JPS5946491A - Heat exchanger of silicon carbide - Google Patents
Heat exchanger of silicon carbideInfo
- Publication number
- JPS5946491A JPS5946491A JP15776282A JP15776282A JPS5946491A JP S5946491 A JPS5946491 A JP S5946491A JP 15776282 A JP15776282 A JP 15776282A JP 15776282 A JP15776282 A JP 15776282A JP S5946491 A JPS5946491 A JP S5946491A
- Authority
- JP
- Japan
- Prior art keywords
- silicon carbide
- silicon
- less
- heat exchanger
- pores
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 33
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 239000010703 silicon Substances 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000012530 fluid Substances 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 238000005192 partition Methods 0.000 claims description 3
- 238000005229 chemical vapour deposition Methods 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052681 coesite Inorganic materials 0.000 abstract description 3
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 230000035699 permeability Effects 0.000 abstract description 3
- 229910052682 stishovite Inorganic materials 0.000 abstract description 3
- 229910052905 tridymite Inorganic materials 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 239000000945 filler Substances 0.000 abstract 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 229910010293 ceramic material Inorganic materials 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
- F28F21/04—Constructions of heat-exchange apparatus characterised by the selection of particular materials of ceramic; of concrete; of natural stone
Landscapes
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は炭化珪素からなる熱交換器の改良に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to improvements in heat exchangers made of silicon carbide.
通常熱交換器は高熱伝導性を有するものとして銅、銅合
金等が低温（２〜３００℃）用として、又高温（１，０
００℃以下）用としてインコネル、ハステロイ等の金属
材料が使用されている。又特にｉ、ｏｏｏ℃以上の高温
用としては金属では耐熱限界を越えることから、コージ
ライト、炭化珪素等のセラミック材料が知られている。Usually, heat exchangers are made of copper, copper alloy, etc., which have high thermal conductivity, and are used for low temperatures (2 to 300 degrees Celsius) or for high temperatures (1,0 degrees Celsius).
Metal materials such as Inconel and Hastelloy are used for temperatures below 00°C. In particular, ceramic materials such as cordierite and silicon carbide are known as they exceed the heat resistance limit of metals for use at high temperatures of i,00° C. or higher.
セラミック材料は一般に耐熱耐蝕性にすぐれているが特
に溶接が困難な点等加工性に難点があり、複雑な形状に
は適さない。Ceramic materials generally have excellent heat and corrosion resistance, but they have difficulties in workability, particularly in that they are difficult to weld, and are not suitable for complex shapes.
又、熱交換器は高度の信頼性が要求され、しかも長寿命
のものである必要があり、これらの点で従来のセラミッ
ク材料では満足すべきものは得られていなかった。例え
ば、コージライト質のものは耐熱、耐スポーリング性は
満足できるにしても、複合成分素地から作られるため均
質性に乏しく実用に耐えるものは得られていない。又、
炭化珪素質のものは熱伝導性は良好ヤあるが、粘土等で
焼結したものであるため熱間荷重に弱く、特に通気性に
問題が残っていた。In addition, heat exchangers are required to have a high degree of reliability and to have a long life, and conventional ceramic materials have not been satisfactory in these respects. For example, cordierite materials may have satisfactory heat resistance and spalling resistance, but because they are made from a composite material, they lack homogeneity and cannot be of practical use. or,
Those made of silicon carbide have good thermal conductivity, but because they are sintered with clay or the like, they are vulnerable to hot loads, and there remain problems, especially in air permeability.
更に高温における耐酸化性に難点があり、ＳｉＯ２の形
成と共に表面及び内部との応力の差が次第に拡大し１、
ついには破壊に至る等持てる特性を充分に発揮し得ない
状態であった。Furthermore, there is a problem with oxidation resistance at high temperatures, and as SiO2 forms, the difference in stress between the surface and the inside gradually increases1.
In the end, it was in a state where it could not fully demonstrate its characteristics, leading to destruction.
本発明は炭化珪素の持つ特性を充分生かすべくその欠点
を究明し、これを改善することによって従来に見られな
い熱交換器を開発したもので再結晶炭化珪素成形体の気
孔をシリコンによって充填し、しかもその不純物をＦ８
５００ ｐｐｍ以下、ＡＬ １０００ ｐＰｍ以下、Ｎ
ａ１００ ｐｐｍ以下の炭化珪素−シリコンからなる高
純度の材料としだものである。In order to make full use of the characteristics of silicon carbide, the present invention has investigated the shortcomings of silicon carbide, and by improving these, we have developed a heat exchanger that has never been seen before.The pores of a recrystallized silicon carbide molded body are filled with silicon. , and the impurities are F8
500 ppm or less, AL 1000 pPm or less, N
It is made of a high purity material made of silicon carbide-silicon with an a content of 100 ppm or less.
即ち、炭化珪素の酸化は炭化珪素自体が酸化されその表
面に５ｉｎ２ の被膜が形成され、この５ｉｎ２ の
被膜が剥離すると新だに露出しだ炭化珪素か酸化を受け
るというような過程で進行する。この場合生成した５ｉ
０２被膜が剥離することなく存在すれば炭化珪素の７ｐ
化は停止するが、この５ｉ０２ 被１７／＋はＦｅ
２０ｓ、へ７２０３等の不純物が存在すると熱的に不安
定な組成に転化しＳ ｉ ０２被膜の剥離に連がるとい
うことが明らかとなった。That is, the oxidation of silicon carbide proceeds in such a way that the silicon carbide itself is oxidized, a 5 in 2 film is formed on its surface, and when this 5 in 2 film is peeled off, the newly exposed silicon carbide is oxidized. In this case, the generated 5i
02 If the film exists without peeling, 7p of silicon carbide
The conversion stops, but this 5i02 17/+ is Fe
It has become clear that the presence of impurities such as 20s and He7203 transforms the composition into a thermally unstable composition, leading to peeling of the Si02 film.
従って本発明のものにおいでは高純度の炭化珪素を使用
し、金属に換算してＦ’Ｐ５００ ｐｐｍ以下、Ａｔ
１０００ ｐｐｍ以下、ＮＡ１００ ｐｐｍ以下とする
ことにより、かつ形成した炭化珪素成形体の気孔を高純
度のシリコンによって充填することによって炭化珪素が
本来持っている耐熱温度１で長時間の使用に耐え、従来
のセラミックス材料では得られなかった熱交換器を提供
するものである。Therefore, in the product of the present invention, high purity silicon carbide is used, and F'P is 500 ppm or less in terms of metal, At
By setting the NA to 1000 ppm or less and the NA to 100 ppm or less, and by filling the pores of the formed silicon carbide molded body with high-purity silicon, it can withstand long-term use at the heat-resistant temperature 1 that silicon carbide originally has, and is This provides a heat exchanger that cannot be obtained using ceramic materials.
以下に本発明の詳細な説明する。The present invention will be explained in detail below.
先ず常法により再結晶炭化珪素成形体を得で試片とした
。First, a recrystallized silicon carbide molded body was obtained by a conventional method to prepare a specimen.
即ち、炭化珪素粉及び炭素粉をフェノールレジンを使用
してパイプ状に成形し、これを炭化焼成した後これを二
分し、一方を、ＨＣｌ ガスによって純化処理し、他
方をそのま＼でいずれにも超高純度シリコンを含浸させ
た。That is, silicon carbide powder and carbon powder are formed into a pipe shape using phenol resin, carbonized and fired, and then divided into two parts. One part is purified with HCl gas, and the other part is left as is. Also impregnated with ultra-high purity silicon.
これらの密度はいずれも３．１ｏ±０．０５’／ｃｃで
あり、室温における曲げ強度は５００〜５５０ＭＰｆＬ
の範囲内にあって、相互の純度と曲げ強度の関係の相関
関係は明確てｄ：ながった。これらを１３５０″Ｇに一
加熱し、パイプ内部に空気及び２係の８０２ガスを含む
重油燃＃、廃ガスを流して１０００時間熱処理した。The density of these is 3.1o±0.05'/cc, and the bending strength at room temperature is 500-550MPfL.
Within the range of d:, the correlation between purity and bending strength was clear. These were heated to 1,350″G, and heat-treated for 1,000 hours by flowing air, heavy oil fuel containing 802 gas from the second stage, and waste gas into the pipe.
その重量増加（減少）及び曲げ強度を測定した結果を表
１に示す。又純化処理したものの自然空気対流下で１３
５０℃に熱処理した場合の経時変化を表２に示す。Table 1 shows the results of measuring the weight increase (decrease) and bending strength. Also, after purification treatment, under natural air convection, 13
Table 2 shows changes over time when heat treated at 50°C.
表１において、実施例１及び参考例１〜３は空気酸化さ
せた場合、実施例２及び参考例４〜６は２チＳ０２含有
の重油燃焼廃ガスによって処理した場合を示している。In Table 1, Example 1 and Reference Examples 1 to 3 show cases in which air oxidation was performed, and Example 2 and Reference Examples 4 to 6 show cases in which treatment was performed with heavy oil combustion waste gas containing 20% S02.
表−２
その結果、実施例１及び２のものケ：を明らかに酸化増
π及び強ハ［変化かり１とんど認と）られす、又不純物
含有量の多いものけ明らかに強度が低下している。尚、
実施例２及び参考例４〜６のものは酸化増量がマイナス
を示しているが、これは詳細な理由は明らかで超−ない
が、おそらく生成した５ｉ０２質被膜が８０２ガスと何
らかの反応を起し、これが揮散することによって減量し
たものと思われる。少なくとも５ｉｎ２ 買被ｊ摸の
形成され易いもの程酸化減量が多くなっており、強度の
低下は特に著しい。Table 2 As a result, the samples of Examples 1 and 2 had a clear oxidation increase in π and the strength [change was almost 1 perceptible], and the samples with a large impurity content had a clear decrease in strength. are doing. still,
The oxidation weight gain of Example 2 and Reference Examples 4 to 6 is negative, and although the detailed reason for this is not clear, it is probably because the formed 5i02 film undergoes some kind of reaction with the 802 gas. , it is thought that the weight was reduced by volatilization. The easier the formation of at least 5 in 2 particles, the greater the oxidation loss, and the decrease in strength is particularly significant.
本発明においてシリコンを充填させ、：） 、１４ ト
ｌ］←１゜再結晶炭化珪素成形体は気孔率が高い／ヒト
）ガス透過性があり、このオまでは隔壁を通じて高温流
体と低温流体の混合か起り熱交換器として適さない。従
って、これをガス不透過性とするためにシリコンを含浸
するものである。その徂：Ｃよ成形体の全ての気孔に充
填されるもの７５（好ましいが、含浸後の気孔率が３チ
以下り）場合にはりＳ用−Ｆ何等不都合ｉ１．ｌ：ない
。In the present invention, the recrystallized silicon carbide molded body is filled with silicon and has a high porosity/human) gas permeability, and up to this point, high-temperature fluid and low-temperature fluid can pass through the partition wall. Not suitable as a mixing or originating heat exchanger. Therefore, it is impregnated with silicon to make it gas impermeable. The following: If all pores of the molded body are filled with C (preferably, but the porosity after impregnation is less than 3 inches), then -F for beam S is inconvenient i1. l:No.
この場合、再結晶炭化珪素成形体の気孔率によってシリ
コン含有量は変化する。熱交換器（とし７て機能するだ
めの強度に影響を力えない範囲で炭化珪素成形体の気孔
率を求めなけｉｚばならないが、そのｆｉ４： ｌＩ’
、 ６．５〜３５％が適当でＪ）す、従って充填さｊし
るシリコンのチ、）も６．５〜３５重量％となることに
なる。（このｊ、［％合、炭イし珪素とシリコンの比重
の差が小さいだめその換ｆ′Ｐ−は無視した。）
実施例においては炭化珪素成形体は再結晶炭化珪素とし
たが、−吹成形体に直接シリコンを含浸させたものでよ
い。更にシリコンを充填した高純度炭化珪素成形体にＣ
ＶＤ法によって炭化珪素を被覆させたものは、この被膜
自体が緻密であり、これ自身が耐酸化耐蝕性に富んだも
のであるため、より一層すぐれた機能を発揮させること
ができる。In this case, the silicon content changes depending on the porosity of the recrystallized silicon carbide molded body. The porosity of the silicon carbide molded body must be determined within a range that does not affect the strength of the vessel that functions as a heat exchanger (fi4: lI'
, 6.5 to 35% by weight is suitable. Therefore, the amount of silicon to be filled is also 6.5 to 35% by weight. (Because the difference in specific gravity between silicon carbide and silicon is small, j, [% ratio, and f'P- are ignored.) In the examples, the silicon carbide molded body was recrystallized silicon carbide, but - A blow-molded body directly impregnated with silicone may be used. Furthermore, C is added to the high-purity silicon carbide molded body filled with silicon.
A product coated with silicon carbide by the VD method has a dense film itself and is highly resistant to oxidation and corrosion, so it can exhibit even better functionality.
本発明によって期待できる効果は形状の単純な二重管式
のみ寿らず、一般に知られている多管式のものでもよく
、又自動車用等のガスタービンエンジンの蓄熱式、伝熱
式の形式にとられれることもなく応用が可能であシ、更
に熱交換器全部に適用する場合だけでなく、必要最小限
の部分のみに適用することも可能である。The effects that can be expected from the present invention are not limited to the simple double-tube type, but also the commonly known multi-tube type, and the heat storage type and heat transfer type of gas turbine engines for automobiles etc. Furthermore, it can be applied not only to the entire heat exchanger, but also to only the minimum necessary part.
Claims (4)
る方式の熱交換器において、該隔壁の少なくとも一部が
、気孔中にシリコンが充填された再結晶炭化珪素成形体
から成り、かつ不純物含有割合が金属状態に換算してＦ
Ｆｅ５００ｐｐ以下、Ａｌ １０００ ｐｐｍ以下、Ｎ
ａ１００ ｐｐｍ以下であることを特徴とする炭化珪素
質熱交換器０(1) In a heat exchanger of a type in which a low-temperature fluid is heated by a high-temperature fluid through a partition wall, at least a part of the partition wall is made of a recrystallized silicon carbide compact whose pores are filled with silicon, and contains impurities. The ratio is F when converted to metal state.
Fe 500ppm or less, Al 1000ppm or less, N
Silicon carbide heat exchanger 0 characterized by having a content of 100 ppm or less
３５重量％であることを特徴とする特許請求の範囲第１
項記載の熱交換器。(2) The silicon content ratio filled in the pores is 6.5~
Claim 1 characterized in that the amount is 35% by weight.
Heat exchanger as described in section.
形体の気孔率が３チ以下であることを特徴とする特許請
求の範囲第１項及び第２項記載の熱交換器。(3) The heat exchanger according to claims 1 and 2, wherein the recrystallized silicon carbide molded body whose pores are filled with silicon has a porosity of 3 or less.
膜が被色されていることをｑｔ（、、徴とする特許請求
の範囲第１項乃至第３項記載の熱交換器。(4) The heat exchanger according to any one of claims 1 to 3, characterized in that at least a part of the surface of the silicon carbide film is colored by a CVD method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15776282A JPS5946491A (en) | 1982-09-10 | 1982-09-10 | Heat exchanger of silicon carbide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15776282A JPS5946491A (en) | 1982-09-10 | 1982-09-10 | Heat exchanger of silicon carbide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5946491A true JPS5946491A (en) | 1984-03-15 |
| JPH026998B2 JPH026998B2 (en) | 1990-02-14 |
Family
ID=15656757
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15776282A Granted JPS5946491A (en) | 1982-09-10 | 1982-09-10 | Heat exchanger of silicon carbide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5946491A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB928683A (en) * | 1958-10-23 | 1963-06-12 | Siemens Ag | A method of producing highly purified silicon carbide |
| US3951587A (en) * | 1974-12-06 | 1976-04-20 | Norton Company | Silicon carbide diffusion furnace components |
| JPS52145419A (en) * | 1976-05-29 | 1977-12-03 | Toshiba Ceramics Co | Manufacture of silicon carbide articles for semiconductor production |
| US4070197A (en) * | 1975-06-25 | 1978-01-24 | Norton Company | Gas tight silicon carbide body |
| JPS5410825A (en) * | 1977-06-24 | 1979-01-26 | Kawasaki Heavy Ind Ltd | Prefiring preventing arrangement for two cycle engine |
| JPS555852A (en) * | 1978-06-28 | 1980-01-17 | Toyo Boseki | Evaporated polyester film |
-
1982
- 1982-09-10 JP JP15776282A patent/JPS5946491A/en active Granted
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB928683A (en) * | 1958-10-23 | 1963-06-12 | Siemens Ag | A method of producing highly purified silicon carbide |
| US3951587A (en) * | 1974-12-06 | 1976-04-20 | Norton Company | Silicon carbide diffusion furnace components |
| US4070197A (en) * | 1975-06-25 | 1978-01-24 | Norton Company | Gas tight silicon carbide body |
| JPS52145419A (en) * | 1976-05-29 | 1977-12-03 | Toshiba Ceramics Co | Manufacture of silicon carbide articles for semiconductor production |
| JPS5410825A (en) * | 1977-06-24 | 1979-01-26 | Kawasaki Heavy Ind Ltd | Prefiring preventing arrangement for two cycle engine |
| JPS555852A (en) * | 1978-06-28 | 1980-01-17 | Toyo Boseki | Evaporated polyester film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH026998B2 (en) | 1990-02-14 |
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