JP2007112712A - Drawing die - Google Patents
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- JP2007112712A JP2007112712A JP2006312494A JP2006312494A JP2007112712A JP 2007112712 A JP2007112712 A JP 2007112712A JP 2006312494 A JP2006312494 A JP 2006312494A JP 2006312494 A JP2006312494 A JP 2006312494A JP 2007112712 A JP2007112712 A JP 2007112712A
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Abstract
Description
本発明は、低摩擦で耐食性、耐摩耗性に優れたジルコニア製の金型部材に関するものであり、例えばボタン電池に使用するステンレス鋼板等の外装ケースを絞り形成加工する工程においてのダイスやパンチ等の金型として好適なものである。 The present invention relates to a die member made of zirconia having low friction and excellent corrosion resistance and wear resistance. For example, a die, a punch or the like in a drawing process of an outer case such as a stainless steel plate used for a button battery It is suitable as a metal mold.
従来、例えば、ボタン電池の外装ステンレス鋼板を絞り形成する金型部材には、高強度で安定した以下の要件が望まれている。 2. Description of the Related Art Conventionally, for example, a mold member for drawing a button battery outer stainless steel plate is required to have the following high and stable requirements.
1)耐摩耗性、耐食性に優れること。 1) Excellent wear resistance and corrosion resistance.
2)ステンレス鋼などの金属との摺動特性が良いこと(低摩擦係数を有すること)。 2) Good sliding properties with metals such as stainless steel (having a low coefficient of friction).
3)衝撃を加えても破損しないこと。 3) It should not be damaged by impact.
4)熱的安定素材であること(凝着反応が起こり難いこと)。 4) It is a thermally stable material (adhesion reaction is unlikely to occur).
そして、このような特性を満足するために、絞り金型部材の材質として、酸化イットリウムを安定化剤として含む一般的なジルコニアセラミックス(特許文献1を参照。)または、これら硬質素材に窒化チタンやDLCコーティングを施したものが多くみられた。
しかしながら、上記セラミックの素材およびこの素材に窒化チタンやDLCコーティングを施した絞り金型は、いずれも全ての要求を満足するものではなかった。 However, none of the ceramic material and the drawing die in which titanium nitride or DLC coating is applied to this material satisfy all the requirements.
即ち、従来のイットリアやマグネシアの安定化剤からなるジルコニアセラミックス製絞り金型は、摩擦係数が高く、熱的安定性も乏しく、被絞り素材を痛めてしまう等の課題があった。 That is, the conventional zirconia ceramic drawing die made of a yttria or magnesia stabilizer has problems such as a high friction coefficient, poor thermal stability, and damage to the drawn material.
さらに、上記硬質素材に窒化チタンやDLCコーティングなどのコーティングを施した絞り金型は、熱膨張係数の違いから剥離が起こり、摩耗し易く寿命が短いといった課題があった。 Furthermore, the drawing die in which the hard material is coated with titanium nitride, DLC coating or the like has a problem that peeling occurs due to a difference in thermal expansion coefficient, and it is easily worn and has a short life.
本発明の目的は、低摩擦で腐食や摩耗が少なく長寿命である絞り金型部材、例えば、ボタン電池用の外装ステンレスケースを絞り形成するのに優れ、外装ケースにダメージを与えることのない絞り金型を提供することにある。 The object of the present invention is to draw a die member having a low friction, corrosion and wear and a long service life, for example, an outer stainless steel case for a button battery, and to prevent the outer case from being damaged. To provide molds.
本発明の絞り金型は、アルミナ(Al2O3)を3.0〜25.0重量%、酸化ディスプロシウム(Dy2O3)およびセリア(CeO2)の少なくとも一方を8.0〜13.0重量%、カーボンを0.8〜4.0重量%、残部がジルコニア(ZrO2)の組成を持ったセラミックスからなることを特徴とする。即ち、本発明は、絞り金型を形成するジルコニアを酸化ディスプロシウム(Dy2O3)およびセリア(CeO2)の少なくとも一方の安定化剤によって部分安定化させ、これとアルミナ(Al2O3)とカーボン(TiCを含む)とを含むセラミックスで形成したことを特徴とする。 The drawing die of the present invention comprises alumina (Al 2 O 3 ) of 3.0 to 25.0 wt%, at least one of dysprosium oxide (Dy 2 O 3 ) and ceria (CeO 2 ) of 8.0 to 13.0 wt%, and carbon. It is characterized by being made of ceramics having a composition of 0.8 to 4.0% by weight and the balance being zirconia (ZrO 2 ). That is, according to the present invention, zirconia forming a drawing die is partially stabilized by at least one stabilizer of dysprosium oxide (Dy 2 O 3 ) and ceria (CeO 2 ), and this is mixed with alumina (Al 2 O 3 ) and ceramics containing carbon (including TiC).
上記組成において、耐食性に優れたジルコニアに高硬度と高強度を得るためにアルミナを添加したが、アルミナが3.0重量%未満では高強度、高硬度の効果が得られず、アルミナが25.0重量%を超えると強度が低下する。 In the above composition, alumina was added to zirconia with excellent corrosion resistance in order to obtain high hardness and high strength, but if the alumina was less than 3.0% by weight, the effect of high strength and high hardness could not be obtained, and alumina was 25.0% by weight. If it exceeds, the strength decreases.
また、安定化剤として添加する酸化ディスプロシウム(Dy2O3)およびセリア(CeO2)の少なくとも一方は、8.0重量%未満であればジルコニア特有の応力誘起変態が有効に起動せず、13.0重量%を超えると焼結性が著しく低下することで粒子間空孔が大きく残留し、結果として強度低下となる。 If at least one of dysprosium oxide (Dy 2 O 3 ) and ceria (CeO 2 ) added as a stabilizer is less than 8.0% by weight, stress-induced transformation peculiar to zirconia does not start effectively, and 13.0 If it exceeds wt%, the sinterability is significantly reduced, leaving large interparticle voids, resulting in a decrease in strength.
また、摺動特性を著しく高くするために含有カーボン量は0.8重量%以上必要となるが、4.0重量%を超えると焼結性が著しく低下する。 In addition, the carbon content is required to be 0.8% by weight or more in order to remarkably improve the sliding characteristics, but if it exceeds 4.0% by weight, the sinterability is significantly lowered.
なお、これらセリア/ディスプロ系安定化剤を用いたジルコニア素材で絞り金型を作製すると、ステンレス鋼板等の被ステンレス金属を絞り加工するときの熱的影響が著しく少なく、安定的な特性を維持することができる。 In addition, when a drawing die is made of a zirconia material using these ceria / displo stabilizers, the thermal effect when drawing a stainless steel plate such as a stainless steel plate is extremely small, and stable characteristics are maintained. be able to.
本発明のジルコニアとアルミナとカーボンとを含むセラミックスで作製した絞り金型によれば、被加工物のステンレス鋼との粒間置換反応が防止でき、さらに高摺動性(低摩擦係数)を有することから、著しく耐摩耗性に優れたものが得られる。 According to the squeezing die made of a ceramic containing zirconia, alumina and carbon according to the present invention, intergranular substitution reaction with the stainless steel of the work piece can be prevented, and furthermore, it has high slidability (low friction coefficient). For this reason, a material having remarkably excellent wear resistance can be obtained.
これにより従来の超硬材と比較して、使用上何ら支障のない硬度、強度および耐食性を有する絞り金型を得ることができる。 As a result, it is possible to obtain a drawing die having hardness, strength and corrosion resistance which does not hinder use in comparison with conventional cemented carbide.
この結果、長期に渡り腐食や摩耗が発生しない摺動部材、および耐摩耗部材として好適に用いることができる。 As a result, it can be suitably used as a sliding member that does not cause corrosion or wear over a long period of time and a wear-resistant member.
図2に示すように、絞り金型は、ダイス6と打ち抜きパンチ7とによって構成される。
As shown in FIG. 2, the drawing die is constituted by a
そして、ニッケルメッキ鋼板1aをダイス6とこれに対応した打ち抜きパンチ7とによって円盤状に打ち抜き、絞り出す。打ち抜かれたステンレス鋼板はダイス6内に押し込まれる際に、切断面をダイス6の側面でシゴかれて打ち抜きに伴うバリ等が除去される。さらに打ち抜きパンチ7がダイス6内に進入し、打ち抜きパンチ7中央部の絞り用受け8と、ダイス6内の絞り用ポンチ9の上昇とに伴う絞り加工により、図2(b)に示すようなボタン型電池の円盤状の外装ケース1bが形成される。
Then, the nickel-plated
本発明によれば、上記ダイス6、打ち抜きパンチ7等の部材を上述したようなジルコニアとアルミナとカーボンとを含むセラミックスで形成することにより、耐久性に優れた絞り金型を得ることができる。
According to the present invention, a drawing die having excellent durability can be obtained by forming members such as the
上記のようにして得られた外装ケース1bをさらに変形させて図1に示すような正極外装ケース1とし、正極電池層3、セパレータ5、負極電池層4を収納して負極封口板2で覆うことによって、ボタン電池を形成する。
The
以下に本発明を実施例で説明する。 Hereinafter, the present invention will be described with reference to examples.
セリア/ディスプロ安定化剤を含むジルコニア粉末と高純度のアルミナ粉末とを所定の量比で配合し、15時間混合粉砕した。 A zirconia powder containing a ceria / displo stabilizer and a high-purity alumina powder were blended at a predetermined quantitative ratio, and mixed and ground for 15 hours.
これを乾燥後、パラフィンワックスを4重量%添加し、1.0ton/cm2の圧力で加圧成形したものを大気雰囲気にて1300℃にて1時間焼成した後に、1500気圧にてHIP処理を施した。 After drying this, 4% by weight of paraffin wax was added and pressure-molded at a pressure of 1.0 ton / cm 2 baked at 1300 ° C. for 1 hour in an air atmosphere and then subjected to HIP treatment at 1500 atm. did.
前記焼結体を粉砕して、ICP(発光分光定量分析装置)により定量分析して得られた値と蛍光X線装置により定性・定量分析して得られた値とを比率換算したものを焼結体組成として表1〜表4に示す。また、同表に示す特性値は以下の方法で評価して得られたものである。 The sintered body is pulverized, and the value obtained by quantitative analysis with an ICP (Emission Spectrometric Quantitative Analysis Device) and the value obtained by qualitative / quantitative analysis with a fluorescent X-ray device are ratio-converted. It shows in Table 1-Table 4 as a body composition. The characteristic values shown in the table are obtained by evaluating by the following method.
得られた焼結体の表面を研削した後、抗折強度を測定した。 After grinding the surface of the obtained sintered body, the bending strength was measured.
また、鏡面研磨した後、ビッカース硬度、摩擦係数、耐摩耗性、抗折強度の測定を行なった。 Further, after mirror polishing, measurements of Vickers hardness, friction coefficient, abrasion resistance, and bending strength were performed.
抗折強度はJISR1601の3点曲げ試験法に従い、ビッカース硬度の測定はJISZ2244試験法に従った。 The bending strength was in accordance with the three-point bending test method of JISR1601, and the Vickers hardness was measured in accordance with the JISZ2244 test method.
摩擦係数の測定および耐摩耗性の評価は、図3に示すようにJISR1613試験方法で、ステンレス(SUS303)製のボール11を用い、各種材質のディスク10上に負荷荷重12を加えながら摺動させるボールオンディスク試験にて行なった。
As shown in FIG. 3, the friction coefficient is measured and the wear resistance is evaluated by a JIS R1613 test method, using a
なお、摩擦係数(μ値=摩擦力(荷重0.5kg・速度0.17m/s・時間10min)/負荷荷重値)と耐摩耗性の評価結果として、摺動部の摩耗痕が確認できないものは◎とし、摩耗痕の深さが1μm以下のものは○とし、深さが1μm以上のものは×とし、ステンレス(SUS303)ボールが凝着したものは△として表した。
この結果として、耐食性に優れたジルコニアは表1の試料No.1の一般的ジルコニアの様にアルミナの比率が3.0重量%以下であれば、表2の試料No.1の様に強度・硬度が低く、表1の試料No.9および試料No.10の一般的なアルミナはアルミナが25.0重量%を超え、表2の試料No.9・試料No.10の様に強度が著しく低下する。 As a result, the zirconia having excellent corrosion resistance was obtained as a sample No. 1 in Table 1. If the alumina ratio is 3.0% by weight or less like the general zirconia of No. 1, the sample No. The strength and hardness are low as shown in FIG. 9 and sample no. The general alumina of 10 has alumina exceeding 25.0% by weight. 9. Sample No. As in 10, the strength decreases significantly.
安定化剤として添加する酸化ディスプロシウム(Dy2O3)およびセリア(CeO2)の少なくとも一方は、表1の試料No.1・試料No.3・試料No.8・試料No.10の様に8.0重量%以下であれば、表2の試料No.1・試料No.3・試料No.8・試料No.10の様に強度が著しく低下し、表1の試料No.7の様に13.0重量%以上であっても、表2の試料No.7の様に強度低下となる。 At least one of dysprosium oxide (Dy 2 O 3 ) and ceria (CeO 2 ) added as a stabilizer is the sample No. 1 in Table 1. 1. Sample No. 3. Sample No. 8. Sample No. If it is 8.0% by weight or less as shown in FIG. 1. Sample No. 3. Sample No. 8. Sample No. As shown in FIG. Even if it is 13.0% by weight or more as shown in FIG. As shown in FIG.
カーボン含有量は表1の試料No.1・試料No.10の様に0.8重量%以下であれば、表2の試料No.1および試料No.10の様に摺動性が低下し、表1の試料No.9の様に4.0重量%以上となると、表2の試料No.9の様に強度が著しく低下、つまり焼結性が著しく低下する。 The carbon content is the sample No. in Table 1. 1. Sample No. If it is 0.8 wt% or less as shown in FIG. 1 and sample no. As shown in FIG. As shown in FIG. As in 9, the strength is significantly reduced, that is, the sinterability is significantly reduced.
よって、範囲外のものは不適である。 Therefore, those outside the range are unsuitable.
1:正極外装ケース
2:負極封口板
3:正極電池層
4:負極電池層
5:セパレータ
6:ダイス
7:打ち抜きパンチ
8:絞り用受け
9:絞り用ポンチ
10:ディスク
11:ボール
12:負荷荷重
13:摺動面
1: Positive electrode outer case 2: Negative electrode sealing plate 3: Positive electrode battery layer 4: Negative electrode battery layer 5: Separator 6: Die 7: Punch punch 8: Receiving punch 9: Punch for drawing
10: Disk
11: Ball
12: Load load
13: Sliding surface
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JP2006312494A JP4936860B2 (en) | 2006-11-20 | 2006-11-20 | Aperture mold |
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JP10371727A Division JP2000192181A (en) | 1998-12-28 | 1998-12-28 | Drawing die |
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US10857695B2 (en) | 2017-07-13 | 2020-12-08 | Fuji Manufacturing Co., Ltd. | Method of surface treatment for ceramic and ceramic article |
Citations (8)
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JPS59232967A (en) * | 1983-06-17 | 1984-12-27 | 東芝タンガロイ株式会社 | Zirconia base sintered body |
JPS6066361A (en) * | 1984-04-12 | 1985-04-16 | Hitachi Metals Ltd | Magnetic head |
JPS61106455A (en) * | 1984-04-12 | 1986-05-24 | 日立金属株式会社 | Zirconia ceramics |
JPH02180754A (en) * | 1988-12-28 | 1990-07-13 | Hitachi Metals Ltd | Slider of magnetic head |
JPH05246760A (en) * | 1991-05-30 | 1993-09-24 | Matsushita Electric Works Ltd | Zirconia-based composite ceramic sintered compact and its production |
JPH08217447A (en) * | 1995-02-14 | 1996-08-27 | Toshiba Corp | Oblique zirconia and production thereof, and zirconia material using the same |
JPH09221352A (en) * | 1995-11-07 | 1997-08-26 | Ngk Spark Plug Co Ltd | Ceramic sintered body and mold made of ceramics |
JP2000192181A (en) * | 1998-12-28 | 2000-07-11 | Kyocera Corp | Drawing die |
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2006
- 2006-11-20 JP JP2006312494A patent/JP4936860B2/en not_active Expired - Fee Related
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS59232967A (en) * | 1983-06-17 | 1984-12-27 | 東芝タンガロイ株式会社 | Zirconia base sintered body |
JPS6066361A (en) * | 1984-04-12 | 1985-04-16 | Hitachi Metals Ltd | Magnetic head |
JPS61106455A (en) * | 1984-04-12 | 1986-05-24 | 日立金属株式会社 | Zirconia ceramics |
JPH02180754A (en) * | 1988-12-28 | 1990-07-13 | Hitachi Metals Ltd | Slider of magnetic head |
JPH05246760A (en) * | 1991-05-30 | 1993-09-24 | Matsushita Electric Works Ltd | Zirconia-based composite ceramic sintered compact and its production |
JPH08217447A (en) * | 1995-02-14 | 1996-08-27 | Toshiba Corp | Oblique zirconia and production thereof, and zirconia material using the same |
JPH09221352A (en) * | 1995-11-07 | 1997-08-26 | Ngk Spark Plug Co Ltd | Ceramic sintered body and mold made of ceramics |
JP2000192181A (en) * | 1998-12-28 | 2000-07-11 | Kyocera Corp | Drawing die |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US10857695B2 (en) | 2017-07-13 | 2020-12-08 | Fuji Manufacturing Co., Ltd. | Method of surface treatment for ceramic and ceramic article |
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