JPH0625035B2 - Method for producing heat-resistant and corrosion-resistant sintered body - Google Patents
Method for producing heat-resistant and corrosion-resistant sintered bodyInfo
- Publication number
- JPH0625035B2 JPH0625035B2 JP63249785A JP24978588A JPH0625035B2 JP H0625035 B2 JPH0625035 B2 JP H0625035B2 JP 63249785 A JP63249785 A JP 63249785A JP 24978588 A JP24978588 A JP 24978588A JP H0625035 B2 JPH0625035 B2 JP H0625035B2
- Authority
- JP
- Japan
- Prior art keywords
- resistant
- sintered body
- corrosion
- present
- sintering
- 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.)
- Expired - Lifetime
Links
- 238000005260 corrosion Methods 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 230000007797 corrosion Effects 0.000 title description 11
- 238000010304 firing Methods 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000011651 chromium Substances 0.000 description 12
- 238000005245 sintering Methods 0.000 description 10
- 239000002131 composite material Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000035939 shock Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910003470 tongbaite Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- -1 borides Chemical class 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007676 flexural strength test Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001272 pressureless sintering Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Products (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、耐熱耐食性焼結体の製造方法に関するもので
ある。本発明によって得られた焼結体は、加熱炉、均熱
炉などの工業用炉や溶融金属に対し優れた耐食性を備え
ているため熱電対の保護管等での使用が期待されるもの
である。The present invention relates to a method for producing a heat-resistant and corrosion-resistant sintered body. Since the sintered body obtained by the present invention has excellent corrosion resistance to industrial furnaces such as heating furnaces and soaking furnaces and molten metal, it is expected to be used in protective tubes for thermocouples and the like. is there.
Cr3C2系セラミック材料は、従来、金属のニッケルやコ
バルトで結合焼結したものや、各種酸化物、窒化物、硼
化物、炭化物、リン化物を焼結助剤として焼結したもの
が提案されている。そして、焼結助剤の添加量は０．５
〜１０重量％で焼結温度は１５００℃以下とされてい
る。Conventionally, Cr 3 C 2 based ceramic materials have been proposed by combining and sintering metal nickel or cobalt, or by sintering various oxides, nitrides, borides, carbides, and phosphides as sintering aids. Has been done. And the addition amount of the sintering aid is 0.5
The sintering temperature is set to 1500 ° C. or lower at 10% by weight.
（特開昭５９−１０７０５８号公報）。(JP-A-59-107058).
しかしながら、耐食性が優れているだけでは実用上問題
が有り、耐熱衝撃性、耐摩耗性、高温強度等の物性が良
好であることが要求される。 Cr3C2系セラミックでこれ
らの条件を全て満すものは無く、本発明はこれらの点を
全て改善したものである。これ迄に１つの改善例として
Cr3C2 の耐熱衝撃性を高めるために各種ウイスカー、フ
アイバーを混入することが示されているが充分な効果が
得られていない。However, only excellent corrosion resistance poses a practical problem, and it is required to have good physical properties such as thermal shock resistance, abrasion resistance, and high temperature strength. No Cr 3 C 2 based ceramic satisfies all of these conditions, and the present invention improves all of these points. As one improvement example so far
It has been shown that various whiskers and fibers are mixed in to improve the thermal shock resistance of Cr 3 C 2 , but sufficient effects have not been obtained.
耐熱衝撃性が良くないのは Cr3C2の熱膨張率が大きいた
めであるので、これを改善するためには複合材をある程
度以上添加して本質的に組織を変える必要がある。本発
明は複合材の添加と焼成温度を従来より高くすることに
よって物性の改良に成功したものである。The reason why the thermal shock resistance is not good is that the thermal expansion coefficient of Cr 3 C 2 is large, and in order to improve this, it is necessary to add a composite material to a certain extent or more and essentially change the structure. The present invention succeeded in improving the physical properties by adding the composite material and raising the firing temperature higher than before.
すなわち、本発明は、ZrB2、TiB2、TiC 、SiC及び TiN
から選ばれた１種以上が０．５〜５０重量％で残部が実
質的に Cr3C2である混合物を温度１６００℃以上で焼成
することを特徴とする耐熱耐食性焼結体の製造方法であ
る。That is, the present invention provides ZrB 2 , TiB 2 , TiC, SiC and TiN.
A method for producing a heat-resistant and corrosion-resistant sintered body, which comprises firing a mixture in which at least one selected from 0.5 to 50% by weight and the balance being substantially Cr 3 C 2 at a temperature of 1600 ° C. or higher. is there.
以下、さらに詳しく本発明について説明する。複合材と
して ZrB2 、 TiB2 、 TiC、SiC 、 TiNを選んだ理由
は、これらが Cr3C2の焼結性を促進する効果を有するだ
けでなく、耐食性、耐熱衝撃性、硬度、強度、破壊靱性
を高める働きをするからである。The present invention will be described in more detail below. ZrB 2, TiB 2, TiC as a composite material, SiC, reason for choosing TiN, not only they have the effect of promoting the sintering of the Cr 3 C 2, corrosion resistance, thermal shock resistance, hardness, strength, This is because it works to increase fracture toughness.
本発明に用いる Cr3C2は純度９９％以上、平均粒径５μ
ｍ以下特に１μｍ以下が好ましく、同様に複合材の ZrB
2 、 TiB2 、 TiC、SiC 、 TiNについても純度９９％以
上、平均粒径１０μｍ以下特に５μｍ以下が好ましい。Cr 3 C 2 used in the present invention has a purity of 99% or more and an average particle size of 5μ.
m or less, especially 1 μm or less, and similarly, ZrB of composite material
With respect to 2 , TiB 2 , TiC, SiC and TiN, the purity is preferably 99% or more and the average particle size is 10 μm or less, particularly 5 μm or less.
通常、これらの微粉末の混合物はそれぞれの微粉末を均
一に混合する事により得られるが、同時に粉砕混合して
も良い。混合物の粒度としては平均粒径１０μｍ以下好
ましくは１μｍ以下である。Usually, a mixture of these fine powders is obtained by uniformly mixing the fine powders, but they may be pulverized and mixed at the same time. The particle size of the mixture is 10 μm or less, preferably 1 μm or less.
粉砕方法としては湿式、乾式が採用される。A wet method or a dry method is adopted as the crushing method.
本発明の焼結体は前記混合物を真空中、アルゴン、ヘリ
ウム、窒素などの中性あるいは還元性の雰囲気下でホッ
トプレス法かプレス成型後常圧焼結法によって得ること
ができる。炭化クロム系セラミックの焼成温度は、従来
１５００℃以下が良いとされていたが、本発明では１６
００℃以上の焼成温度が必要であることを見い出したも
のである。焼成時間については３０分〜１０時間程度で
あるが、原料組成、原料粒度により適宜選択される。ま
た焼結方法としては常圧焼結、ホツプレス焼結さらにＨ
ＩＰ法も有効である。The sintered body of the present invention can be obtained by subjecting the mixture to a hot press method or a pressureless sintering method after press molding in a neutral or reducing atmosphere such as argon, helium or nitrogen in a vacuum. The firing temperature of chromium carbide-based ceramics has been conventionally considered to be 1500 ° C. or lower, but in the present invention, it is 16
It was found that a firing temperature of 00 ° C. or higher is necessary. The firing time is about 30 minutes to 10 hours, and is appropriately selected depending on the raw material composition and the raw material particle size. The sintering methods include atmospheric pressure sintering, hot press sintering and H
The IP method is also effective.
本発明の ZrB2 、 TiB2 、 TiC、SiC 、 TiNの少なくと
も１種以上からなる複合材の添加量は０．５〜５０重量
％である。０．５重量％未満では焼結性、強度、硬度な
どの面で充分でなく、一方、５０重量％をこえては Cr3
C2本来の性質が損われる。The additive amount of the composite material of the present invention made of at least one of ZrB 2 , TiB 2 , TiC, SiC and TiN is 0.5 to 50% by weight. If it is less than 0.5% by weight, the sinterability, strength and hardness are not sufficient, while if it exceeds 50% by weight, Cr 3
The original properties of C 2 are impaired.
これら複合材の効果としては、焼結性の向上と CR3C2の
微細な結晶を析出させることによって高強度、高靱性化
するだけでなく複合材固有の性質である高融点、高硬
度、高耐食性等の性能を付与できるものである。本発明
の複合材の組み合せにより特性の異った焼結体を製造す
ることも可能である。The effects of these composite materials are not only high strength and high toughness due to improvement of sinterability and precipitation of fine crystals of CR 3 C 2 , but also high melting point, high hardness, which are properties unique to composite materials, It is possible to impart performances such as high corrosion resistance. It is also possible to produce sintered bodies having different characteristics by combining the composite materials of the present invention.
炭化クロムには Cr3C2以外に Cr7C3、 Cr4C 等が知らて
いるが、これらを本発明に用いることもできる。Although Cr 7 C 3 , Cr 4 C and the like are known as chromium carbide in addition to Cr 3 C 2 , these can also be used in the present invention.
実施例１ 純度９９％以上の Cr3C2粉末（平均粒径４〜５μｍ）と
ZrB2 、 TiB2 、 TiC、SiC 、 TiNの各粉末（平均粒径
３〜４μｍ）の１種以上を所定量計量後ボールミル混合
した後ＣＩＰ（２．７ton ／cm2、３分間）成型し真空
雰囲気下において所定の温度、時間で常圧焼結した。得
られた焼結体の物性を表−１に示す。実験No.１〜８は
比較例、実験No.９〜２２は本発明例である。Example 1 Cr 3 C 2 powder having a purity of 99% or more (average particle size 4 to 5 μm)
A predetermined amount of one or more of ZrB 2 , TiB 2 , TiC, SiC, and TiN powders (average particle diameter 3 to 4 μm) was weighed in a predetermined amount, mixed in a ball mill, and then CIP (2.7 ton / cm 2 , 3 minutes) and vacuum formed. Sintering was carried out under atmospheric pressure at a predetermined temperature for a predetermined time. Table 1 shows the physical properties of the obtained sintered body. Experiment Nos. 1 to 8 are comparative examples, and Experiments Nos. 9 to 22 are examples of the present invention.
なお、表に示した物性は次のようにして測定した。The physical properties shown in the table were measured as follows.
(1) 耐熱衝撃性は、急冷強度測定法で求めた。供試体
は３×４×４０mmの曲げ強度試験片を用い、電気炉内で
所定の温度で加熱し、一定時間（１時間）保持後炉の下
に設置してある０℃の水中へ降下させて試験片を急冷し
た。その試験片の曲げ強度を測定し強度が低下したとき
の加熱温度と水の温度（０℃）との差をΔＴとした。(1) The thermal shock resistance was determined by the quenching strength measurement method. The test piece is a 3 × 4 × 40 mm flexural strength test piece, heated at a predetermined temperature in an electric furnace, held for a certain time (1 hour), and then lowered into water at 0 ° C. installed under the furnace. The test piece was quenched. The bending strength of the test piece was measured, and the difference between the heating temperature and the water temperature (0 ° C.) when the strength decreased was defined as ΔT.
(2) 耐食性は、３×４×４０mmの試験片を４５０℃、
１時間Ar雰囲気下で鉛の溶湯に浸漬しその侵食量から判
定した。侵食量は腐食部分、スケール等を削り落した後
の重量減少とした。(2) Corrosion resistance is measured at 450 ℃ for 3 × 4 × 40mm test pieces.
It was immersed in a molten lead for 1 hour in an Ar atmosphere and judged from the amount of corrosion. The amount of erosion was defined as the weight loss after scraping off the corroded parts and scales.
○……異状なし、△……やや侵食、×……かなり侵食 (3) 相対密度はアルキメデス法で測定した。○ …… No abnormality, △ …… Slightly eroded, × …… Remarkably eroded (3) The relative density was measured by the Archimedes method.
本実施例（実験No.９〜２２）は、比較例（実験No.１〜
８）に比べて耐熱衝撃性と耐食性が共に優れていること
がわかる。 This example (Experiment No. 9 to 22) is a comparative example (Experiment No. 1 to No. 1).
It can be seen that both thermal shock resistance and corrosion resistance are superior to 8).
実施例２ 実施例１の実験No.１３について焼成温度を変えて相対
密度を求めた。その結果を表−２に示す。実験No.２３
〜２５は比較例、実験No.２６〜２７は本発明例であ
る。これより焼成温度としては、１６００℃以上が必要
であることがわかる。Example 2 Regarding Experiment No. 13 of Example 1, the relative density was obtained by changing the firing temperature. The results are shown in Table-2. Experiment No.23
25 to 25 are comparative examples, and Experiment Nos. 26 to 27 are examples of the present invention. From this, it can be seen that the firing temperature needs to be 1600 ° C. or higher.
〔発明の効果〕 本発明によって得られた耐熱耐食性焼結体は、高強度、
高耐食、耐熱衝撃性、導電性等に優れているので、熱電
対の保護管、金属加工用ダイス、ヒーター、温度センサ
ー等の幅広い分野で使用することができる。また、金属
と同様に放電加工ができるので複雑形状品にも容易に対
応することができる。 [Effects of the Invention] The heat-corrosion-resistant sintered body obtained by the present invention has high strength,
Since it has excellent corrosion resistance, thermal shock resistance, and conductivity, it can be used in a wide range of fields such as thermocouple protection tubes, metal working dies, heaters, and temperature sensors. Further, since it is possible to perform electric discharge machining like metal, it is possible to easily deal with a product having a complicated shape.
Claims (1)
選ばれた１種以上が０．５〜５０重量％で残部が実質的
に Cr3C2である混合物を温度１６００℃以上で焼成する
ことを特徴とする耐熱耐食性焼結体の製造方法。1. A mixture comprising 0.5 to 50% by weight of one or more selected from ZrB 2 , TiB 2 , TiC, SiC and TiN and the balance being substantially Cr 3 C 2 at a temperature of 1600 ° C. or higher. A method for producing a heat-corrosion-resistant sintered body, which comprises firing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63249785A JPH0625035B2 (en) | 1987-10-06 | 1988-10-05 | Method for producing heat-resistant and corrosion-resistant sintered body |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62-250727 | 1987-10-06 | ||
| JP25072787 | 1987-10-06 | ||
| JP63249785A JPH0625035B2 (en) | 1987-10-06 | 1988-10-05 | Method for producing heat-resistant and corrosion-resistant sintered body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01201076A JPH01201076A (en) | 1989-08-14 |
| JPH0625035B2 true JPH0625035B2 (en) | 1994-04-06 |
Family
ID=26539487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63249785A Expired - Lifetime JPH0625035B2 (en) | 1987-10-06 | 1988-10-05 | Method for producing heat-resistant and corrosion-resistant sintered body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0625035B2 (en) |
-
1988
- 1988-10-05 JP JP63249785A patent/JPH0625035B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01201076A (en) | 1989-08-14 |
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