TWI845233B - Tool material for firing - Google Patents
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- TWI845233B TWI845233B TW112111849A TW112111849A TWI845233B TW I845233 B TWI845233 B TW I845233B TW 112111849 A TW112111849 A TW 112111849A TW 112111849 A TW112111849 A TW 112111849A TW I845233 B TWI845233 B TW I845233B
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- 239000000463 material Substances 0.000 title claims abstract description 54
- 238000010304 firing Methods 0.000 title claims abstract description 36
- 239000010410 layer Substances 0.000 claims abstract description 159
- 239000000758 substrate Substances 0.000 claims abstract description 50
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002344 surface layer Substances 0.000 claims abstract description 39
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 38
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 18
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 10
- VIJYFGMFEVJQHU-UHFFFAOYSA-N aluminum oxosilicon(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Si+2]=O VIJYFGMFEVJQHU-UHFFFAOYSA-N 0.000 claims abstract description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000292 calcium oxide Substances 0.000 claims abstract description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 5
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003381 stabilizer Substances 0.000 claims abstract description 5
- 229910052849 andalusite Inorganic materials 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 55
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 26
- 238000007667 floating Methods 0.000 abstract description 16
- 239000002223 garnet Substances 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 23
- 239000001301 oxygen Substances 0.000 description 23
- 229910052760 oxygen Inorganic materials 0.000 description 23
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 20
- 229910052710 silicon Inorganic materials 0.000 description 19
- 239000010703 silicon Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000377 silicon dioxide Substances 0.000 description 15
- 235000012239 silicon dioxide Nutrition 0.000 description 15
- 239000002994 raw material Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 9
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- 238000005507 spraying Methods 0.000 description 8
- 229910052681 coesite Inorganic materials 0.000 description 7
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- 229910052905 tridymite Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007750 plasma spraying Methods 0.000 description 4
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- 239000007789 gas Substances 0.000 description 3
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- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101001121408 Homo sapiens L-amino-acid oxidase Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 102100026388 L-amino-acid oxidase Human genes 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 101100012902 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) FIG2 gene Proteins 0.000 description 1
- 101100233916 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) KAR5 gene Proteins 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
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- 229910052863 mullite Inorganic materials 0.000 description 1
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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Abstract
本發明提供一種燒製用道具材料，即使重複使用於燒製亦能抑制表面氧化矽的浮上，因此對燒製後的製品中的品質的影響較小，再者可以較以往更高速的條件來燒製。本發明提供一種燒製用道具材料，係於由碳化矽所構成之基材以及前述基材的表面中之至少載置被燒製物之部分依序形成有：氧化膜；底層，係以富鋁紅柱石為主成分的氧化鋁的總含量為65質量%以上至95質量%以下之氧化鋁-氧化矽材質，且厚度為1μm以上至30μm以下；中間層，係氧化鋁為95質量%以上至99.9質量%以下，且厚度為1μm以上至30μm以下；以及表面層，係由將氧化鈣或者氧化釔作為穩定劑的穩定化氧化鋯所構成，且厚度為1μm以上至30μm以下；前述底層、前述中間層以及前述表面層的孔隙率均為5%以下。 The present invention provides a firing tool material which can suppress the floating of surface silicon oxide even when repeatedly used for firing, thereby having less impact on the quality of the fired product, and can be fired at a higher speed than before. The present invention provides a material for a tool for firing, wherein an oxide film is sequentially formed on a substrate composed of silicon carbide and at least a portion of the surface of the substrate on which the fired object is placed: a bottom layer, which is an aluminum oxide-silicon oxide material with a total aluminum oxide content of 65% to 95% by mass and rich aluminum garnet as the main component, and a thickness of 1μm to 30μm; an intermediate layer, which is an aluminum oxide content of 95% to 99.9% by mass and a thickness of 1μm to 30μm; and a surface layer, which is composed of stabilized zirconium oxide using calcium oxide or yttrium oxide as a stabilizer and a thickness of 1μm to 30μm; the porosity of the bottom layer, the intermediate layer and the surface layer is all less than 5%.
Description
本發明係有關於一種燒製用道具材料，例如有關於固定器(setter)、棚架板、匣鉢(saggar)等燒製用道具材料。 The present invention relates to a baking prop material, such as a setter, a shelf board, a saggar, etc.
從前，將被燒製物載置於燒製用道具並進行被燒製物的燒製、熱處理。氧化鋁-氧化矽質、氧化鋁-氧化矽-氧化鎂質、氧化鎂-氧化鋁-氧化鋯質、碳化矽質等耐熱性優異的陶瓷材料使用於此燒製用道具材料。特別是，碳化矽質的陶瓷材料因耐熱強度及抗潛變性(creep resistance)優異，故為較佳的材料。 In the past, the fired object was placed on a firing tool and fired and heat-treated. Ceramic materials with excellent heat resistance such as alumina-silicon oxide, alumina-silicon oxide-magnesium oxide, magnesium oxide-alumina-zirconia, and silicon carbide are used as the firing tool material. In particular, silicon carbide ceramic materials are preferred because of their excellent heat resistance and creep resistance.
此外，燒製用道具材料的基材係由碳化矽所構成，氧化鋁層或氧化鋯層形成於此基材的表面之技術亦為人所知。 In addition, the substrate of the material of the tool for firing is made of silicon carbide, and the technology of forming an aluminum oxide layer or a zirconium oxide layer on the surface of this substrate is also known.
例如，專利文獻1揭示有一種碳化矽質燒製用道具材料，碳化矽質基材的表觀孔隙率(apparent porosity)為20%以上且表觀比重為3.20以下，二氧化矽層形成於前述碳化矽質基材表層的碳化矽結晶表面，而且在前述碳化矽質基材的至少載置被燒製物之部分被覆有ZrO2(二氧化鋯)及Al2O3(氧化鋁)中的至少一者。
For example,
由於將如前述般的表面設有多層構造的碳化矽作為基材的燒製用道具材料的機械性質及熱性質的特性優異，因此可謀求薄壁化、長壽命化。再者，藉由二氧化矽層預先形成於基材的表面，可改善因碳化矽基材的氧化反 應等對爐內氛圍(atmosphere)的影響、被覆層的剝離、被燒製物的變色等燒結異常等缺點。 Since the mechanical and thermal properties of the firing tool material using silicon carbide with a multi-layer structure on the surface as described above as the base material are excellent, thinning and long life can be achieved. Furthermore, by forming a silicon dioxide layer on the surface of the base material in advance, it is possible to improve the shortcomings of sintering abnormalities such as the influence of the oxidation reaction of the silicon carbide base material on the furnace atmosphere, the peeling of the coating layer, and the discoloration of the fired product.
順便一提，在二氧化矽層預先形成於碳化矽基材表面時，因重複使用導致來自前述二氧化矽層的矽及氧逐漸地浮上至氧化鋯被覆層表面且沒多久會露出。而且，前述矽及氧係與在此道具材料上所載置的被燒製物反應，有導致使電子零件燒製中的良率降低的缺點之虞。因此，如上所述的碳化矽質的道具材料較佳為即使重複使用也可抑制來自基材(二氧化矽層)的矽及氧的浮上且不會產生與被燒製物的反應之構成。 By the way, when a silicon dioxide layer is formed on the surface of a silicon carbide substrate in advance, silicon and oxygen from the silicon dioxide layer gradually float to the surface of the zirconia coating layer due to repeated use and are exposed soon. Moreover, the silicon and oxygen react with the fired object placed on this tool material, which may lead to a disadvantage of reducing the yield of electronic parts firing. Therefore, the silicon carbide tool material as described above is preferably a structure that can suppress the floating of silicon and oxygen from the substrate (silicon dioxide layer) even if it is repeatedly used and does not react with the fired object.
關於此點，專利文獻2記載有：在形成氧化覆膜(氧化矽層)的碳化矽基材的表面形成以富鋁紅柱石(mullite)為主成分且厚度為30μm至300μm的底層，在底層上形成由穩定的氧化鋯所構成的表面層，藉此抑制來自碳化矽基材(氧化矽層)的矽及氧浮上至氧化鋯質表面層，且即使重複使用也謀求長壽命化。 In this regard, Patent Document 2 states that: a base layer with a thickness of 30μm to 300μm and containing aluminum-rich mullite as the main component is formed on the surface of a silicon carbide substrate on which an oxide film (silicon oxide layer) is formed, and a surface layer composed of stable zirconia is formed on the base layer, thereby suppressing silicon and oxygen from the silicon carbide substrate (silicon oxide layer) from floating up to the zirconia surface layer, and extending the life even if it is repeatedly used.
另外，專利文獻3記載有一種燒製用道具材料，將燒製物載置並跟前述被燒製物一起收容於燒製爐內，前述燒製用道具材料由碳化矽燒結體所構成，富鋁紅柱石、氧化鋁、氧化鋯的各層係以電漿熔射法等進一步地形成於至少載置被燒製物之部分的碳化矽燒結體的表面的SiO2(二氧化矽層)層。 In addition, Patent Document 3 describes a firing tool material, which places a fired object and is housed in a firing furnace together with the fired object. The firing tool material is composed of a silicon carbide sintered body, and each layer of aluminum-rich andalusite, aluminum oxide, and zirconium oxide is further formed by plasma spraying or the like on the surface of the silicon carbide sintered body at least at a portion where the fired object is placed. A SiO 2 (silicon dioxide layer) layer is formed.
再者，專利文獻3記載有：富鋁紅柱石、氧化鋁、氧化鋯的各層由於越薄則熱膨脹的影響越小，因此較佳為儘量減薄，氧化鋯膜的膜厚為10μm至200μm左右、富鋁紅柱石膜的膜厚為10μm至200μm左右、氧化鋁膜的膜厚為10μm至200μm左右。 Furthermore, Patent Document 3 states that the thinner the layers of andalusite, aluminum oxide, and zirconium oxide are, the smaller the effect of thermal expansion is, so it is better to reduce the thickness as much as possible. The thickness of the zirconium oxide film is about 10μm to 200μm, the thickness of the andalusite film is about 10μm to 200μm, and the thickness of the aluminum oxide film is about 10μm to 200μm.
[先前技術文獻] [Prior Art Literature]
[專利文獻] [Patent Literature]
[專利文獻1]日本特開2006-117472號公報。 [Patent Document 1] Japanese Patent Publication No. 2006-117472.
[專利文獻2]日本特開2009-234817號公報。 [Patent Document 2] Japanese Patent Publication No. 2009-234817.
[專利文獻3]日本特開2019-11238號公報。 [Patent Document 3] Japanese Patent Publication No. 2019-11238.
順便一提，如上所述，在專利文獻1所記載的發明中，在碳化矽基材表面預先形成二氧化矽層(氧化矽層)時，因重複使用導致來自前述二氧化矽層(氧化矽層)的矽及氧逐漸地向氧化鋯被覆層表面的方向浮上且沒多久會露出於表面。而且，存在下述課題：前述矽及氧係與在此道具材料上所載置的被燒製物反應，導致使被燒製體的良率降低。
By the way, as mentioned above, in the invention described in
此外，在專利文獻2所記載的發明中存在下述課題：由於形成於基板上的膜較厚，厚度為30μm至300μm，且熱容量較大，因此不適於更高速化的燒製製程。 In addition, the invention described in Patent Document 2 has the following problem: Since the film formed on the substrate is relatively thick, with a thickness of 30μm to 300μm, and has a large heat capacity, it is not suitable for a higher-speed firing process.
再者，如專利文獻3所記載的發明存在下述課題：即使在具有依序形成於基材表面的氧化膜、中間層(底層)以及表面層的燒製用道具材料中，矽及氧也會通過中間層及表面層並與所載置的被燒製物反應，從而使良率降低。亦即，存在下述課題：若將疊層於基材上的各種層的厚度變薄，則雖然可改善溫度隨從性，然而難以得到抑制來自形成於基材的SiO2層之矽及氧的浮上之功效。 Furthermore, the invention described in Patent Document 3 has the following problem: even in a firing tool material having an oxide film, an intermediate layer (bottom layer), and a surface layer sequentially formed on the surface of a substrate, silicon and oxygen pass through the intermediate layer and the surface layer and react with the fired product placed thereon, thereby reducing the yield. In other words, there is the following problem: if the thickness of the various layers stacked on the substrate is reduced, although the temperature compliance can be improved, it is difficult to obtain the effect of suppressing the floating of silicon and oxygen from the SiO2 layer formed on the substrate.
本發明係有鑑於上述課題而研創，目的在於提供一種溫度隨從性 優異且充分抑制矽及氧的浮上之碳化矽質的燒製用道具材料。 This invention was developed in view of the above-mentioned problem, and its purpose is to provide a tool material for firing silicon carbide that has excellent temperature compliance and fully suppresses the floating of silicon and oxygen.
本發明的特徵在於：具備氧化膜、底層、中間層以及表面層；前述氧化膜係形成於由碳化矽所構成的基材的表面中之至少載置被燒製物之部分；前述底層係形成於前述氧化膜的表面，且為以富鋁紅柱石為主成分的氧化鋁的總含量為65質量%以上至95質量%以下之氧化鋁-氧化矽質，且厚度為1μm以上至30μm以下；前述中間層係形成於前述底層的表面，氧化鋁為95質量%以上至99.9質量%以下，且厚度為1μm以上至30μm以下；前述表面層係形成於前述中間層的表面，由將氧化鈣或氧化釔作為穩定劑的穩定化氧化鋯所構成，且厚度為1μm以上至30μm以下；前述底層、前述中間層及前述表面層的孔隙率均為5%以下。 The invention is characterized in that: it has an oxide film, a bottom layer, an intermediate layer and a surface layer; the oxide film is formed on at least a portion of the surface of a substrate composed of silicon carbide where a fired product is placed; the bottom layer is formed on the surface of the oxide film and is an aluminum oxide-silicon oxide material in which the total content of aluminum oxide containing aluminum-rich andalusite as a main component is 65 mass % or more and 95 mass % or less, and the thickness is 1 μm or more and 30 μm or less; The intermediate layer is formed on the surface of the bottom layer, and the aluminum oxide is 95 mass% or more and 99.9 mass% or less, and the thickness is 1 μm or more and 30 μm or less; the surface layer is formed on the surface of the intermediate layer, and is composed of stabilized zirconium oxide using calcium oxide or yttrium oxide as a stabilizer, and the thickness is 1 μm or more and 30 μm or less; the porosity of the bottom layer, the intermediate layer and the surface layer is less than 5%.
其中，前述氧化膜較佳為SiO2層。此外，至少載置被燒製物之部分的基材的厚度較佳為1.5mm以上至4mm以下。 The oxide film is preferably a SiO 2 layer. In addition, the thickness of at least the portion of the substrate on which the fired product is placed is preferably 1.5 mm to 4 mm.
藉由具有相關的構成，可作為溫度隨從性優異且充分抑制矽及氧的浮上之碳化矽質的燒製用道具材料。 By having such a structure, it can be used as a tool material for firing silicon carbide that has excellent temperature compliance and fully suppresses the floating of silicon and oxygen.
根據本發明，相較於先前技術，不需要採用較為複雜的構造或製造方法，可提供溫度隨從性優異且充分抑制矽及氧的浮上之碳化矽質的燒製用道具材料。 According to the present invention, compared with the prior art, there is no need to adopt a more complicated structure or manufacturing method, and a tool material for firing of silicon carbide with excellent temperature compliance and sufficient suppression of the floating of silicon and oxygen can be provided.
1:底層 1: Bottom layer
2:中間層 2: Middle layer
3:表面層 3: Surface layer
D:深度 D: Depth
L:界面 L: Interface
L1:潛入寬度 L1: Diving width
L2:潛入寬度 L2: Diving width
S1:一端部 S1: one end
S2:另一端部 S2: The other end
X:基準線 X: Baseline
W:寬度 W: Width
Z:基材 Z: Base material
[圖1]係用以說明侵入部的剖面圖(省略中間層、表面層)。 [Figure 1] is a cross-sectional view used to illustrate the intrusion part (the middle layer and surface layer are omitted).
[圖2]係顯示在底層、中間層形成有侵入部的狀態之剖面圖(省略表面層)。 [Figure 2] is a cross-sectional view showing a state where an intrusion portion is formed in the bottom layer and the middle layer (the surface layer is omitted).
[圖3]係用以說明潛入部的剖面圖(省略表面層)。 [Figure 3] is a cross-sectional view used to illustrate the submerged part (surface layer omitted).
[圖4]係用以說明表面層潛入至中間層之潛入部的剖面圖。 [Figure 4] is a cross-sectional view used to illustrate the penetration of the surface layer into the middle layer.
以下，說明本發明的實施形態。 The following describes the implementation of the present invention.
本發明的特徵在於：具備氧化膜、底層、中間層以及表面層；前述氧化膜係形成於由碳化矽所構成的基材的表面中之至少載置被燒製物之部分；前述底層係形成於前述氧化膜的表面，且為以富鋁紅柱石為主成分的氧化鋁的總含量為65質量%以上至95質量%以下之氧化鋁-氧化矽質，厚度為1μm以上至30μm以下；前述中間層係形成於前述底層的表面，氧化鋁為95質量%以上至99.9質量%以下，厚度為1μm以上至30μm以下；前述表面層係形成於前述中間層的表面，由將氧化鈣或氧化釔作為穩定劑的穩定化氧化鋯所構成，厚度為1μm以上至30μm以下；前述底層、前述中間層及前述表面層的孔隙率均為5%以下。 The invention is characterized in that: it has an oxide film, a bottom layer, an intermediate layer and a surface layer; the oxide film is formed on at least a portion of the surface of a substrate composed of silicon carbide where a fired product is placed; the bottom layer is formed on the surface of the oxide film and is an aluminum oxide-silicon oxide material with a total aluminum oxide content of 65 mass % or more and 95 mass % or less of aluminum oxide having aluminum-rich andalusite as a main component, and a thickness of 1 μm or more and 30 μm or less; The intermediate layer is formed on the surface of the bottom layer, and the aluminum oxide is 95% to 99.9% by mass, and the thickness is 1μm to 30μm; the surface layer is formed on the surface of the intermediate layer, and is composed of stabilized zirconium oxide using calcium oxide or yttrium oxide as a stabilizer, and the thickness is 1μm to 30μm; the porosity of the bottom layer, the intermediate layer, and the surface layer is less than 5%.
首先，本發明的基材係由碳化矽所形成。作為前述本發明的基材，例如如專利文獻1至3所記載可舉例包含碳化矽與不可避免雜質(無法避免的雜質)的燒結體。
First, the substrate of the present invention is formed of silicon carbide. As the substrate of the present invention, for example, a sintered body containing silicon carbide and inevitable impurities (unavoidable impurities) can be cited as described in
此外，作為本發明的基材，只要可用作燒製用道具材料的碳化矽即可，不需要具備特別的條件等的碳化矽。 In addition, as the substrate of the present invention, any silicon carbide that can be used as a material for a firing tool is sufficient, and silicon carbide that meets special conditions is not required.
本發明在至少載置被燒製物之部分的碳化矽燒結體的表面形成有氧化膜(由SiO2所構成的膜)。 In the present invention, an oxide film (a film composed of SiO 2 ) is formed on the surface of at least the portion of the silicon carbide sintered body on which the sintered product is placed.
如此，藉由在碳化矽燒結體的表面形成有氧化膜(由SiO2所構成的膜)，可抑制基材(碳化矽)的氧化，並且可抑制隨著基材(碳化矽)氧化而來的燒製爐內的氧濃度的變化。再者，藉由經由氧化膜(由SiO2所構成的膜)，也提高碳化矽燒結體的表面與底層之間的密著性。 Thus, by forming an oxide film (film composed of SiO2 ) on the surface of the silicon carbide sintered body, oxidation of the substrate (silicon carbide) can be suppressed, and changes in oxygen concentration in the sintering furnace caused by oxidation of the substrate (silicon carbide) can be suppressed. Furthermore, by passing through the oxide film (film composed of SiO2 ), the adhesion between the surface of the silicon carbide sintered body and the underlying layer is also improved.
其中，載置被燒製物之部分係指包括被燒製物直接接觸的部位與其周邊區域。此種被燒製物直接接觸的部位與其周邊區域係意味著燒製用燒結體的一個主表面的一部分，然而並不限制於此，亦可為一個主表面整體。此外，只要沒有特別的問題，氧化膜亦可形成於燒製用道具材料的整個表面。 The portion on which the fired object is placed refers to the portion directly contacted by the fired object and its surrounding area. Such portion directly contacted by the fired object and its surrounding area means a portion of a main surface of the fired body, but it is not limited to this and may also be the entire main surface. In addition, as long as there is no special problem, the oxide film may also be formed on the entire surface of the firing tool material.
此氧化膜係由SiO2所構成的膜，可在大氣、氧、含氧的混合氣體中的任一氣體氛圍下以800℃以上至1600℃以下加熱，藉此將基材表面氧化而形成。 This oxide film is a film composed of SiO2 and can be formed by oxidizing the surface of the substrate by heating at a temperature of 800°C to 1600°C in an atmosphere of any one of air, oxygen, and a mixed gas containing oxygen.
作為前述氧化膜的形成方法，只要得到所需要的膜厚及緊密度，即可應用前述方法之外的方法。 As a method for forming the aforementioned oxide film, as long as the required film thickness and density are obtained, methods other than the aforementioned method may be applied.
此外，氧化膜的膜厚並未特別限定，然而較佳為0.5μm以上至1.5μm以下的範圍。氧化膜的膜厚若小於0.5μm，則無法得到抑制基材(碳化矽)的氧化的功效。另一方面，氧化膜的膜厚若超過1.5μm，則功效大致相同，反而有因熱膨脹率差所產生的應力而產生裂縫之虞。 In addition, the thickness of the oxide film is not particularly limited, but is preferably in the range of 0.5μm to 1.5μm. If the thickness of the oxide film is less than 0.5μm, the effect of suppressing the oxidation of the substrate (silicon carbide) cannot be obtained. On the other hand, if the thickness of the oxide film exceeds 1.5μm, the effect is roughly the same, and there is a risk of cracks due to stress caused by the difference in thermal expansion coefficient.
前述氧化膜之上具備底層、中間層及表面層；前述底層係以富鋁紅柱石為主成分的氧化鋁的總含量為65質量%以上至95質量%以下之氧化鋁-氧化矽質，厚度為1μm以上至30μm以下；前述中間層係形成於前述底層的表面，氧化鋁為95質量%以上至99.9質量%以下，厚度為1μm以上至30μm以下；前述表面層係形成於前述中間層的表面，由將氧化鈣或氧化釔作為穩定劑的穩定化氧 化鋯所構成，厚度為1μm以上至30μm以下。 The oxide film has a bottom layer, an intermediate layer and a surface layer; the bottom layer is an aluminum oxide-silicon oxide with a total aluminum oxide content of 65% to 95% by mass and rich aluminum garnet as the main component, and a thickness of 1μm to 30μm; the intermediate layer is formed on the surface of the bottom layer, and the aluminum oxide content is 95% to 99.9% by mass, and the thickness is 1μm to 30μm; the surface layer is formed on the surface of the intermediate layer, and is composed of stabilized zirconium oxide with calcium oxide or yttrium oxide as a stabilizer, and the thickness is 1μm to 30μm.
在本發明中，前述底層係用以抑制來自由碳化矽所構成的基材的矽及氧的浮上，中間層係用以緩和由碳化矽所構成的基材與由氧化鋯質所構成的表面層之間的熱膨脹差所產生的應力，表面層係與被燒製物之反應性較低的材料(氧化鋯)。 In the present invention, the bottom layer is used to suppress the floating of silicon and oxygen from the substrate composed of silicon carbide, and the middle layer is used to alleviate the stress generated by the thermal expansion difference between the substrate composed of silicon carbide and the surface layer composed of zirconia. The surface layer is a material (zirconia) with low reactivity with the sintered object.
本發明的第一特徵在於：將底層、中間層、表面層的各層厚度設為1μm以上至30μm以下。尤其相對於專利文獻2中將前述各層厚設為30μm以上至300μm以下(較佳為50μm以上至250μm以下)，本發明中設為較薄，於此點有所不同。 The first feature of the present invention is that the thickness of each layer of the base layer, the intermediate layer, and the surface layer is set to be greater than 1μm and less than 30μm. In particular, compared with the thickness of each layer set to be greater than 30μm and less than 300μm (preferably greater than 50μm and less than 250μm) in Patent Document 2, the thickness of each layer in the present invention is set to be thinner, which is different in this respect.
由於相較於先前技術的膜厚，形成於基材上的底層、中間層、表面層的各層厚度較薄，因此使各層各自的熱容量下降，投入燒製爐並升溫時即使升溫速度較以往更高也不容易產生龜裂。此處所謂的較以往更高速的升溫速度係指較佳為1100℃/分以上。 Compared with the film thickness of the previous technology, the thickness of the bottom layer, middle layer, and surface layer formed on the substrate is thinner, so the heat capacity of each layer is reduced, and it is not easy to produce cracks even if the heating rate is higher than before when it is put into the firing furnace and heated. Here, the faster heating rate than before means preferably above 1100℃/min.
各層厚若超過30μm，則各層各自的熱容量上升，經過以本發明中的升溫速度的重複導致龜裂及裂縫的產生，而無法耐受使用。僅從熱容量的觀點來看，雖然各層厚度越薄越佳，然而若低於1μm，則因為強度及耐久性根本不足以及以如此薄度來進行均勻的製膜使製造成本上升等理由故不佳。本發明的底層、中間層、表面層的各層厚度較佳為5μm以上至25μm以下。 If the thickness of each layer exceeds 30μm, the heat capacity of each layer will increase, and repeated heating at the rate of the present invention will cause cracks and cracks, and the layer will not be able to withstand use. From the perspective of heat capacity alone, the thinner the thickness of each layer, the better. However, if it is less than 1μm, it is not good because the strength and durability are not enough, and the uniform film formation with such a thin thickness increases the manufacturing cost. The thickness of each layer of the base layer, middle layer, and surface layer of the present invention is preferably 5μm or more and 25μm or less.
此外，在專利文獻2中，認為「底層的厚度若小於30μm，則無法充分得到抑制矽及氧浮上至氧化鋯質表面層的功效；另一方面，厚度若超過300μm，上述功效不能再提高，而且成為整個道具材料的薄壁化的障礙，高重量、高成本等缺點較大」。 In addition, Patent Document 2 states that "if the thickness of the bottom layer is less than 30μm, the effect of suppressing the floating of silicon and oxygen to the zirconia surface layer cannot be fully achieved; on the other hand, if the thickness exceeds 300μm, the above effect cannot be improved, and it becomes an obstacle to the thinning of the entire tool material, resulting in greater disadvantages such as high weight and high cost."
然而，在專利文獻2中，並未提及作為道具材料的熱容量，也未提出針對此點解決的方法之具體方案。 However, Patent Document 2 does not mention the heat capacity of the prop material, nor does it propose a specific solution to this problem.
此外，在專利文獻2中，認為各層厚度若過薄，則無法充分得到抑制來自碳化矽基材(氧化膜(由SiO2所構成的膜)的矽及氧的浮上的功效。關於此點，本發明也是如此，僅將各層設為較薄則會發生同樣的問題。 In addition, in Patent Document 2, it is considered that if the thickness of each layer is too thin, the effect of suppressing the floating of silicon and oxygen from the silicon carbide substrate (oxide film (film composed of SiO2 )) cannot be fully obtained. Regarding this point, the same is true for the present invention, and the same problem will occur if each layer is simply made thinner.
對此，作為本發明的第二特徵，將各層亦即底層、中間層及表面層的孔隙率設為均為5%以下。 In this regard, as a second feature of the present invention, the porosity of each layer, namely the bottom layer, the middle layer and the surface layer, is set to be less than 5%.
本發明的發明人們發現藉由如此將孔隙率設為預定的數值以下，可充分抑制來自由碳化矽所構成的基材的矽及氧的浮上。 The inventors of the present invention have found that by setting the porosity to a predetermined value or less, the floating of silicon and oxygen from the substrate composed of silicon carbide can be sufficiently suppressed.
在各層內存在較多孔隙時，認為使氧化矽成分濃度相對高，因各層內的氧化矽成分濃度以及與表面層的表層部(與燒製氛圍的接触面)之間的氧化矽成分的濃度梯度的增加而使擴散速度變快並促進矽及氧的浮上。 When there are more pores in each layer, the concentration of silicon oxide components is relatively high, and the concentration gradient of silicon oxide components in each layer and between the surface layer (the contact surface with the firing atmosphere) increases, which speeds up the diffusion rate and promotes the floating of silicon and oxygen.
如前述，從抑制矽及氧的浮上的觀點來看，雖然孔隙率越小越佳，然而若將孔隙率設為小於1%，由於成為包含面內均一性的確保之高成本的製造條件，故不佳。孔隙率較佳為3%以上至5%以下。 As mentioned above, from the perspective of suppressing the floating of silicon and oxygen, the smaller the porosity, the better. However, if the porosity is set to less than 1%, it will become a high-cost manufacturing condition including ensuring the uniformity within the surface, so it is not good. The porosity is preferably greater than 3% and less than 5%.
本發明可利用電漿熔射形成各層(底層、中間層及表面層)。此外，此時，當作為各層的原料所使用的粉末應用粒徑較小的粉末時，形成有如上述般的孔隙率5%以下的層。 The present invention can form each layer (bottom layer, middle layer and surface layer) by plasma spraying. In addition, at this time, when the powder used as the raw material of each layer is a powder with a smaller particle size, a layer with a porosity of less than 5% as described above is formed.
作為一例，較佳為原料的粒度範圍落於10μm以上至45μm以下的規格品。 For example, the preferred raw material is one with a particle size range of 10μm to 45μm.
此外，在專利文獻3中，將各層的厚度設為10μm至200μm，作為一例將氧化鋯層與富鋁紅柱石層的厚度設為30μm。另一方面，在專利文獻3中，將基材本身的孔隙率設為較大，如15%至60%，而且將基材的厚度為較薄，如 0.2mm至1mm，藉此可謀求輕量化、低熱容量化，並可使燒製用道具材料的溫度迅速地隨從爐內溫度。 In addition, in Patent Document 3, the thickness of each layer is set to 10μm to 200μm, and as an example, the thickness of the zirconia layer and the aluminum-rich andalusite layer is set to 30μm. On the other hand, in Patent Document 3, the porosity of the substrate itself is set to be relatively large, such as 15% to 60%, and the thickness of the substrate is set to be relatively thin, such as 0.2mm to 1mm, thereby achieving lightweight and low heat capacity, and allowing the temperature of the burning tool material to quickly follow the temperature in the furnace.
相對於此，本發明對基材本身不設定特別的限制，亦即即使設為較專利文獻3所記載的基材更厚或使用孔隙率更小，也可使溫度隨從性優異。 In contrast, the present invention does not impose any special restrictions on the substrate itself, that is, even if the substrate is thicker or has a smaller porosity than that described in Patent Document 3, the temperature compliance can be excellent.
此外，藉此，相較於專利文獻3所記載的道具材料，藉由將基材變厚，而可使道具材料不容易破裂。或者，藉由設孔隙率為較小而提高緊密度，可得到提高強度的道具材料。 In addition, compared with the tool material described in Patent Document 3, the tool material can be made less likely to break by making the base material thicker. Alternatively, a tool material with improved strength can be obtained by reducing the porosity and increasing the density.
具體而言，在本發明中，即使至少載置被燒製物之部分的基材的厚度為1.5mm以上至4mm以下，不僅強度及耐久性均優異，而且溫度隨從性優異且可抑制氧化矽的表面浮上，成為極為優異的燒製用道具材料，故更佳。 Specifically, in the present invention, even if the thickness of at least the portion of the substrate on which the fired object is placed is 1.5 mm or more and 4 mm or less, not only is the strength and durability excellent, but the temperature compliance is excellent and the surface floating of silicon oxide can be suppressed, making it an extremely excellent firing tool material, which is better.
其中，本發明在燒製用道具材料的任意的切斷面中，將底層、中間層及表面層的至少任一者侵入至基材的部位界定為侵入部，將前述侵入部的深度作為D，將前述侵入部的寬度作為W時，較佳為W≦30μm且D/W≧1。 Among them, in the present invention, in any cross-section of the material for firing tools, the portion where at least one of the bottom layer, the middle layer and the surface layer intrudes into the substrate is defined as the intrusion portion, and when the depth of the intrusion portion is D and the width of the intrusion portion is W, it is preferred that W≦30μm and D/W≧1.
藉由採用上述構成，可有效抑制如本發明般的形成有膜厚較薄的溶射膜時成為問題的膜剝離(溶射膜的密著性的降低)。 By adopting the above structure, it is possible to effectively suppress film peeling (reduction in adhesion of the sprayed film) which is a problem when a thin sprayed film is formed as in the present invention.
本發明的侵入部係利用燒製用道具材料的任意的切斷面來界定。此切斷面係可利用例如光學顯微鏡觀察。此外，觀察的部位及倍率並未特別限制，然而只要能明確地識別某種程度的凹凸之程度即可。 The intrusion part of the present invention is defined by an arbitrary cross-section of the material of the burning tool. This cross-section can be observed using, for example, an optical microscope. In addition, the observation location and magnification are not particularly limited, but as long as a certain degree of concavity and convexity can be clearly identified, it will suffice.
作為一例，可舉例觀察範圍係一邊為300μm至1200μm的矩形狀區域且倍率為100倍至400倍，較佳為一邊為600μm的矩形狀區域且倍率為200倍。關於侵入部，由於溶射膜的凹凸相對於層厚較大，因此取得這種程度的面積來判斷侵入部的尺寸(大小)較佳。 For example, the observation range is a rectangular area with a side of 300μm to 1200μm and a magnification of 100 to 400 times, preferably a rectangular area with a side of 600μm and a magnification of 200 times. As for the intrusion part, since the projection film has a larger concave and convex shape relative to the layer thickness, it is better to obtain an area of this degree to judge the size of the intrusion part.
接著，在上述區域內，將底層、中間層及表面層的至少任一者侵入至基材的部位作為侵入部，將侵入部的深度作為D，將侵入部的寬度作為W時，W≦30μm且D/W≧1。 Next, in the above region, the portion where at least one of the bottom layer, the intermediate layer, and the surface layer intrudes into the substrate is defined as the intrusion portion, the depth of the intrusion portion is defined as D, and the width of the intrusion portion is defined as W, W≦30μm and D/W≧1.
如圖1所示，在燒製用道具材料的任意的切斷面中觀察任意的區域時，關注基材Z與底層1(實際上也含有包含中間層、表面層的形態)的界面L，畫平行於觀察畫面的橫邊的線，將此線作為基準線X。此基準線X亦可從觀察畫面以目視來測量，亦可用公知的圖像解析軟體。或者，亦可利用與算術平均粗糙度Ra(JISB0601：1994)同樣的方式計算。 As shown in Figure 1, when observing any area in any cross-section of the material for the burning tool, pay attention to the interface L between the substrate Z and the bottom layer 1 (actually also including the morphology including the middle layer and the surface layer), draw a line parallel to the horizontal side of the observation screen, and use this line as the reference line X. This reference line X can also be measured visually from the observation screen, or it can be calculated using known image analysis software. Alternatively, it can also be calculated in the same way as the arithmetic mean roughness Ra (JISB0601: 1994).
侵入部係指相對於與圖1所示的基準線X垂直的方向，底層、中間層、表面層的至少一個進入至基準線X的下方的部位。接著，如圖1所示，基於基準線X取出任意的侵入部時，將侵入部的深度作為D，將侵入部的寬度作為W，以W≦30μm且D/W≧1的關係是否成立來判斷。 The intrusion part refers to the part where at least one of the bottom layer, middle layer, and surface layer enters below the baseline X in the direction perpendicular to the baseline X shown in Figure 1. Next, as shown in Figure 1, when an arbitrary intrusion part is taken out based on the baseline X, the depth of the intrusion part is D, the width of the intrusion part is W, and the relationship of W≦30μm and D/W≧1 is determined.
其中，底層1若較厚時，則如圖1所示僅在底層1形成有侵入部。底層1若較薄時，則如圖2所示有可能因形成於底層1上的中間層2的一部分侵入而形成侵入部。此外，也假定中間層2較薄，且形成於中間層2上的表面層也形成侵入部。
If the
W≦30μm且D/W≧1的形態係凹陷的深度相對於凹陷的直徑大於1的狀態。一般而言，為了加強溶射膜的侵入，認為較佳為凹凸較大，亦即凹陷的深度相對於凹陷的直徑較深。 The morphology of W≦30μm and D/W≧1 is a state where the depth of the depression is greater than 1 relative to the diameter of the depression. Generally speaking, in order to enhance the penetration of the spray film, it is considered better to have a larger concave-convex shape, that is, the depth of the depression is deeper relative to the diameter of the depression.
然而，在形成有如本發明般三層構造的膜且各層的厚度為1μm至30μm的情況下，難以僅在層形成相對於深度方向具有充分深度的凹陷。若基材的凹凸變大，則雖然達成較深的凹陷，然而此時容易出現溶射膜的層的厚度不 均，有作為保護層的功能有問題的顧慮。 However, when a three-layer film is formed as in the present invention and the thickness of each layer is 1μm to 30μm, it is difficult to form a depression with sufficient depth relative to the depth direction only in the layer. If the unevenness of the substrate becomes larger, a deeper depression can be achieved, but the thickness of the layer of the spray film is likely to be uneven, and there is a concern that the function as a protective layer may be problematic.
因此，本發明中，發現藉由將凹凸的凹陷的直徑和深度控制為預定範圍，即使保護層較薄且基材的表面較為平滑，也可充分確保層的定錨(anchor)效應的範圍。若侵入部的寬度W過大，則由於相對於層厚的上限30μm無法充分確保層的厚度的區域存在得較多，因此有使層的耐久性降低之虞。若侵入部的深度D與侵入部的寬度W的比例亦即D/W小於1，則有無法充分得到定錨效應或抑制矽及氧的浮上的功效的顧慮。 Therefore, in the present invention, it is found that by controlling the diameter and depth of the concave-convex depression to a predetermined range, the range of the anchor effect of the layer can be fully ensured even if the protective layer is thin and the surface of the substrate is smooth. If the width W of the intrusion portion is too large, there are more areas where the thickness of the layer cannot be fully ensured relative to the upper limit of the layer thickness of 30μm, so there is a risk of reducing the durability of the layer. If the ratio of the depth D of the intrusion portion to the width W of the intrusion portion, that is, D/W, is less than 1, there is a concern that the anchor effect or the effect of suppressing the floating of silicon and oxygen cannot be fully obtained.
為了得到W≦30μm且D/W≧1，可藉由適當控制基材的表面狀態、用以形成溶射膜的原料粉的尺寸、溶射溫度等而得到。作為一例，較佳為設基材中之形成溶射膜之面的凹凸為Ra(算術平均粗糙度)且設為4μm至6μm的範圍，設Ry(最大高度)為25μm至35μm的範圍，設底層的原料粉的尺寸為15μm至40μm的範圍。 In order to obtain W≦30μm and D/W≧1, it can be obtained by properly controlling the surface state of the substrate, the size of the raw material powder used to form the spray film, the spray temperature, etc. As an example, it is better to set the concave-convex surface of the substrate on which the spray film is formed to Ra (arithmetic mean roughness) and set it to the range of 4μm to 6μm, set Ry (maximum height) to the range of 25μm to 35μm, and set the size of the raw material powder of the bottom layer to the range of 15μm to 40μm.
此外，為了使本發明更為優異，在任意的切斷面中形成中間層潛入至底層的背側的狀態並將此作為潛入部時，較佳為潛入寬度L1滿足L1≦1μm的束縛點在600μm的觀察範圍中有平均一個以上。圖3顯示用以說明此種態樣的模式圖。將基準線X上存在的任意的凹陷的一端部S1作為起點，將在此凹陷靠近基材側的部位朝平行於基準線X的方向進展的凹陷的端部作為另一端部S2。接著，將平行於基準線X的一端部S1與另一端部S2之間的距離作為L1，將此L1作為滑入部。此外，含有L1的鑰匙狀的部位稱為束縛點。 In addition, in order to make the present invention more excellent, when the state in which the intermediate layer is infiltrated to the back side of the bottom layer is formed in any cut surface and this is used as the infiltration part, it is preferable that the infiltration width L1 satisfies L1≦1μm and there is an average of more than one constraint point in the observation range of 600μm. FIG3 shows a schematic diagram for illustrating this state. Take one end S1 of any depression existing on the reference line X as the starting point, and take the end of the depression that progresses in the direction parallel to the reference line X at the part of the depression close to the substrate side as the other end S2. Then, the distance between the one end S1 parallel to the reference line X and the other end S2 is L1, and this L1 is used as the sliding part. In addition, the key-shaped part containing L1 is called the constraint point.
再者，也形成表面層3潛入至中間層2的背側的潛入部，潛入部的潛入寬度L2滿足L2≧1μm的束縛點在600μm的觀察範圍中可有平均一個以上。圖4顯示此種態樣。基本的定義類似於圖3的L1。 Furthermore, a penetration portion is formed in which the surface layer 3 penetrates into the back side of the intermediate layer 2, and the penetration width L2 of the penetration portion satisfies that there is an average of more than one constraint point where L2 ≧ 1 μm in the observation range of 600 μm. Figure 4 shows this state. The basic definition is similar to L1 in Figure 3.
如此，在中間層2潛入至底層1的背側而且表面層3潛入至中間層2的背側時，即使溶射膜較薄，溶射膜的剝離抑制功效也更為堅固，一邊發揮本發明的功效，一邊使耐久性及可靠性更為優異。
In this way, when the middle layer 2 is embedded in the back side of the
[實施例] [Implementation example]
以下，根據實施例具體說明本發明，然而本發明並不限制於如下所示的實施例。 The present invention is described below in detail based on the embodiments, but the present invention is not limited to the embodiments shown below.
將燒結後的殘碳為小於5.0重量%的量的甲基纖維素(methyl cellulose)系的黏合劑添加至市售的碳化矽粉末原料並混合而得混合物。接著，將水添加至前述混合物並混練，藉由壓製成形而獲得多孔質成形體。 A methyl cellulose-based binder having a carbon residue of less than 5.0% by weight after sintering is added to a commercially available silicon carbide powder raw material and mixed to obtain a mixture. Then, water is added to the above mixture and kneaded, and a porous molded body is obtained by pressing.
接著，在Ar氛圍下以預定的數值來變化燒製溫度與燒製時間並燒結前述多孔質成形體，然後在氧濃度為4%且剩下由氮所構成的氛圍下以1500℃燒製3小時並實施氧化處理，將以SiO2為主成分的氧化膜形成於此燒結體表面。此種以SiO2為主成分的氧化膜的厚度為1μm。 Next, the porous molded body is sintered in an Ar atmosphere while changing the sintering temperature and sintering time by predetermined values, and then sintered at 1500°C for 3 hours in an atmosphere with an oxygen concentration of 4% and the remainder being nitrogen, and an oxidation treatment is performed to form an oxide film with SiO2 as the main component on the surface of the sintered body. The thickness of the oxide film with SiO2 as the main component is 1 μm.
藉此，製備縱300mm×橫300mm×厚度2mm、平均孔隙率23%的板狀的基材。 In this way, a plate-shaped substrate with a length of 300mm, a width of 300mm, a thickness of 2mm and an average porosity of 23% was prepared.
接著，以具有表1所示的各層的厚度、孔隙率之方式，利用電漿熔射依序在前述基材的一表面形成富鋁紅柱石覆膜(底層)、在富鋁紅柱石覆膜(底層)上的氧化鋁覆膜(中間層)以及進一步在氧化鋁覆膜(中間層)上的氧化鋯覆膜(被覆層)，從而作為評估用的各燒製用道具材料。 Next, an aluminum-rich andalusite film (bottom layer), an aluminum oxide film (intermediate layer) on the aluminum-rich andalusite film (bottom layer), and a zirconium oxide film (coating layer) on the aluminum oxide film (intermediate layer) were sequentially formed on one surface of the aforementioned substrate by plasma spraying in a manner having the thickness and porosity of each layer shown in Table 1, thereby serving as various firing tool materials for evaluation.
此外，藉由公知的方法，亦即藉由適時調整電漿熔射時的溫度、氣體流量、原料的供給速度、原料粒徑的變更、其他條件，藉此進行孔隙率的控制。此外，使用各溶射材料的原料粒徑均為75μm以下(或45μm以下)的各溶射材料。 In addition, the porosity is controlled by a known method, that is, by timely adjusting the temperature, gas flow rate, raw material supply speed, change of raw material particle size, and other conditions during plasma spraying. In addition, the raw material particle size of each spraying material used is 75μm or less (or 45μm or less).
[評估] [evaluate]
針對上述各燒製用道具材料，用如下所示的方法評估孔隙率、温度追隨性、表面氧化矽量及耐剥離性。 For each of the above-mentioned firing tool materials, the porosity, temperature tracking performance, surface silicon oxide content, and peeling resistance were evaluated using the following method.
[孔隙率] [Porosity]
孔隙率係從掃描式電子顯微鏡(SEM；Scanning Electron Microscope)所得的剖面圖像計算。將上述燒製用道具材料切斷而得的試驗片用環氧樹脂固化，再用金剛石膏(diamond paste)研磨切斷面，利用SEM以500倍的倍率拍攝電子題微鏡照片。計算圖像上的孔隙的面積相對於各溶射材質的面積作為孔隙率。 The porosity is calculated from the cross-sectional images obtained by scanning electron microscope (SEM). The test piece obtained by cutting the above-mentioned burning tool material is cured with epoxy resin, and then the cut surface is polished with diamond paste. The electron microscope photo is taken at a magnification of 500 times using SEM. The area of pores on the image is calculated relative to the area of each molten material as the porosity.
[溫度隨從性] [Temperature compliance]
關於温度追隨性，安裝熱電偶至上述燒製用道具材料的表面，以700℃/min的升溫速度投入至連續搬送式剝落試驗爐，測定爐內温度與製品表面温度的偏差，偏差若落在3℃以內則為合格。 Regarding temperature tracking, a thermocouple is installed on the surface of the above-mentioned firing tool material, and it is placed in a continuous conveyor peeling test furnace at a heating rate of 700℃/min. The deviation between the temperature inside the furnace and the surface temperature of the product is measured. If the deviation is within 3℃, it is qualified.
[耐剥離性] [Peeling resistance]
以目視來觀察上述溫度隨從性的試驗後的燒製用道具材料表面，並確認有無溶射的膜的剥離，若未確認到剝離則為合格。 Visually observe the surface of the firing tool material after the above temperature compliance test and check whether the film sprayed is peeled off. If no peeling is confirmed, it is qualified.
[表面氧化矽量] [Surface silicon oxide content]
表面氧化矽量係以上述燒製用道具材料的陶瓷電子零件的燒製試驗及螢光X射線分析來評估。 The amount of silicon oxide on the surface is evaluated by firing tests and fluorescent X-ray analysis of ceramic electronic parts made of the above-mentioned firing tool materials.
切出縱150mm×橫50mm×厚度2mm的試樣，將直徑4mm×高度3mm的鈦酸鋇成形體載置，將氮及氫(99：1)的混合潮濕氣體流入，設置於將氧分壓調整為10-19atm至10-21atm的弱還原氛圍的電爐，在600℃至1350℃之間重複熱循環。 A sample with a length of 150 mm, a width of 50 mm, and a thickness of 2 mm was cut out, and a barium titanate formed body with a diameter of 4 mm and a height of 3 mm was placed on it. A mixed humid gas of nitrogen and hydrogen (99:1) was flowed into the sample. The sample was placed in an electric furnace with a weak reducing atmosphere with an oxygen partial pressure adjusted to 10-19 atm to 10-21 atm, and thermal cycles were repeated between 600°C and 1350°C.
重複此熱循環30次後，對於載置鈦酸鋇成形体的固定器試樣表面之四處(直徑20mm)以螢光X射線分析來測定表面氧化矽量(質量%)，數值若落在0.3%以內 則為合格。 After repeating this thermal cycle 30 times, the surface silicon oxide content (mass %) of the four locations of the fixture sample (diameter 20mm) on which the barium titanate formed body is placed is measured by fluorescent X-ray analysis. If the value falls within 0.3%, it is considered qualified.
[綜合評估] [Comprehensive evaluation]
關於綜合評估，若上述温度追隨性、表面氧化矽量及耐剥離性的三個項目均為合格，則為合格(○)；若任一個項目不滿足基準，則為不合格(×)。彙整各燒製用道具材料的條件及評估結果表示於如下表1。 Regarding the comprehensive evaluation, if the three items of temperature tracking, surface silicon oxide content and peeling resistance are all qualified, it is qualified (○); if any item does not meet the standard, it is unqualified (×). The conditions and evaluation results of each firing tool material are summarized in the following Table 1.
從表1的結果顯而易見，落在本發明(實施例)的範圍內，作為燒製用道具材料具有良好的特性。 It is obvious from the results in Table 1 that they fall within the scope of the present invention (embodiment) and have good properties as a material for firing tools.
具體而言，此實施例1的評估項目全部為合格。
Specifically, all evaluation items of this
實施例2係各層的層厚全部為上限。相較於實施例1，雖然溫度隨從性稍微差，然而為合格；雖然表面氧化矽量也為上限附近，然而為合格；其他評估結果也良好。 In Example 2, the thickness of each layer is at the upper limit. Compared with Example 1, although the temperature compliance is slightly worse, it is qualified; although the amount of surface silicon oxide is also near the upper limit, it is qualified; other evaluation results are also good.
實施例3係各層的層厚全部為下限。相較於實施例1，雖然因各層的厚度較薄導致表面氧化矽量為仍接近上限之值，然而為合格；其他評估結果也良好。 In Example 3, the thickness of each layer is all at the lower limit. Compared with Example 1, although the surface silicon oxide amount is still close to the upper limit due to the thinner thickness of each layer, it is qualified; other evaluation results are also good.
實施例4係各層的孔隙率接近上限5%。相較於實施例1，雖然因孔隙率較大導致表面氧化矽量接近上限，然而為合格；其他評估結果也良好。 In Example 4, the porosity of each layer is close to the upper limit of 5%. Compared with Example 1, although the surface silicon oxide amount is close to the upper limit due to the larger porosity, it is qualified; other evaluation results are also good.
作為較佳的例子，實施例5係各層的厚度分別為5μm、實施例6係各層的厚度分別為25μm。相較於實施例1，實施例5的溫度隨從性及實施例6的氧化矽量分別良好。 As a better example, the thickness of each layer in Example 5 is 5μm, and the thickness of each layer in Example 6 is 25μm. Compared with Example 1, the temperature compliance of Example 5 and the amount of silicon oxide in Example 6 are good.
比較例1係各層的層厚為40μm，超過本發明的範圍的30μm。 In Comparative Example 1, the thickness of each layer is 40μm, which exceeds the range of 30μm of the present invention.
此時，雖然孔隙率低於本發明的範圍的5%，然而表面氧化矽量超過合格線的0.3%，故為不合格。 At this time, although the porosity is lower than the range of 5% of the present invention, the amount of silicon oxide on the surface exceeds the qualified line of 0.3%, so it is unqualified.
比較例2係各層的層厚為100μm，超過本發明的範圍的30μm。因此，在溫度隨從性的方面，温度的偏差超過3℃，此點為不合格。此外，由於作為以溶射法 形成層時的傾向，一邊使原料粒徑相同，一邊將層厚增厚，導致孔隙率上升，因此相較於比較例1，孔隙率較大，大於4%。 In Comparative Example 2, the thickness of each layer is 100μm, which exceeds the range of 30μm of the present invention. Therefore, in terms of temperature compliance, the temperature deviation exceeds 3°C, which is unqualified. In addition, since the tendency when forming the layer by the spraying method is to make the raw material particle size the same while increasing the layer thickness, the porosity increases, so the porosity is larger than that of Comparative Example 1, greater than 4%.
相較於比較例2，比較例3將原料粒徑加大，並刻意增大各層的孔隙率。此時相較於比較例2，溫度隨從性嚴重變差。 Compared with Comparative Example 2, Comparative Example 3 increases the particle size of the raw material and deliberately increases the porosity of each layer. At this time, compared with Comparative Example 2, the temperature compliance is seriously deteriorated.
相較於比較例3，比較例4將各層的厚度進一步增厚。此時，相較於比較例3，溫度隨從性稍微變差。 Compared with Comparative Example 3, Comparative Example 4 further increases the thickness of each layer. At this time, the temperature compliance is slightly worse than that of Comparative Example 3.
相較於比較例4，比較例5將各層的厚度再進一步增厚。此時，相較於比較例4，溫度隨從性更為變差。由此可知，各層的厚度係對溫度隨從性帶來較大影響。此外，由於為原料粒徑較大且孔隙率較高的膜，故膜厚過厚，因此基材與溶射膜之間的熱膨張差變大造成剥離。 Compared with Comparative Example 4, Comparative Example 5 further increases the thickness of each layer. At this time, the temperature compliance is worse than that of Comparative Example 4. It can be seen that the thickness of each layer has a greater impact on the temperature compliance. In addition, since it is a film with a larger raw material particle size and a higher porosity, the film thickness is too thick, so the thermal expansion difference between the substrate and the sprayed film increases, causing peeling.
此外，相較於比較例1，比較例3、4的表面氧化矽量較低的理由係後者的原料粒徑較前者的更大，使各層中的每單位體積的粒界佔據的比例相對減小。依此認為，由於氧化矽優先擴散粒界，因此粒界較少的比較例3、4的表面氧化矽量較低。 In addition, the reason why the amount of surface silicon oxide in Comparative Examples 3 and 4 is lower than that in Comparative Example 1 is that the particle size of the raw material in the latter is larger than that in the former, which makes the proportion of grain boundaries per unit volume in each layer relatively smaller. Based on this, it is believed that since silicon oxide diffuses grain boundaries first, the amount of surface silicon oxide in Comparative Examples 3 and 4 with fewer grain boundaries is lower.
比較例6係底層的層厚低於本發明的範圍的1μm。此時發現若三層的其中任一層的層厚過薄，則表面氧化矽量增加，而為不合格。 In Comparative Example 6, the thickness of the bottom layer is lower than the range of 1μm of the present invention. It was found that if the thickness of any of the three layers is too thin, the amount of silicon oxide on the surface increases, resulting in failure.
比較例7係中間層的層厚超過本發明的範圍的30μm。此時發現若三層的其中任一層的層厚過厚，則溫度隨從性超過3℃，溫度隨從性變差，而為不合格。此外，此也認為由於原料粒徑較小的緊密膜且膜厚過厚，因此基材與溶射膜之間的熱膨張差造成剥離。 In Comparative Example 7, the thickness of the intermediate layer exceeds the range of 30μm of the present invention. It was found that if the thickness of any of the three layers is too thick, the temperature compliance exceeds 3°C, the temperature compliance deteriorates, and it is unqualified. In addition, it is also believed that the thermal expansion difference between the substrate and the spray film caused the peeling due to the small particle size of the raw material and the thick film.
比較例8係表面層的孔隙率超過本發明的範圍的5%。此時發現若三層的其中任一層的孔隙率過高，則表面氧化矽量超過0.3%，而此點為不合格。 In Comparative Example 8, the porosity of the surface layer exceeds the range of the present invention by 5%. It is found that if the porosity of any of the three layers is too high, the amount of silicon oxide on the surface exceeds 0.3%, which is unqualified.
順便一提，實施例1中，W為28μm且D/W為1.5。其中，以變更溶射條件(增加噴吹量)來形成為使W為33μm且D/W為1.3的底層，其他儘量與實施例1同等的方式而製造實施例7。接著，連續實施溫度隨從性的試驗20次後，評估耐剝離性。 By the way, in Example 1, W is 28μm and D/W is 1.5. Among them, Example 7 was manufactured in the same manner as Example 1 by changing the spraying conditions (increasing the spraying amount) to form a base layer with W of 33μm and D/W of 1.3. Then, after the temperature compliance test was continuously performed 20 times, the peeling resistance was evaluated.
相較於實施例1，實施例7係在上述評估後確認到一處有輕微的剝離。亦即在更嚴苛的使用條件下，相較於實施例1，實施例7稍微差。 Compared with Example 1, Example 7 was confirmed to have slight peeling after the above evaluation. That is, under more stringent use conditions, Example 7 is slightly worse than Example 1.
其中，以變更溶射條件(稍微減少噴吹量)來形成W為27μm且D/W為0.9的底層，其他儘量與實施例1同等的方式而製造實施例8。接著，與實施例7同樣，連續實施溫度隨從性的試驗20次後，評估耐剝離性。 Among them, Example 8 was manufactured by changing the spraying conditions (slightly reducing the spraying amount) to form a base layer with W of 27μm and D/W of 0.9, and the rest was as similar as Example 1. Then, as in Example 7, the temperature compliance test was continuously carried out 20 times, and the peeling resistance was evaluated.
其結果，相較於實施例1，實施例8在上述評估後仍確認到一處有輕微的剝離。 As a result, compared with Example 1, Example 8 still confirmed slight peeling after the above evaluation.
再者，以變更溶射條件(變更噴吹量與溫度)來形成為W為32μm且D/W為0.85的底層，其他儘量與實施例1同等的方式而製造實施例9。接著，與實施例7、8同樣，連續實施溫度隨從性的試驗20次後，評估耐剝離性。 Furthermore, Example 9 was manufactured by changing the spraying conditions (changing the spraying amount and temperature) to form a base layer with W of 32μm and D/W of 0.85, and the other conditions were as similar as Example 1. Then, as in Examples 7 and 8, the temperature compliance test was continuously performed 20 times, and the peeling resistance was evaluated.
其結果，相較於實施例1，實施例9在上述評估後確認到共三處有輕微的剝離。相較於實施例7、8，W和D/W的兩者均不在較佳範圍的實施例9仍稍微差。 As a result, compared with Example 1, Example 9 was confirmed to have slight peeling in three places after the above evaluation. Compared with Examples 7 and 8, Example 9, in which both W and D/W were not within the optimal range, was still slightly worse.
此外，針對溫度隨從性與氧化矽量，實施例7至9均為合格。 In addition, in terms of temperature compliance and silicon oxide content, Examples 7 to 9 are all qualified.
如上所述，藉由使用本發明的燒製用道具材料，由於温度追隨性較高，且即使重複使用於燒製，表面氧化矽的浮上也較少，因此對燒製後的製品中的品質的影響較小，再者可以較以往更高速的條件來燒製，有助於生產性的提升。 As described above, by using the firing tool material of the present invention, the temperature tracking property is high, and even if it is used repeatedly for firing, the floating of surface silicon oxide is small, so the impact on the quality of the fired product is small. In addition, it can be fired at a higher speed than before, which helps to improve productivity.
Claims (3)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022-070920 | 2022-04-22 | ||
| JP2022070920 | 2022-04-22 | ||
| JP2023-040728 | 2023-03-15 | ||
| JP2023040728A JP2023160735A (en) | 2022-04-22 | 2023-03-15 | Tool material for firing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW202406884A TW202406884A (en) | 2024-02-16 |
| TWI845233B true TWI845233B (en) | 2024-06-11 |
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