JPH08246001A - Nickel superfine powder for multilayer ceramic capacitor - Google Patents
Nickel superfine powder for multilayer ceramic capacitorInfo
- Publication number
- JPH08246001A JPH08246001A JP7050905A JP5090595A JPH08246001A JP H08246001 A JPH08246001 A JP H08246001A JP 7050905 A JP7050905 A JP 7050905A JP 5090595 A JP5090595 A JP 5090595A JP H08246001 A JPH08246001 A JP H08246001A
- Authority
- JP
- Japan
- Prior art keywords
- particle size
- nickel
- average particle
- powder
- ceramic capacitor
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000000843 powder Substances 0.000 title claims abstract description 25
- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 14
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 19
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims description 79
- 238000009826 distribution Methods 0.000 claims description 17
- 239000012808 vapor phase Substances 0.000 claims description 5
- 239000007772 electrode material Substances 0.000 abstract description 5
- 150000002815 nickel Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 19
- 230000032798 delamination Effects 0.000 description 15
- 238000010304 firing Methods 0.000 description 13
- 239000013078 crystal Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 241000269820 Euthynnus affinis Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、積層セラミックコンデ
ンサーの内部電極にも用いられるニッケル超微粉に関す
るものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultrafine nickel powder which is also used as an internal electrode of a monolithic ceramic capacitor.
【0002】[0002]
【従来の技術】積層セラミックスコンデンサーは、セラ
ミックス誘電体と内部電極とを交互に層状に重ねて圧着
し、これを焼成して一体化したものであり、近年電子部
品として急速に成長している。この積層セラミックスコ
ンデンサーの内部電極としては卑金属であるニッケルが
用いられつつある。2. Description of the Related Art A laminated ceramic capacitor is one in which ceramic dielectrics and internal electrodes are alternately laminated in layers and pressure-bonded, and these are fired to be integrated, and have rapidly grown as electronic parts in recent years. Nickel, which is a base metal, is being used for the internal electrodes of the multilayer ceramic capacitor.
【0003】特開平1-136910号公報には、純度99%以
上、粒径 0.1〜 0.3μm のニッケル粉を湿式法で製造す
る方法が開示されているが、実際にペーストを試作して
電子部品の電極に使用したという記述はない。しかしな
がら、本発明者らの調査では、従来の湿式法によるニッ
ケル粉をペーストにして積層セラミックコンデンサーの
電極とする場合、焼成時に体積変化が大きくデラミネー
ションやクラックの発生が多発しやすいことが判明し
た。これは、ニッケル粉の製造温度が低温(< 100℃)
のため結晶が大きく成長しないこと(微細な1次粒子の
集合体)により過焼結が発生しやすいため、あるいは焼
成時に酸化膨張するためと考えられる。Japanese Unexamined Patent Publication No. 1-136910 discloses a method of manufacturing nickel powder having a purity of 99% or more and a particle size of 0.1 to 0.3 μm by a wet method. However, a paste is actually manufactured as a trial product to produce an electronic component. There is no description that it was used for the electrode. However, in the investigation by the present inventors, it has been found that when nickel powder by a conventional wet method is used as a paste to form an electrode of a multilayer ceramic capacitor, the volume change is large during firing and delamination and cracks are likely to occur frequently. . This is because the manufacturing temperature of nickel powder is low (<100 ℃).
Therefore, it is considered that over-sintering is likely to occur due to the fact that crystals do not grow large (aggregates of fine primary particles), or that the crystals expand due to oxidation during firing.
【0004】また、特開昭64-80007号公報には、平均粒
径 1.0μm 、純度99.9%のニッケル粉末を用いた磁器コ
ンデンサー用電極ペーストが開示されており、焼成時の
クラックや剥離を防止することを目的として、ペースト
に炭化物粉末を添加することが示されている。しかしな
がら、クラックの発生等に及ぼすニッケル粉自体の特性
の影響については示されていない。Further, JP-A-64-80007 discloses an electrode paste for porcelain capacitors which uses nickel powder having an average particle size of 1.0 μm and a purity of 99.9%, and prevents cracks and peeling during firing. For the purpose of doing so, it has been shown to add carbide powder to the paste. However, the influence of the characteristics of the nickel powder itself on the occurrence of cracks is not shown.
【0005】焼成時のクラックや剥離の発生を防止する
ことが積層セラミックコンデンサー製造に要求される重
要な技術であり、クラックや剥離が発生しにくい、低抵
抗な電極材料としてのニッケル粉の開発が望まれてい
た。Preventing cracks and peeling during firing is an important technique required for manufacturing a monolithic ceramic capacitor, and the development of nickel powder as a low-resistance electrode material in which cracks and peeling hardly occur Was wanted.
【0006】[0006]
【発明が解決しようとする課題】本発明は、このような
従来技術の問題点に鑑み、積層セラミックコンデンサー
製造工程におけるクラックや剥離が発生しにくい、低抵
抗な電極材料としてのニッケル粉を提供することを目的
とする。SUMMARY OF THE INVENTION In view of the above problems of the prior art, the present invention provides nickel powder as a low resistance electrode material in which cracks and peeling are less likely to occur in the manufacturing process of a laminated ceramic capacitor. The purpose is to
【0007】[0007]
【課題を解決するための手段】本発明は、平均粒径が
0.1〜 1.0μm で、かつタップ密度が(1)式で表され
る条件を満足する積層セラミックコンデンサー用ニッケ
ル超微粉であり、その粒度分布の幾何標準偏差が 2.0以
下、かつ平均結晶子径が平均粒径の 0.2倍以上であるの
が望ましく、さらには塩化ニッケル蒸気の気相水素還元
方法によって製造されるのが望ましい。According to the present invention, the average particle size is
Nickel ultra-fine powder for laminated ceramic capacitors that has a tap density of 0.1 to 1.0 μm and that satisfies the condition expressed by equation (1), and has a geometric standard deviation of 2.0 or less and an average crystallite size of average. The particle size is preferably 0.2 times or more of the particle size, and more preferably manufactured by the vapor phase hydrogen reduction method of nickel chloride vapor.
【0008】 タップ密度≧−2.5 ×(平均粒径)2+ 7.0×(平均粒径)+ 0.6 ・・・ (1)式 なお、前記した塩化ニッケル蒸気の気相水素還元方法
は、蒸発るつぼを有する蒸発部と、この蒸発部から不活
性ガスで搬送される塩化ニッケル蒸気と供給された水素
とを所定の温度で接触させる反応部と、反応部からの発
生ニッケル粉を含む反応ガスを間接冷却する冷却部と
を、連続配置した反応器を用いるのが望ましい。Tap density ≧ −2.5 × (average particle size) 2 + 7.0 × (average particle size) +0.6 (1) Equation (1) In addition, the vapor phase hydrogen reduction method of nickel chloride vapor described above uses an evaporation crucible. The vaporizing part which has, the reaction part for contacting the supplied hydrogen chloride and the supplied hydrogen chloride with the inert gas from this vaporizing part at a predetermined temperature, and the indirect cooling of the reaction gas containing the nickel powder generated from the reaction part It is desirable to use a reactor in which the cooling section and the cooling section are continuously arranged.
【0009】[0009]
【作用】本発明者らが種々のニッケル粉について実験し
た結果、積層セラミックコンデンサー製造工程における
クラックや剥離の発生しにくい低抵抗な電極材料とし
て、ニッケル微粉に要求される特性は次ぎのとおりであ
った。まず、平均粒径が 0.1〜 1.0μm の範囲に限定さ
れる。平均粒径が 0.1μm 未満では、積層セラミックス
コンデンサー焼成時にニッケル層が過焼結により収縮し
ポーラスなものとなって電気抵抗が高くなり、あるいは
デラミネーションやクラックを発生するので望ましくな
い。一方、 1.0μm 超では、積層セラミックスコンデン
サーの電極層の薄層化が困難なばかりでなく、表面の凹
凸が大きくなりクラックの原因となる。なお、平均粒径
は電子顕微鏡写真を画像解析して求めた個数基準の粒度
分布における50%粒子径(d50)である。As a result of experiments conducted by the present inventors on various nickel powders, the following characteristics are required for nickel fine powders as a low-resistance electrode material that is unlikely to cause cracks or peeling in the manufacturing process of multilayer ceramic capacitors. It was First, the average particle size is limited to the range of 0.1 to 1.0 μm. If the average particle size is less than 0.1 μm, the nickel layer shrinks due to oversintering during firing of the multilayer ceramic capacitor to become porous, resulting in high electrical resistance, or delamination or cracks are generated, which is not desirable. On the other hand, if it exceeds 1.0 μm, not only is it difficult to reduce the thickness of the electrode layer of the multilayer ceramic capacitor, but also unevenness on the surface becomes large, which causes cracks. The average particle size is the 50% particle size (d50) in the number-based particle size distribution obtained by image analysis of electron micrographs.
【0010】次に、粉末の充填性を示す指標であるタッ
プ密度が(1)式で表される条件を満足することが、積
層セラミックコンデンサー焼成時にデラミネーションや
クラックを防止し電極の低抵抗化、長寿命化の必須条件
であることがわかった。 タップ密度≧−2.5 ×(平均粒径)2+ 7.0×(平均粒径)+ 0.6 ・・・ (1)式 なお、タップ密度は、ホソカワミクロン(株)製パウダ
ーテスター(カップ容量100ml 、50φ×51mm)により、
タップリフト18mm、タッピング回数 180回の条件で測定
した値である。Next, it is necessary that the tap density, which is an index showing the filling property of the powder, satisfies the condition represented by the formula (1) so that delamination and cracks can be prevented during firing of the multilayer ceramic capacitor to lower the resistance of the electrode. , It was found to be an essential condition for extending the life. Tap density ≥ -2.5 x (average particle size) 2 + 7.0 x (average particle size) + 0.6 (1) Formula Note that the tap density is a powder tester manufactured by Hosokawa Micron Co., Ltd. (cup volume 100 ml, 50φ x 51 mm). ),
The values are measured under the conditions of tap lift 18 mm and tapping frequency 180 times.
【0011】図1はセラミックスグリーンシートに電極
材を印刷して焼成試験したときのクラック、デラミネー
ション発生率を、タップ密度と平均粒径との関係で示し
たものである。(1)式を満足する領域ではクラック、
デラミネーション発生率が10%以下である。また、タッ
プ密度が(2)式を満たすのが好ましく、この場合のク
ラック、デラミネーション発生率は5%以下となってい
る。FIG. 1 shows the crack and delamination occurrence rates when the electrode material was printed on a ceramic green sheet and subjected to a firing test, as a relationship between the tap density and the average particle diameter. Cracks in the area that satisfies the formula (1),
Delamination occurrence rate is 10% or less. Further, it is preferable that the tap density satisfies the expression (2), and the crack and delamination occurrence rates in this case are 5% or less.
【0012】 タップ密度≧−2.5 ×(平均粒径)2+ 7.0×(平均粒径)+ 0.8 ・・・ (2)式 さらには、タップ密度が(3)式を満たすのがより好ま
しく、クラック、デラミネーション発生率は1%以下と
なっている。 タップ密度≧−2.5 ×(平均粒径)2+ 7.0×(平均粒径)+ 1.0 ・・・ (3)式 さらに、粒度分布の幾何標準偏差が 2.0以下、かつ平均
結晶子径が平均粒径の0.2倍以上であることが好まし
い。粒度分布の幾何標準偏差が 2.0を超えると粗大な粒
子が混入するので、膜厚が不均一となってクラックの原
因となり好ましくない。結晶子径は結晶性を意味し、粒
子の焼結の難易と関係する。すなわち、結晶子径が小さ
いほど粒子は焼結しやすく、積層セラミックスコンデン
サーの焼成時、結晶子径が小さいニッケル粉を電極層と
して用いた場合、ニッケル層が過焼結により収縮してし
まうのである。発明者らは、許容結晶子径を求めるべく
実験を繰り返した結果、平均粒径が 0.1〜 1.0μm の範
囲で粒度分布の幾何標準偏差が 2.0以下、かつ平均結晶
子径が平均粒径の 0.2倍以上であれば、焼成時にデラミ
ネーションやクラックが発生しないことを見い出した。
ここで、粒度分布の幾何標準偏差は個数基準の粒度分布
における50%粒子径(d50)と積算ふるい下84.3%径
(d84.3)の比(d84.3/d50)で求められ、平均結晶
子径はX線回折ピークの半値巾から求められる。Tap density ≧ −2.5 × (average particle size) 2 + 7.0 × (average particle size) +0.8 Equation (2) Furthermore, it is more preferable that the tap density satisfies Equation (3), and cracks The delamination rate is less than 1%. Tap density ≥ -2.5 × (average particle size) 2 + 7.0 × (average particle size) + 1.0 (3) Formula Furthermore, the geometric standard deviation of the particle size distribution is 2.0 or less, and the average crystallite size is the average particle size. It is preferably 0.2 times or more. When the geometric standard deviation of the particle size distribution exceeds 2.0, coarse particles are mixed in, and the film thickness becomes nonuniform, which is a cause of cracks, which is not preferable. The crystallite size means crystallinity and is related to the difficulty of sintering particles. That is, the smaller the crystallite size, the easier the particles are to sinter, and when nickel powder with a small crystallite size is used as the electrode layer during firing of the multilayer ceramic capacitor, the nickel layer shrinks due to oversintering. . As a result of repeated experiments to find an allowable crystallite size, the inventors have found that the geometric standard deviation of the particle size distribution is 2.0 or less and the average crystallite size is 0.2 of the average particle size in the range of the average particle size of 0.1 to 1.0 μm. It has been found that if it is more than twice, delamination and cracks do not occur during firing.
Here, the geometric standard deviation of the particle size distribution is calculated by the ratio (d84.3 / d50) of the 50% particle size (d50) in the number-based particle size distribution and the 84.3% size under the cumulative sieving (d84.3), and the average crystal The child diameter can be obtained from the half width of the X-ray diffraction peak.
【0013】なお、ニッケル純度は99.5重量%以上が好
ましく、99.5重量%未満では焼成時にデラミネーション
やクラックが発生しやすいだけでなく、電極としての特
性が低下(比抵抗が大きくなる)する。このような特徴
を持つニッケル粉の製造方法としては,塩化ニッケルの
気相水素還元法が挙げられる。従来の湿式法は、ニッケ
ル粉の製造温度が低温(< 100℃)であるのに対し、塩
化ニッケルの気相水素還元法は、製造温度が高温(1000
℃付近)であるため、結晶が大きく成長(微細な1次粒
子の集合体でない)することによって焼成時にの過焼結
が発生しにくい。また、気相水素還元法では、粒形状が
球状となり、純度99.5重量%以上のものが得やすい有利
な点もある。上記特徴を持つニッケル粉を効率よく製造
するために、反応器を用いて塩化ニッケル蒸気と水素を
化学反応させる方法が適している。具体的には、塩化ニ
ッケル蒸気濃度(分圧)を0.05〜 0.3とし、かつ塩化ニ
ッケル蒸気と水素を1004℃(1277K)〜1453℃(1726
K)の温度で化学反応させる。The nickel purity is preferably 99.5% by weight or more, and if it is less than 99.5% by weight, not only delamination and cracks are likely to occur during firing, but also the characteristics as an electrode deteriorate (the specific resistance increases). As a method for producing nickel powder having such characteristics, there is a vapor phase hydrogen reduction method of nickel chloride. In the conventional wet method, the production temperature of nickel powder is low (<100 ° C), whereas in the vapor phase hydrogen reduction method of nickel chloride, the production temperature is high (1000
Since the temperature is around 0 ° C.), the crystals grow large (not the aggregate of fine primary particles), so that oversintering at the time of firing hardly occurs. In addition, the gas-phase hydrogen reduction method has an advantage in that the particles have a spherical shape and a purity of 99.5% by weight or more is easily obtained. In order to efficiently produce the nickel powder having the above characteristics, a method of chemically reacting nickel chloride vapor with hydrogen using a reactor is suitable. Specifically, the nickel chloride vapor concentration (partial pressure) is 0.05 to 0.3, and the nickel chloride vapor and hydrogen are 1004 ° C (1277K) to 1453 ° C (1726 ° C).
The chemical reaction is carried out at the temperature of K).
【0014】[0014]
実施例1 図2に示すような反応器1を用い,蒸発部2のルツボ3
に原料の塩化ニッケルを入れ、10リットル/分のアルゴ
ンガス4中に濃度(分圧)が 8.0×10-2なるように加
熱、蒸発させた。この原料混合ガスを蒸発部2の下流に
位置する1050℃(1323K)に設定した反応部5へ輸送
し、反応部5の中央ノズル6から下向きに5リットル/
分の割合で供給される水素7と接触・混合させて反応を
起こさせた。発生したニッケル粉はガスとともに冷却部
9を通過させた後、図示省略した捕集装置で回収した。
なお、図中、8は熱電対を示す。Example 1 Using a reactor 1 as shown in FIG. 2, a crucible 3 in an evaporation section 2 was used.
Nickel chloride as a raw material was put in, and the mixture was heated and evaporated in argon gas 4 at 10 l / min so that the concentration (partial pressure) was 8.0 × 10 -2 . This raw material mixed gas is transported to the reaction section 5 located at the downstream of the evaporation section 2 and set at 1050 ° C. (1323 K), and the central nozzle 6 of the reaction section 5 delivers 5 liter / down.
The reaction was caused by contacting and mixing with hydrogen 7 supplied at a rate of min. The generated nickel powder was passed through the cooling unit 9 together with the gas, and then collected by a collector (not shown).
In the figure, 8 indicates a thermocouple.
【0015】この生成粉の比表面積は 2.7m2/g、電子
顕微鏡観察による平均粒径0.25μm、粒度分布のバラツ
キを示す幾何標準偏差 1.4の粒度が揃った微粉末である
ことが確認された。また、このニッケル粉のX線回折パ
ターンから算出した平均結晶子径は 0.2μm であり、平
均粒径と比較すると、単結晶あるいは数個の結晶からな
る結晶性に優れた多結晶であることが示された。It was confirmed that the produced powder had a specific surface area of 2.7 m 2 / g, an average particle size of 0.25 μm as observed by an electron microscope, and a uniform particle size with a geometric standard deviation of 1.4 indicating variations in particle size distribution. . The average crystallite size calculated from the X-ray diffraction pattern of this nickel powder was 0.2 μm, and compared with the average particle size, it was a single crystal or a polycrystal consisting of several crystals with excellent crystallinity. Was shown.
【0016】酸素含有量 0.3重量%を含む以外はほとん
ど不純物を含まず、純度99.5重量%以上であった。ま
た、タップ密度は2.5g/cm3 であり、平均粒径は0.25μ
m であることから(1)式を満たしている。 実施例2 実施例1において、塩化ニッケルの蒸気濃度(分圧)が
1.0×10-1、反応部1070℃(1343K)とした以外は同じ
条件でニッケル粉を製造した。Almost no impurities were contained except that the oxygen content was 0.3% by weight, and the purity was 99.5% by weight or more. The tap density is 2.5 g / cm 3 and the average particle size is 0.25μ.
Since it is m, Equation (1) is satisfied. Example 2 In Example 1, the vapor concentration (partial pressure) of nickel chloride was
Nickel powder was produced under the same conditions, except that the reaction zone was 1070 ° C (1343K) at 1.0 x 10 -1 .
【0017】この生成粉の比表面積は 1.7m2/g、平均
粒径 0.4μm 、粒度分布の幾何標準偏差は 1.5であり,
形状はほぼ完全な球状であった。図3に電子顕微鏡によ
り撮影したニッケル超微粉の粒子構造を示す。なお、純
度は99.5重量%であった。また、平均結晶子径は 0.2μ
m であり、単結晶あるいは数個の結晶からなる結晶性に
優れた多結晶であることが示された。The specific surface area of this product powder is 1.7 m 2 / g, the average particle size is 0.4 μm, and the geometric standard deviation of the particle size distribution is 1.5.
The shape was almost perfect sphere. FIG. 3 shows the particle structure of ultrafine nickel powder photographed by an electron microscope. The purity was 99.5% by weight. The average crystallite size is 0.2μ
It was m 2 and was shown to be a single crystal or a polycrystal composed of several crystals with excellent crystallinity.
【0018】タップ密度は3.7g/cm3 であり、平均粒径
0.4μm であることから(1)式を満たしている。 実施例3 実施例1において、塩化ニッケルの蒸気濃度(分圧)が
1.0×10-1、反応部1100℃(1373K)とした以外は同じ
条件でニッケル粉を製造した。The tap density is 3.7 g / cm 3 , and the average particle size is
Since it is 0.4 μm, it satisfies the formula (1). Example 3 In Example 1, the vapor concentration (partial pressure) of nickel chloride was
Nickel powder was produced under the same conditions except that the reaction zone was set to 1.0 × 10 −1 and the reaction zone was set to 1100 ° C. (1373 K).
【0019】この生成粉の比表面積は0.85m2/g、平均
粒径 0.8μm 、粒度分布の幾何標準偏差は 1.7であり、
形状はほぼ球状であった。また、平均結晶子径は0.25μ
m であり、純度99.5重量%であった。タップ密度は4.6g
/cm3 であり、平均粒径0.8μm であることから(1)
式を満たしている。The specific surface area of this product powder was 0.85 m 2 / g, the average particle size was 0.8 μm, and the geometric standard deviation of the particle size distribution was 1.7.
The shape was almost spherical. The average crystallite size is 0.25μ.
m 2 and the purity was 99.5% by weight. Tap density is 4.6g
/ Cm 3 and average particle size of 0.8 μm (1)
Meets the formula.
【0020】実施例4 実施例1において、塩化ニッケルの蒸気濃度(分圧)が
2.0×10-1、反応部1010℃(1283K)とした以外は同じ
条件でニッケル粉を製造した。この生成粉の比表面積は
1.0m2/g、平均粒径 0.6μm 、粒度分布の幾何標準偏
差は 1.5であり、形状はほぼ完全な球状であった。Example 4 In Example 1, the vapor concentration (partial pressure) of nickel chloride was
Nickel powder was produced under the same conditions except that the reaction zone was 1010 ° C. (1283 K) at 2.0 × 10 −1 . The specific surface area of this product powder is
The particle size was 1.0 m 2 / g, the average particle size was 0.6 μm, the geometric standard deviation of the particle size distribution was 1.5, and the shape was almost perfect.
【0021】また、平均結晶子径は 0.2μm であり、純
度は99.5重量%であった。タップ密度は4.2g/cm3 であ
り、平均粒径 0.6μm であることから(1)式を満たし
ている。 実施例5 実施例1において、塩化ニッケルの蒸気濃度(分圧)が
1.2×10-1、反応部1020℃(1293K)とした以外は同じ
条件でニッケル粉を製造した。The average crystallite size was 0.2 μm and the purity was 99.5% by weight. Since the tap density is 4.2 g / cm 3 and the average particle size is 0.6 μm, the formula (1) is satisfied. Example 5 In Example 1, the vapor concentration (partial pressure) of nickel chloride was
Nickel powder was produced under the same conditions except that the reaction zone was 1.2 × 10 −1 and the reaction zone was 1020 ° C. (1293 K).
【0022】この生成粉の比表面積は 1.5m2/g、平均
粒径0.45μm 、粒度分布の幾何標準偏差は 1.6であり、
形状はほぼ球状であった。また、平均結晶子径は0.15μ
m であり、純度99.5重量%以上であった。タップ密度は
4.0g/cm3 であり、平均粒径0.45μm であることから
(1)式を満たしている。The specific surface area of this product powder is 1.5 m 2 / g, the average particle size is 0.45 μm, and the geometric standard deviation of the particle size distribution is 1.6.
The shape was almost spherical. The average crystallite size is 0.15μ
m 2, and the purity was 99.5% by weight or more. Tap density is
Since it is 4.0 g / cm 3 and the average particle size is 0.45 μm, the formula (1) is satisfied.
【0023】実施例6 実施例1において、塩化ニッケルの蒸気濃度(分圧)が
5.0×10-2、反応部1015℃(1333K)とした以外は同じ
条件でニッケル粉を製造した。この生成粉の比表面積は
3.2m2/g、電子顕微鏡観察による平均粒径0.15μm、
平均結晶子径 0.1μm であり、純度99.5重量%の粉末で
あった。Example 6 In Example 1, the vapor concentration (partial pressure) of nickel chloride was
5.0 × 10 -2, except that a reaction section 1015 ℃ (1333K) to produce nickel powder under the same conditions. The specific surface area of this product powder is
3.2 m 2 / g, average particle size 0.15 μm by electron microscope observation,
The powder had an average crystallite size of 0.1 μm and a purity of 99.5% by weight.
【0024】タップ密度は2.0g/cm3 であり、平均粒径
0.15μm であることから(1)式を満たしている。 実施例7 実施例1において、塩化ニッケルの蒸気濃度(分圧)が
2.2×10-1、反応部1110℃(1383K)とした以外は同じ
条件でニッケル粉を製造した。The tap density is 2.0 g / cm 3 , and the average particle size is
Since it is 0.15 μm, it satisfies the equation (1). Example 7 In Example 1, the vapor concentration (partial pressure) of nickel chloride was
Nickel powder was produced under the same conditions except that the reaction zone was 1110 ° C. (1383 K) at 2.2 × 10 −1 .
【0025】この生成粉の比表面積は0.75m2/g、平均
粒径 1.0μm 、粒度分布の幾何標準偏差は2.1 、平均結
晶子径は 0.2μm であり、純度99.5重量%以上であっ
た。タップ密度は5.15g/cm3 であり、平均粒径 1.0μm
であることから(1)式を満たしている。 実施例8 実施例1において、塩化ニッケルの蒸気濃度(分圧)が
1.4×10-1、反応部1170℃(1433K)とした以外は同じ
条件でニッケル粉を製造した。The product powder had a specific surface area of 0.75 m 2 / g, an average particle size of 1.0 μm, a geometric standard deviation of the particle size distribution of 2.1, an average crystallite size of 0.2 μm, and a purity of 99.5% by weight or more. Tap density was 5.15 g / cm 3, average particle diameter 1.0μm
Therefore, the expression (1) is satisfied. Example 8 In Example 1, the nickel chloride vapor concentration (partial pressure) was
Nickel powder was produced under the same conditions except that the reaction zone was 1.4 × 10 −1 and the reaction zone was 1170 ° C. (1433 K).
【0026】この生成粉の比表面積は0.75m2/g、平均
粒径 0.9μm 、粒度分布の幾何標準偏差は1.9 、平均結
晶子径は0.09μm であり、純度99.5重量%以上であっ
た。タップ密度は4.9g/cm3 であり、平均粒径 0.9μm
であることから(1)式を満たしている。 比較例1 実施例1において、塩化ニッケルの蒸気濃度(分圧)が
5.0×10-2、反応部 950℃(1333K)とした以外は同じ
条件でニッケル粉を製造した。The product powder had a specific surface area of 0.75 m 2 / g, an average particle size of 0.9 μm, a geometric standard deviation of particle size distribution of 1.9, an average crystallite size of 0.09 μm, and a purity of 99.5% by weight or more. Tap density is 4.9g / cm 3 , average particle size is 0.9μm
Therefore, the expression (1) is satisfied. Comparative Example 1 In Example 1, the vapor concentration (partial pressure) of nickel chloride was
Nickel powder was produced under the same conditions except that the reaction section was 950 ° C. (1333 K) at 5.0 × 10 -2 .
【0027】この生成粉の比表面積は 3.3m2/g、電子
顕微鏡観察による平均粒径0.15μmの立方体、八面体等
の晶癖を有する粉末であった。タップ密度は 1.45g/cm
3 であり、平均粒径0.15μm であることから(1)式を
満たしていない。 比較例2 実施例1において、塩化ニッケルの蒸気濃度(分圧)が
4.0×10-1、反応部1110℃(1333K)とした以外は同じ
条件でニッケル粉を製造した。The produced powder had a specific surface area of 3.3 m 2 / g and was a powder having a crystal habit such as a cubic or octahedron having an average particle size of 0.15 μm as observed by an electron microscope. Tap density is 1.45g / cm
Since the average particle size is 3 and the average particle size is 0.15 μm, the formula (1) is not satisfied. Comparative Example 2 In Example 1, the vapor concentration (partial pressure) of nickel chloride was
Nickel powder was produced under the same conditions except that the reaction zone was set to 4.0 × 10 -1 , 1110 ° C (1333K).
【0028】この生成粉の比表面積は 0.9m2/g、電子
顕微鏡観察による平均粒径 1.1μm、粒度分布の幾何標
準偏差は 2.2であり、数μm の異常成長粒子が混在して
いた。タップ密度は5.3g/cm3 であり、平均粒径 1.1μ
m であることから(1)式を満たしている。The produced powder had a specific surface area of 0.9 m 2 / g, an average particle size of 1.1 μm as observed by an electron microscope, a geometric standard deviation of particle size distribution of 2.2, and several μm of abnormal growth particles were mixed. Tap density was 5.3 g / cm 3, an average particle diameter of 1.1μ
Since it is m, Equation (1) is satisfied.
【0029】比較例3 硫酸ニッケルを水に溶かしたニッケル濃度2.5mol/l 、
pH 9.0の溶液に還元剤として水素化ホウ素ナトリウムを
0.05mol /l 添加し、得られた沈殿物を真空中で乾燥し
ニッケル粉末を作製した。この生成粉の比表面積は 2.0
m2/g、電子顕微鏡観察による平均粒径 0.4μm、ほぼ
球状に近い形状を示した。粒度分布の幾何標準偏差は
1.6であり、平均結晶子径は0.04μm であった。Comparative Example 3 Nickel sulfate was dissolved in water to obtain a nickel concentration of 2.5 mol / l,
Sodium borohydride as a reducing agent in a solution of pH 9.0
0.05 mol / l was added, and the obtained precipitate was dried in vacuum to prepare a nickel powder. The specific surface area of this product powder is 2.0
The particle size was m 2 / g, the average particle size was 0.4 μm as observed by an electron microscope, and the shape was almost spherical. Geometric standard deviation of particle size distribution is
The average crystallite size was 1.6 and the average crystallite size was 0.04 μm.
【0030】タップ密度は2.5g/cm3 であり、平均粒径
0.4μm であることから(1)式を満たしていない。 比較例4 比較例3と同様に湿式法によりニッケル粉を製造した。
ニッケル濃度3.0mol/l 、pH 9.0の溶液に還元剤として
水素化ホウ素ナトリウムを0.05mol /l 添加し、得られ
た沈殿物を大気中で乾燥しニッケル粉末を作製した。The tap density is 2.5 g / cm 3 , and the average particle size is
Since it is 0.4 μm, equation (1) is not satisfied. Comparative Example 4 Nickel powder was produced by a wet method in the same manner as in Comparative Example 3.
0.05 mol / l of sodium borohydride as a reducing agent was added to a solution having a nickel concentration of 3.0 mol / l and a pH of 9.0, and the obtained precipitate was dried in the air to prepare a nickel powder.
【0031】この生成粉の比表面積は 3.1m2/g、電子
顕微鏡観察による平均粒径 0.5μm、ほぼ球状に近い形
状を示した。粒度分布の幾何標準偏差は 1.8であり、平
均結晶子径は0.08μm 、純度は97重量%(酸素 1.8重量
%)であった。タップ密度は2.9g/cm3 であり、平均粒
径 0.5μm であることから(1)式を満たしていない。The produced powder had a specific surface area of 3.1 m 2 / g, an average particle size of 0.5 μm as observed by an electron microscope, and had a nearly spherical shape. The geometric standard deviation of the particle size distribution was 1.8, the average crystallite size was 0.08 μm, and the purity was 97% by weight (oxygen 1.8% by weight). Since the tap density is 2.9 g / cm 3 and the average particle size is 0.5 μm, the formula (1) is not satisfied.
【0032】実施例1〜8、比較例1〜4で得られたそ
れぞれのニッケル粉のペーストを用いて積層セラミック
スコンデンサーを作製し、焼成時のデラミネーションの
発生の有無を調べた。ペースト化にはニッケル粉 100重
量部に対し、バインダとしてエチルセルロース 2.5重量
部、溶媒としてテレピネオール10重量部を添加し、3本
ロールミルで混練した。このペーストを、誘電体の厚さ
が約30μm のグリーンシート上に厚みが4μm になるよ
うに印刷した。電極と誘電体層を交互に30層積み重ねて
圧着したのち切断して、乾燥、脱バインダー後、1200℃
の水素−窒素混合ガス中で焼成した。得られた積層コン
デンサーの大きさは、縦 3.2×横 2.5×厚さ0.9mm であ
った。A laminated ceramic capacitor was manufactured using the nickel powder pastes obtained in Examples 1 to 8 and Comparative Examples 1 to 4, and the occurrence of delamination during firing was examined. To form a paste, 2.5 parts by weight of ethyl cellulose as a binder and 10 parts by weight of terpineol as a solvent were added to 100 parts by weight of nickel powder, and the mixture was kneaded by a three-roll mill. This paste was printed on a green sheet having a dielectric thickness of about 30 μm to a thickness of 4 μm. Alternately, 30 layers of electrodes and dielectric layers are stacked, pressure-bonded, cut, dried, debindered, and 1200 ℃
It was fired in a hydrogen-nitrogen mixed gas of. The size of the obtained multilayer capacitor was 3.2 × 2.5 (horizontal) × 0.9 mm (thick).
【0033】得られた積層コンデンサーのクラックやデ
ラミネーションの有無を30個について調べた結果を表1
に示した。The results of examining the presence or absence of cracks and delamination of 30 of the obtained multilayer capacitors are shown in Table 1.
It was shown to.
【0034】[0034]
【表1】 [Table 1]
【0035】実施例に示すように、本発明の特性を満足
するニッケル粉を用いた場合にはクラックやデラミネー
ションは見られなかった。一方、比較例では本発明の特
性のいずれかが満足しないためにクラックやデラミネー
ションが発生している。As shown in the examples, when nickel powder satisfying the characteristics of the present invention was used, neither crack nor delamination was observed. On the other hand, in Comparative Example, cracks and delamination occur because any of the characteristics of the present invention is not satisfied.
【0036】[0036]
【発明の効果】本発明により、内部電極の薄層化、低抵
抗化、ならびに焼成時のデラミネーションやクラックの
発生を低下させることが達成できた。According to the present invention, it is possible to achieve a thin internal electrode, a low resistance, and a reduction in delamination and cracking during firing.
【図1】クラック、デラミネーションの発生率を、タッ
プ密度、平均粒径との関係で示すグラフである。FIG. 1 is a graph showing the rate of occurrence of cracks and delamination as a function of tap density and average particle size.
【図2】本発明によるニッケル超微粉を得るのに有利な
反応器の概略説明図である。FIG. 2 is a schematic illustration of a reactor advantageous for obtaining ultrafine nickel powder according to the present invention.
【図3】本発明のニッケル超微粉の粒子構造を示す電子
顕微鏡写真である。FIG. 3 is an electron micrograph showing the particle structure of the nickel ultrafine powder of the present invention.
1 反応器 2 蒸発部 3 ルツボ 5 反応部 7 水素 9 冷却部 1 Reactor 2 Evaporator 3 Crucible 5 Reaction 7 Hydrogen 9 Cooling
───────────────────────────────────────────────────── フロントページの続き (72)発明者 大塚 研一 千葉県千葉市中央区川崎町1番地 川崎製 鉄株式会社技術研究所内 (72)発明者 小笠原 修悦 東京都港区芝公園2丁目4番1号 川鉄鉱 業株式会社内 (72)発明者 濱田 尚夫 東京都港区芝公園2丁目4番1号 川鉄鉱 業株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Kenichi Otsuka, 1 Kawasaki-cho, Chuo-ku, Chiba-shi, Chiba Prefecture Technical Research Laboratory, Kawasaki Steel Co., Ltd. No. Kawakawa Mining Co., Ltd. (72) Inventor Nao Hamada 2-4-1 Shiba Koen, Minato-ku, Tokyo No. Kawakawa Mining Co., Ltd.
Claims (3)
プ密度が(1)式で表される条件を満足する積層セラミ
ックコンデンサー用ニッケル超微粉。 タップ密度≧−2.5 ×(平均粒径)2+ 7.0×(平均粒径)+ 0.6 ・・・ (1)式1. An ultrafine nickel powder for a multilayer ceramic capacitor, which has an average particle size of 0.1 to 1.0 μm and a tap density satisfying the condition represented by the formula (1). Tap density ≥ -2.5 x (average particle size) 2 + 7.0 x (average particle size) + 0.6 (1) Formula
つ平均結晶子径が平均粒径の 0.2倍以上であることを特
徴とする請求項1記載の積層セラミックコンデンサー用
ニッケル超微粉。2. The nickel ultrafine powder for a multilayer ceramic capacitor according to claim 1, wherein the geometric standard deviation of the particle size distribution is 2.0 or less, and the average crystallite size is 0.2 times or more the average particle size.
よって製造されたことを特徴とする請求項1または2記
載の積層セラミックコンデンサー用ニッケル超微粉。3. The ultrafine nickel powder for a monolithic ceramic capacitor according to claim 1, which is produced by a vapor phase hydrogen reduction method of nickel chloride vapor.
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JP05090595A JP3197454B2 (en) | 1995-03-10 | 1995-03-10 | Ultra fine nickel powder for multilayer ceramic capacitors |
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Cited By (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10106351A (en) * | 1996-09-30 | 1998-04-24 | Kyocera Corp | Conductive paste |
WO1998024577A1 (en) * | 1996-12-02 | 1998-06-11 | Toho Titanium Co., Ltd. | Process for the production of metal powder and equipment therefor |
EP0925861A2 (en) * | 1997-12-25 | 1999-06-30 | Kawatetsu Mining Co., LTD. | Nickel ultrafine powder |
WO1999042237A1 (en) * | 1998-02-20 | 1999-08-26 | Toho Titanium Co., Ltd. | Process for the production of powdered nickel |
JPH11339554A (en) * | 1998-03-19 | 1999-12-10 | Toray Ind Inc | Conductive powder, conductive paste, plasma display and substrate therefor |
WO2000003823A1 (en) * | 1998-07-15 | 2000-01-27 | Toho Titanium Co., Ltd. | Metal powder |
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1995
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