isoionic anti-plasma etching of low output aspect, can obtain satisfying the actual result who uses.Relative therewith, the hot spray coating of comparative example 101～106 then can not obtain the result that identical anti-plasma etching aspect can satisfy actual use.
Claims (12)
1. thermal spray powder, contain raw material powder granulation and sintering obtains in atmosphere or oxygen yttrium oxide granulation-sintering particle, the median size that constitutes the primary particle of described yttrium oxide granulation-sintering particle is 0.5～1.5 μ m and more than or equal to 1.11 times of the median size of described raw material powder.
2. thermal spray powder as claimed in claim 1 is characterized in that, the median size of described yttrium oxide granulation-sintering particle is 20～60 μ m.
3. thermal spray powder as claimed in claim 1 or 2 is characterized in that, the cumulative volume of the pore of diameter below 3 μ m in described yttrium oxide granulation-sintering particle is smaller or equal to 0.2cm
3/ g.
4. thermal spray powder as claimed in claim 1 or 2 is characterized in that, the diameter Distribution of the pore in described yttrium oxide granulation-sintering particle has peak value in 0.06～2 mu m range.
5. thermal spray powder as claimed in claim 1 or 2 is characterized in that, the Bulk Specific Gravity of described yttrium oxide granulation-sintering particle is more than or equal to 1.2.
6. thermal spray powder contains raw material powder granulation and sintering obtains in atmosphere or oxygen yttrium oxide granulation-sintering particle, and the median size that constitutes the primary particle of described yttrium oxide granulation-sintering particle is 3～8 μ m.
7. thermal spray powder as claimed in claim 6 is characterized in that, the median size of described yttrium oxide granulation-sintering particle is 20～60 μ m.
8. as claim 6 or 7 described thermal spray powders, it is characterized in that the cumulative volume of the pore of diameter below 6 μ m in described yttrium oxide granulation-sintering particle is 0.1～0.3cm
3/ g.
9. as claim 6 or 7 described thermal spray powders, it is characterized in that the diameter Distribution of the pore in described yttrium oxide granulation-sintering particle has peak value in 0.4～4 mu m range.
10. as claim 6 or 7 described thermal spray powders, it is characterized in that the Bulk Specific Gravity of described yttrium oxide granulation-sintering particle is 0.8～1.4.
11., it is characterized in that thermal spray powder is used to form hot spray coating by the atmos plasma thermospray as claim 1,2,6 or 7 described thermal spray powders.
12. the formation method of a hot spray coating contains and will form the operation of hot spray coating by the atmos plasma thermospray as claim 1,2,6 or 7 described thermal spray powders.
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| JP2005289173A JP4981292B2 (en) | 2005-09-30 | 2005-09-30 | Thermal spray powder and method of forming thermal spray coating |
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| JP2005289172A JP4981291B2 (en) | 2005-09-30 | 2005-09-30 | Thermal spray powder and method of forming thermal spray coating |
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| Publication number | Publication date |
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| CN1940119B (en) | 2010-09-22 |
| JP2007100140A (en) | 2007-04-19 |
| JP4981291B2 (en) | 2012-07-18 |
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