TWI870614B - Ceramic spherical body and manufacturing method thereof - Google Patents
Ceramic spherical body and manufacturing method thereofDownload PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
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- 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
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/486—Fine ceramics
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
- C04B2235/786—Micrometer sized grains, i.e. from 1 to 100 micron
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Abstract
Translated fromChineseDescription
Translated fromChinese本發明係關於陶瓷球形體。The present invention relates to a ceramic spherical body.
電子材料用途所使用之粉末的微粉碎、或油墨用途的顏料之分散時，廣泛採取使用粉碎用介質施行粉碎的球磨機、振動研磨機、砂磨機、珠磨機等粉碎機。此種粉碎機用的磨球、磨珠等粉碎用介質(以下亦簡稱「介質」)，係使用以耐磨損性、耐碰撞性等優異的二氧化鋯作為主成分之陶瓷燒結體。When finely grinding powders used in electronic materials or dispersing pigments used in inks, ball mills, vibration mills, sand mills, bead mills and other pulverizers that use pulverizing media are widely used. The grinding media (hereinafter referred to as "media") such as grinding balls and beads used in such pulverizers are ceramic sintered bodies with zirconium dioxide as the main component, which has excellent wear resistance and collision resistance.
以二氧化鋯作為主成分的陶瓷燒結體係有揭示：藉由限定ZrO2與Y2O3的組成比率，並控制Al2O3量及SiO2量，而提升耐久性及耐磨損性的介質(例如專利文獻1)。A ceramic sintered body with zirconium dioxide as the main component is disclosed: by limiting the composition ratio of ZrO2 and Y2 O3 and controlling the amount of Al2 O3 and SiO2 , the durability and wear resistance of the medium are improved (for example, Patent Document 1).
專利文獻1：日本專利特開2001-316178號公報Patent document 1: Japanese Patent Publication No. 2001-316178
近年特別在提升被粉碎物之性能的目的下，更進一步要求粒子微細化，隨此情形擴大利用300μm以下的粉碎用微小徑介質。微小徑介質一般係利用例如：滾動造粒成形法、液中造粒成形法、電漿熔融成形法等進行製造，不管何種造粒方法均係在成形過程中，會受粒子的成長履歷、熱履歷、表面張力等影響，而在介質表面上存在波浪形狀。In recent years, in order to improve the performance of the crushed material, the particle size has been further refined, and the use of micro-diameter media below 300μm for crushing has been expanded accordingly. Micro-diameter media are generally manufactured using methods such as rolling granulation, liquid granulation, and plasma melting. Regardless of the granulation method, the particle growth history, thermal history, surface tension, etc. will affect the formation process, and there will be wavy shapes on the surface of the medium.
此種介質表面的波浪係局部性曲率半徑較小的地方。由本發明者等檢討的結果，得知當介質彼此之間、介質與被粉碎物、以及介質與裝置壁面進行碰撞時，介質表面波浪地方的接觸面積較小，若施加較高壓力，結果會成為容易生成介質破損的要因。特別在水中將被粉碎物與介質混合於粉碎機等之中，施行長時間粉碎/分散的情況，會有水溫提高、陶瓷燒結體進行劣化、容易發生破損之情形。The waves on the surface of the medium are the places where the local radius of curvature is smaller. The inventors of the present invention have examined and found that when the media collide with each other, the medium and the crushed object, and the medium and the wall of the device, the contact area of the waves on the surface of the medium is smaller. If a higher pressure is applied, it will become a factor that easily generates medium damage. In particular, when the crushed object and the medium are mixed in water in a grinder, etc., and the crushing/dispersion is carried out for a long time, the water temperature will rise, the ceramic sintered body will deteriorate, and it will be easy to break.
本發明目的在於提供：可用為粉碎機所用之磨球、磨珠等介質，且即使在常溫狀態與水溫較高之狀態下施行粉碎/分散，仍不易發生破損的陶瓷球形體。The purpose of the present invention is to provide: a ceramic spherical body that can be used as a grinding ball, grinding bead and other media for a pulverizer, and is not easily damaged even when pulverizing/dispersing at room temperature or at a relatively high water temperature.
即，為解決上述課題，本發明的陶瓷球形體，係以二氧化鋯為主成分，正方晶比例係80容量%以上且95容量%以下、單斜晶比例係5容量%以下的陶瓷球形體；其中，將平均粒徑設為X(μm)時，直徑成為X/2(μm)的該球形體截面、與該球形體表面的正交線部中，最大高度波浪Wz(μm)係平均粒徑X(μm)的0.5%以上且1.2%以下。That is, in order to solve the above-mentioned problem, the ceramic sphere of the present invention is a ceramic sphere with zirconium dioxide as the main component, a tetragonal crystal ratio of 80 volume % or more and 95 volume % or less, and a monoclinic crystal ratio of 5 volume % or less; wherein, when the average particle size is set to X (μm), the maximum height wave Wz (μm) in the cross section of the sphere with a diameter of X/2 (μm) and the orthogonal line portion of the sphere surface is 0.5% or more and 1.2% or less of the average particle size X (μm).
本發明之陶瓷球形體係即使在常溫狀態及水溫較高狀態下被用以施行被粉碎物的粉碎/分散，仍可發揮抑制陶瓷球形體破損的效果。The ceramic sphere of the present invention can still inhibit the damage of the ceramic sphere even when it is used to crush/disperse the crushed material at room temperature or at a higher water temperature.
1:陶瓷球形體直徑1: Ceramic spherical body diameter
2:成為X/2(μm)的直徑2: The diameter becomes X/2 (μm)
3:直徑成為X/2(μm)的陶瓷球形體截面與該球形體表面的交線部3: The intersection of the cross section of a ceramic spherical body with a diameter of X/2 (μm) and the surface of the spherical body
4:最大高度波浪Wz的測定方向4: Measurement direction of maximum height wave Wz
5:最大高度波浪Wz的測定分佈之例5: Example of measurement distribution of maximum height wave Wz
圖1係本發明之陶瓷球形體的最大高度波浪Wz之測定位置、測定方向、及實際測定的波浪分佈例圖。測定圖中的z軸方向之最大高度波浪，x軸、y軸係其正交的平面。Figure 1 is a diagram showing the measured position, measured direction, and actual measured wave distribution of the maximum height wave Wz of the ceramic sphere of the present invention. The maximum height wave in the z-axis direction in the measurement diagram is orthogonal to the x-axis and y-axis.
本發明的陶瓷球形體係由以二氧化鋯為主成分的陶瓷燒結體構成。另外，於以下之本說明書中，最終製品的陶瓷燒結體(即，粉碎用介質以外，在製造步驟中經一次以上燒結而獲得的中間體陶瓷燒結體)，稱為「中間燒結體」。又，將最終製品陶瓷燒結體及中間燒結體二者簡稱為「燒結體」。The ceramic spherical body of the present invention is composed of a ceramic sintered body with zirconium dioxide as the main component. In addition, in the following description, the ceramic sintered body of the final product (that is, the intermediate ceramic sintered body obtained by sintering more than once in the manufacturing step except for the pulverizing medium) is referred to as the "intermediate sintered body". In addition, the final product ceramic sintered body and the intermediate sintered body are both referred to as "sintered body".
本發明的陶瓷球形體係藉由將以二氧化鋯為主成分的陶瓷原料粉末(以下簡稱為「原料粉末」)成形為球狀而獲得。此處，本說明書中「以二氧化鋯為主成分」係指二氧化鋯比率達90重量%以上，若二氧化鋯比率佔總成分的93重量%以上，便可獲得特別高的強度，故較佳。The ceramic sphere of the present invention is obtained by forming a ceramic raw material powder (hereinafter referred to as "raw material powder") with zirconium dioxide as the main component into a spherical shape. Here, "with zirconium dioxide as the main component" in this specification means that the ratio of zirconium dioxide is 90% by weight or more. If the ratio of zirconium dioxide accounts for 93% by weight of the total components or more, a particularly high strength can be obtained, which is preferred.
陶瓷的各成分含量係依如下便可求得。首先，將陶瓷試料使用萬能試驗機施行壓碎，再將壓碎片約0.3g裝入白金坩堝中，利用硫酸氫鉀熔解。將其利用稀硝酸溶解並定溶，使用ICP發光分光分析法定量各金屬元素，更將其換算為氧化物並求取含量。以下，若本發明之陶瓷球形體的成分有依金屬元素表記，則亦有依氧化物表記的情況。The content of each component of the ceramic can be obtained as follows. First, the ceramic sample is crushed using a universal testing machine, and then about 0.3g of the crushed pieces are placed in a platinum crucible and melted using potassium hydrogen sulfate. It is dissolved and fixed using dilute nitric acid, and each metal element is quantified using ICP emission spectrometry, and it is converted into oxides and the content is obtained. In the following, if the composition of the ceramic sphere of the present invention is expressed in terms of metal elements, it is also expressed in terms of oxides.
再者，本發明的陶瓷球形體係除上述主成分之外，較佳係依氧化物換算而含有氧化釔(Y2O3)、氧化鈰(CeO2)、氧化鋁(Al2O3)、氧化鎂(MgO)、氧化鈣(CaO)等。該等具安定化劑機能，可提升陶瓷球形體的強度、韌性。其中，較佳係含有氧化釔。氧化釔含量係陶瓷球形體中的氧化釔/二氧化鋯之莫耳比，較佳為4.6/95.4以上且5.6/94.4以下、更佳為4.8/95.2以上且5.5/94.5以下。Furthermore, the ceramic sphere of the present invention preferably contains yttrium oxide (Y2 O3 ), zirconia (CeO2 ), aluminum oxide (Al2 O3 ), magnesium oxide (MgO), calcium oxide (CaO) and the like in terms of oxide conversion in addition to the above main components. These have a stabilizer function and can enhance the strength and toughness of the ceramic sphere. Among them, yttrium oxide is preferably contained. The yttrium oxide content is the molar ratio of yttrium oxide/zirconia in the ceramic sphere, preferably 4.6/95.4 or more and 5.6/94.4 or less, and more preferably 4.8/95.2 or more and 5.5/94.5 or less.
本發明之陶瓷球形體係正方晶比例為80容量%以上且95容量%以下、單斜晶比例為5容量%以下。若正方晶含量達80容量%以上，施加應力時，正方晶會變異為單斜晶並體積膨脹，便可抑制介質龜裂，但若未滿80容量%則此項效果會有變小的情況。另一方面，若正方晶含量大於95容量%，則在高溫水中容易發生劣化，因而若長時間施行粉碎/分散等，會有導致水溫上升的情況，進而有造成陶瓷球形體容易破損的情況。又，就從防止破損的觀點，單斜晶的比例越少越好，較佳係在5容量%以下。更佳係3容量%以下、特佳係1容量%以下。然而，在陶瓷球形體的製造步驟中，為使表面形狀呈平滑，一般會施行後述濕式研磨或後洗淨，在濕式研磨時的水溫上升、或研磨後的洗淨、乾燥過程中，因為單斜晶至少會形成0.1%以上，因而一般無法完全歸零。陶瓷球形體的各結晶相比例係可利用粉末X射線繞射法進行測定。The ceramic sphere of the present invention has a tetragonal crystal ratio of more than 80% by volume and less than 95% by volume, and a monoclinic crystal ratio of less than 5% by volume. If the tetragonal crystal content is more than 80% by volume, when stress is applied, the tetragonal crystal will transform into a monoclinic crystal and expand in volume, thereby suppressing medium cracking. However, if the tetragonal crystal content is less than 80% by volume, this effect will be reduced. On the other hand, if the tetragonal crystal content is greater than 95% by volume, it is easy to deteriorate in high-temperature water. Therefore, if the pulverization/dispersion is performed for a long time, the water temperature may rise, and the ceramic sphere may be easily damaged. In addition, from the perspective of preventing damage, the smaller the monoclinic crystal ratio, the better, preferably less than 5% by volume. More preferably, it is less than 3% by volume, and particularly preferably, it is less than 1% by volume. However, in the manufacturing process of ceramic spheres, wet grinding or post-cleaning is generally performed to make the surface shape smooth. During the rise in water temperature during wet grinding or the washing and drying process after grinding, at least 0.1% of monoclinic crystals will be formed, so it is generally impossible to completely return to zero. The proportion of each crystal phase in the ceramic sphere can be measured using powder X-ray diffraction.
本發明的陶瓷球形體係將平均粒徑設為X(μm)時，使直徑成為X/2(μm)的該球形體截面、與該球形體表面的正交線部中，最大高度波浪Wz(μm)係平均粒徑X(μm)的0.5%以上且1.2%以下、即，(Wz/X)×100係0.5以上且1.2以下。一般最大高度波浪會隨粒子粒徑變大，故本發明利用最大高度波浪除以平均粒徑的商值進行評價。若(Wz/X)×100大於1.2，則粉碎中的陶瓷球形體間、或陶瓷球形體與被粉碎物等碰撞時，陶瓷球形體會生成局部性壓力集中，結果導致容易發生破損。(Wz/X)×100較佳係1.0以下。又，若(Wz/X)×100小於0.5，便欠缺工業製品生產性。The ceramic spherical body of the present invention is such that when the average particle size is set to X (μm), the maximum height wave Wz (μm) in the cross section of the spherical body with a diameter of X/2 (μm) and the orthogonal line portion of the spherical body surface is greater than 0.5% and less than 1.2% of the average particle size X (μm), that is, (Wz/X)×100 is greater than 0.5 and less than 1.2. Generally, the maximum height wave increases with the particle size, so the present invention uses the quotient of the maximum height wave divided by the average particle size for evaluation. If (Wz/X)×100 is greater than 1.2, the ceramic spherical body will generate local pressure concentration when the ceramic spherical bodies being crushed collide with each other or when the ceramic spherical body collides with the crushed object, resulting in easy damage. (Wz/X)×100 is preferably less than 1.0. Furthermore, if (Wz/X)×100 is less than 0.5, the industrial product productivity will be insufficient.
此處，平均粒徑X係拍攝陶瓷球形體後，使用影像分析‧計測軟體便可測定。具體係指依如下測定的值。針對陶瓷球形體的集合體使用數位式顯微鏡依倍率10~200倍拍攝。使用影像分析‧計測軟體，並以測定用影像的亮度為基準，將拍攝影像施行二值化。二值化影像利用最小均方施行圓形圖形分離，計算出經分離的各圓直徑，並設為各陶瓷球形體的直徑。將1000個陶瓷球形體直徑的數量平均值設為平均粒徑X。Here, the average particle size X can be measured by using image analysis and measurement software after photographing the ceramic spheres. Specifically, it refers to the value measured as follows. Use a digital microscope to photograph the aggregate of ceramic spheres at a magnification of 10 to 200 times. Use image analysis and measurement software to binarize the photographed image based on the brightness of the measurement image. The binarized image is separated into circular shapes using the least mean square method, and the diameter of each separated circle is calculated and set as the diameter of each ceramic sphere. The numerical average of the diameters of 1,000 ceramic spheres is set as the average particle size X.
再者，「最大高度波浪Wz」係根據JIS B 0601：2013，如圖1所示，針對小於陶瓷球形體直徑1、成為X/2直徑2的該球形體截面、與該球形體表面的正交線部3，從上方4利用雷射顯微鏡觀察陶瓷球形體便可求得。縮小最大高度波浪Wz的方法係可例如：一邊在後述滾動造粒機內僅添加水，一邊進行長時間滾動。Furthermore, the "maximum height wave Wz" is based on JIS B 0601:2013, as shown in Figure 1, and can be obtained by observing the ceramic sphere from above 4 using a laser microscope for the cross section of the sphere that is smaller than the diameter 1 of the ceramic sphere and becomes the diameter 2 of X/2, and the orthogonal line portion 3 of the surface of the sphere. The method of reducing the maximum height wave Wz is, for example, to add only water to the rolling granulator described later while rolling for a long time.
本發明之陶瓷球形體的內部缺陷率較佳係0.5%以下。此處所謂「內部缺陷」係指陶瓷球形體內部的龜裂或空孔。內部缺陷係藉由研削陶瓷球形體，將內部缺陷率形成0.5%以下，便可更加抑制陶瓷球形體之破損。將內部缺陷率設為0.5%以下的方法，係可例如：對所獲得之陶瓷球形體施行後述的熱間均壓處理，或施行後述降低成形體之表面波浪之步驟等。The internal defect rate of the ceramic sphere of the present invention is preferably below 0.5%. Here, "internal defects" refer to cracks or pores inside the ceramic sphere. The internal defects are formed below 0.5% by grinding the ceramic sphere, which can further suppress the damage of the ceramic sphere. The method of setting the internal defect rate below 0.5% can be, for example, performing the hot-pressing treatment described later on the obtained ceramic sphere, or performing the step of reducing the surface wave of the formed body described later.
本發明之陶瓷球形體的平均粒徑X較佳係30μm以上且300μm以下。藉由平均粒徑X達30μm以上，便可輕易地進行被粉碎物與陶瓷球形體的分離，能防止陶瓷球形體混入。藉由平均粒徑X在300μm以下，便可將被粉碎物均勻且微小地施行粉碎、分散。平均粒徑X係利用後述篩式分級等便可設為上述範圍。The average particle size X of the ceramic spheres of the present invention is preferably greater than 30μm and less than 300μm. When the average particle size X is greater than 30μm, the crushed material and the ceramic spheres can be easily separated, and the ceramic spheres can be prevented from mixing. When the average particle size X is less than 300μm, the crushed material can be crushed and dispersed uniformly and finely. The average particle size X can be set to the above range by using the sieve classification described later.
本發明之陶瓷球形體的最小粒徑係0.7X(μm)以上，最大粒徑較佳係1.3X(μm)以下。藉由最小粒徑達0.7X以上，被粉碎物與陶瓷球形體便可輕易分離，俾能防止陶瓷球形體混入。又，藉由最大粒徑在1.3X(μm)以下，便可將粉碎後的被粉碎物設為均勻粒度分佈。最小粒徑與最大粒徑係依照與前述平均粒徑X的測定同樣，使用影像分析‧計測軟體，將經圓形圖分離的各圓直徑之最小值設為最小粒徑，將最大值設為最大粒徑便可測定。最小粒徑與最大粒徑係利用後述篩式分級等便可設為上述範圍。The minimum particle size of the ceramic sphere of the present invention is 0.7X (μm) or more, and the maximum particle size is preferably 1.3X (μm) or less. By having a minimum particle size of 0.7X or more, the crushed material and the ceramic sphere can be easily separated to prevent the ceramic sphere from mixing. In addition, by having a maximum particle size of 1.3X (μm) or less, the crushed material can be set to a uniform particle size distribution after crushing. The minimum particle size and the maximum particle size are determined in the same way as the determination of the above-mentioned average particle size X, using image analysis and measurement software, and the minimum value of the diameter of each circle separated by the pie chart is set as the minimum particle size, and the maximum value is set as the maximum particle size. The minimum particle size and the maximum particle size can be set to the above range by using the sieve classification described later.
另外，因陶瓷球形體製造過程中的不均勻性，會導致較難使所有粒子均形成球形狀，一般情況係正球性較差的粒子存在有1~數%程度。特別係橢圓形狀物會有依橢圓短軸通過開口寬度較等值圓直徑小之分級網的可能性，或者相反會有依橢圓長軸被開口寬度較等值圓直徑大之分級網捕捉的可能性，亦有偏移陶瓷球形體粒度分佈外之值存在的可能性。所以，較佳為利用抽樣的粒徑評價，依能排除如上述特殊形狀之粒子之影響的方式，不使用最小粒徑與最大粒徑，而利用1%粒徑(D1)、99%粒徑(D99)定義，更能正確掌握陶瓷球形體的粒徑範圍，故較佳。所以，本發明之陶瓷球形體較佳係D1達0.7X(μm)以上、D99在1.3X(μm)以下。D1、D99係可依照與最小粒徑、最大粒徑的同樣手法進行評價。In addition, due to the unevenness in the manufacturing process of ceramic spheres, it is difficult to make all particles spherical. Generally, there are 1 to several % of particles with poor sphericity. In particular, elliptical objects may pass through the grading net with a smaller opening width than the equivalent circle diameter according to the short axis of the ellipse, or conversely, they may be captured by the grading net with a larger opening width than the equivalent circle diameter according to the long axis of the ellipse. There is also the possibility of deviation from the value of the ceramic sphere particle size distribution. Therefore, it is better to use the particle size evaluation of sampling. In order to exclude the influence of particles with special shapes as mentioned above, the minimum particle size and maximum particle size are not used, but the 1% particle size (D1) and 99% particle size (D99) are used to define the particle size range of the ceramic sphere. Therefore, the ceramic sphere of the present invention preferably has a D1 of 0.7X (μm) or more and a D99 of 1.3X (μm) or less. D1 and D99 can be evaluated in the same way as the minimum particle size and maximum particle size.
本發明之陶瓷球形體係可依照各種方法製造。以下，一例係針對利用滾動造粒成形法施行的製造例之詳細內容進行說明。The ceramic spherical body of the present invention can be manufactured according to various methods. The following is an example of the detailed content of the manufacturing example using the rolling granulation molding method.
原料粉末首先使用滾動造粒成形法成形為球狀。滾動造粒成形法係藉由在旋轉的轉鼓內，交錯添加陶瓷原料粉末、及含有黏結劑與水分的液體黏結劑，而形成球狀微粒，然後藉由對微粒及粉末賦予旋轉連動使粒子成長，而製作球狀成形體的方法。The raw material powder is first formed into a spherical shape using a rolling granulation method. The rolling granulation method is a method of forming spherical particles by alternately adding ceramic raw material powder and a liquid binder containing a binder and water in a rotating drum, and then giving the particles and powder a rotating linkage to make the particles grow to produce a spherical molded body.
其次，所獲得之成形體降低表面波浪的步驟係將至少重量100kg以上之成形體在滾動造粒機內，一邊僅添加水，一邊更進行至少10小時以上、較佳約20小時、更佳為30小時以上的滾動。藉此，對成形體表面施行平坦化，而縮小表面波浪。此步驟中，滾動造粒機中的水分率較佳係設為較造粒成長時高出2~5%。藉此，藉由陶瓷球形體表層形成含較多水分之狀態，承受滾動壓力時可使粒子移動(可塑性變形)較為容易，結果可使凸部分平坦化，便可獲得最大高度波浪Wz較小的平滑陶瓷球形體。又，為使過剩水分不會造成粒子間凝聚，必需每隔一定經過時間為掌握滾動造粒中的粒子之加濕狀態而目視觀察外觀，或抽樣少量樣品施行粒子狀態之顯微鏡觀察，或者一邊掌握水分率、容積密度等表示加濕狀態的物理量等施行品質管理，一邊進行滾動。Secondly, the step of reducing the surface ripples of the obtained molded body is to place the molded body weighing at least 100 kg in a rolling granulator, while adding only water, and rolling for at least 10 hours, preferably about 20 hours, and more preferably more than 30 hours. In this way, the surface of the molded body is flattened and the surface ripples are reduced. In this step, the moisture content in the rolling granulator is preferably set to be 2~5% higher than that during granulation growth. In this way, the surface of the ceramic sphere is formed to contain more water, which makes it easier for the particles to move (plastic deformation) when subjected to rolling pressure. As a result, the convex part can be flattened, and a smooth ceramic sphere with a smaller maximum height wave Wz can be obtained. In addition, in order to prevent excess water from causing agglomeration between particles, it is necessary to visually observe the appearance of the particles during rolling granulation at regular intervals to grasp the humidification state of the particles, or to take a small amount of samples for microscopic observation of the particle state, or to perform quality control while grasping physical quantities such as moisture content and bulk density that indicate the humidification state, while rolling.
再者，上述降低表面波浪的步驟亦具有促進成形體緻密化的效果，亦能有效降低內部缺陷率。Furthermore, the above-mentioned step of reducing surface waves also has the effect of promoting the densification of the formed body and can effectively reduce the internal defect rate.
因為依此獲得的成形體含有水分，因而若直接提供而進行後述燒結步驟，因成形體內部的水分急遽蒸發，會有導致成形體發生龜裂的可能性。所以，成形體在提供進行燒結步驟之前，便使用乾燥機等進行使成形體內部水分逐漸減少的乾燥步驟。Since the molded body obtained in this way contains water, if it is directly provided for the sintering step described later, the water inside the molded body will evaporate rapidly, which may cause the molded body to crack. Therefore, before the molded body is provided for the sintering step, a drying step is performed using a dryer to gradually reduce the water content inside the molded body.
依此，藉由施行將所成形且經乾燥步驟的成形體放入匣缽等之中，利用煅燒爐進行煅燒的燒結步驟，除去黏結劑與消除粉末粒子結合，便可獲得陶瓷燒結體。燒結步驟時，較佳為依1350~1450℃施行1~3小時之煅燒。Thus, by placing the formed and dried body into a sintering furnace and calcining it, the binder is removed and the powder particles are eliminated to obtain a ceramic sintered body. During the sintering step, it is preferred to calcine at 1350~1450℃ for 1~3 hours.
經過燒結步驟的燒結體可直接(或更進一步經後述研磨後)使用為粉碎用介質。但是，為能更進一步減少粉碎用介質的缺陷，較佳為施行後述的熱間均壓步驟。以下，針對在燒結步驟後更進一步施行熱間均壓步驟的情況進行說明。另外，於沒有施行熱間均壓步驟的情況，前述燒結步驟後的燒結體並非最終製品的「中間燒結體」；於有施行熱間均壓步驟的情況，在以下說明中記為「中間燒結體」。The sintered body after the sintering step can be used directly (or further after grinding as described below) as a pulverizing medium. However, in order to further reduce the defects of the pulverizing medium, it is better to perform the hot-pressing step described below. The following is a description of the case where the hot-pressing step is further performed after the sintering step. In addition, in the case where the hot-pressing step is not performed, the sintered body after the sintering step is not the "intermediate sintered body" of the final product; in the case where the hot-pressing step is performed, it is recorded as the "intermediate sintered body" in the following description.
如前述，由燒結步驟所獲得的中間燒結體，較佳為提供進行熱間均壓(Hot Isostatic Pressing)處理(以下稱「HIP處理」)的熱間均壓步驟。HIP處理係對被處理物同時施加高溫與等向性壓力的處理，藉由對中間燒結體施行HIP處理，便可在不致使形狀變化之情況下，除去中間燒結體內部殘存的空隙與龜裂等缺陷。As mentioned above, the intermediate sintered body obtained by the sintering step is preferably subjected to a hot isostatic pressing step (hereinafter referred to as "HIP treatment"). HIP treatment is a treatment in which high temperature and isotropic pressure are applied to the object to be treated at the same time. By performing HIP treatment on the intermediate sintered body, the defects such as residual voids and cracks inside the intermediate sintered body can be removed without causing shape changes.
HIP處理較佳為依較燒結步驟中的燒結溫度低0℃~50℃之溫度實施。若為更低的溫度，HIP處理中的二氧化鋯等陶瓷粉末擴散不足，會有殘留缺陷的情況。另一方面，若HIP處理的溫度高於燒結溫度，則因中間燒結體進行粒成長而會導致強度降低，且會有強度變動趨大的情況。HIP處理的溫度更佳係較燒結步驟的燒結溫度低0℃~40℃之溫度、特佳係低0℃~30℃的溫度。The HIP treatment is preferably carried out at a temperature 0℃~50℃ lower than the sintering temperature in the sintering step. If the temperature is lower, the ceramic powder such as zirconia in the HIP treatment will not diffuse sufficiently, and there will be residual defects. On the other hand, if the temperature of the HIP treatment is higher than the sintering temperature, the strength will decrease due to the grain growth of the intermediate sintered body, and there will be a tendency for the strength to vary greatly. The temperature of the HIP treatment is more preferably 0℃~40℃ lower than the sintering temperature in the sintering step, and particularly preferably 0℃~30℃ lower.
HIP處理的壓力係為能除去缺陷，較佳為足夠壓力，若依100MPa以上之壓力施行處理，便可毫無問題地施行處理。為能形成高壓狀態，較佳為在Ar氣體環境中施行處理。The pressure of HIP treatment is sufficient to remove defects. If the treatment is carried out at a pressure of more than 100MPa, the treatment can be carried out without any problems. In order to form a high pressure state, it is better to carry out the treatment in an Ar gas environment.
依如上述獲得的燒結體係可直接使用為粉碎用介質，更進一步使用例如：滾筒研磨裝置、球磨機、珠磨機等裝置研磨表面，便可獲得更高品質的粉碎用介質。The sintered body obtained as described above can be directly used as a grinding medium. If the surface is further ground using a device such as a drum grinder, ball mill, or bead mill, a higher quality grinding medium can be obtained.
再者，燒結體較佳為利用分級步驟進行分級。利用分級步驟便可設為所需的平均粒徑、最小粒徑及最大粒徑。分級方法係可例如：使用篩網狀篩進行分級的篩式分級等。篩分級亦可使兩層篩重疊，利用1次操作分離粒徑相對大的粗粉、與粒徑相對小的微粉。Furthermore, the sintered body is preferably graded using a grading step. The grading step can be used to set the desired average particle size, minimum particle size, and maximum particle size. The grading method can be, for example, sieve grading using a mesh sieve. The sieve grading can also overlap two layers of sieves to separate coarse powder with a relatively large particle size and fine powder with a relatively small particle size in one operation.
另外，關於上述表面研磨步驟，經本發明者等檢討的結果，發現特別係使用具較高攪拌能量的珠磨機裝置施行濕式研磨，便可獲得更良好的表面平滑性。表面平滑性係在濕式分散製程中會大幅影響陶瓷球形體磨損量的因子，當表面平滑性較差的情況、即表面凹凸較大或較多的情況，若陶瓷球形體間、或者陶瓷球形體與被分散物間發生碰撞時，凸形狀部分容易被研削，而增加陶瓷球形體之主要成分二氧化鋯的磨損量，結果對被分散物的品質造成大幅影響。特別已知在本發明之陶瓷球形體介質之主要用途，將積層陶瓷電容器製造用高介電原料，所使用的鈦酸鋇粉末施行濕式分散的步驟時，因會導致陶瓷球形體磨損的二氧化鋯成分混入於鈦酸鋇中，便會影響抑制鈦酸鋇的燒結反應，而損及燒結後的鈦酸鋇之初級粒徑的均勻性。此種初級粒徑的不均勻程度會使電容器之電氣特性(電容、介電損失等)惡化、或在形成每1層厚度未滿1μm的較薄之誘電體層時助長表面凹凸，導致在形成平坦積層構造的製程中成為阻礙要因。所以，在鈦酸鋇的濕式分散步驟中，依高精度管理混入被粉碎物中的二氧化鋯之磨損量，較佳係磨損量少且安定的陶瓷球形體介質。為實現此點，必需確保陶瓷球形體表面的平滑性。In addition, regarding the above-mentioned surface grinding step, the inventors have examined and found that, in particular, wet grinding using a bead mill with a higher stirring energy can achieve better surface smoothness. Surface smoothness is a factor that greatly affects the amount of wear of ceramic spheres during the wet dispersion process. When the surface smoothness is poor, that is, when the surface is larger or more uneven, if collisions occur between ceramic spheres or between ceramic spheres and dispersed materials, the convex portions are easily ground off, increasing the amount of wear of zirconium dioxide, the main component of the ceramic spheres, and thus greatly affecting the quality of the dispersed materials. It is particularly known that in the main application of the ceramic spherical dielectric of the present invention, when the barium titanate powder used in the manufacture of multilayer ceramic capacitors is subjected to the wet dispersion step, the zirconium dioxide component that causes the ceramic spherical body to wear is mixed into the barium titanate, which will affect the inhibition of the sintering reaction of the barium titanate and damage the uniformity of the primary particle size of the sintered barium titanate. Such unevenness of primary particle size can deteriorate the electrical characteristics (capacitance, dielectric loss, etc.) of the capacitor, or promote surface unevenness when forming a thinner inductive layer with a thickness of less than 1μm, which becomes an obstacle in the process of forming a flat laminated structure. Therefore, in the wet separation step of barium titanate, the wear amount of zirconium dioxide mixed in the pulverized material is managed with high precision, and a ceramic spherical medium with less wear and stability is preferred. To achieve this, the smoothness of the surface of the ceramic sphere must be ensured.
使用上述珠磨機裝置的研磨步驟中，為能獲得良好表面平滑性的重要製程因子，係研磨材的種類(素材、粒徑)、及其漿濃度、攪拌速度(圓周速度)、處理時間。為使自重能如微小尺寸陶瓷球形體般的輕，在研磨表面時必需使用較高的研磨能量。研磨材較佳為使用切削力較高的碳化矽(SiC)或氧化鋁(Al2O3)，粒徑越大則切削力越高，相反的，粒徑越小則越能降低切削傷，故較能更輕易地獲得平滑表面。所以，從生產效率之觀點，最初先利用較大粒徑的研磨材施行粗研磨後，再使用較小粒徑的研磨材施行拋光研磨便屬有效，粗研磨用較佳為使用粒徑3~10μm程度的粒徑，拋光研磨用較佳為使用0.5~2μm程度的粒徑。又，研磨材的漿濃度，從研磨處理中防止研磨材自身之凝聚的觀點，較佳係設為1~5重量%程度。同樣地從防止凝聚之觀點，較佳為配合研磨材種類添加分散劑0.3~3重量%程度。裝置運轉條件的攪拌速度(圓周速度)，從生產能力之觀點係越快越好，但若過快會導致陶瓷球形體表面上容易附著研磨材之殘渣，故就從兼顧的觀點較佳係設為8~14m/s範圍。處理時間係依照裝置規格、陶瓷球形體尺寸、研磨材種類等而有所不同，較佳係至少2小時以上、更佳係4小時以上。又，待研磨處理結束後，藉由利用未含研磨材而僅有水者、或僅含有水與分散劑者施行處理，便可除去陶瓷球形體表面上附著的殘渣，較佳係施行0.5~2小時左右。In the grinding step using the above-mentioned bead mill, the important process factors for obtaining good surface smoothness are the type of abrasive (material, particle size), its slurry concentration, stirring speed (circumferential speed), and processing time. In order to make the self-weight as light as a micro-sized ceramic sphere, a higher grinding energy must be used when grinding the surface. The abrasive is preferably silicon carbide (SiC) or alumina (Al2 O3 ) with higher cutting force. The larger the particle size, the higher the cutting force. On the contrary, the smaller the particle size, the less cutting damage can be caused, so it is easier to obtain a smooth surface. Therefore, from the perspective of production efficiency, it is effective to use a larger particle size abrasive for rough grinding first, and then use a smaller particle size abrasive for polishing. It is better to use a particle size of about 3~10μm for rough grinding, and a particle size of about 0.5~2μm for polishing. In addition, the slurry concentration of the abrasive is preferably set to about 1~5% by weight from the perspective of preventing the abrasive from agglomerating itself during the grinding process. Similarly, from the perspective of preventing agglomeration, it is better to add a dispersant of about 0.3~3% by weight according to the type of abrasive. The stirring speed (circumferential speed) of the device operation conditions is as fast as possible from the perspective of production capacity, but if it is too fast, it will easily cause the residue of the grinding material to adhere to the surface of the ceramic sphere, so from the perspective of comprehensive consideration, it is better to set it in the range of 8~14m/s. The treatment time varies according to the device specifications, the size of the ceramic sphere, the type of grinding material, etc. It is better to be at least 2 hours, and more preferably 4 hours. In addition, after the grinding treatment is completed, the residue attached to the surface of the ceramic sphere can be removed by using a grinding material without grinding material and only water, or a grinding material containing only water and dispersant. It is better to perform it for about 0.5~2 hours.
使用如上述珠磨機依適當條件施行濕式研磨的結果，例如若以滾筒研磨方式，相對於表面粗糙度Ra=20~40nm程度的平滑性可獲得Ra=2~10nm的平滑性。為形成2nm以下必需使用更微小之粒徑研磨材，依長時間或高圓周速度施行研磨，但卻容易發生研磨材之凝聚，結果會有混入製品的顧慮，所以利用本發明施行的製法較佳為設為上述表面粗糙度範圍。表面粗糙度Ra係使用原子力顯微鏡(AFM)便可評價。另外，本發明係抽樣10個陶瓷球形體進行評價，將平均值設為表面粗糙度值Ra。The result of wet grinding under appropriate conditions using a bead mill such as the one mentioned above, for example, if a drum grinding method is used, a smoothness of Ra=2~10nm can be obtained relative to a smoothness of Ra=20~40nm. In order to form a surface roughness below 2nm, a finer particle size abrasive must be used, and grinding must be performed for a long time or at a high peripheral speed, but the abrasive is prone to aggregation, resulting in the concern of mixing into the product, so the method implemented by the present invention is preferably set to the above surface roughness range. The surface roughness Ra can be evaluated using an atomic force microscope (AFM). In addition, the present invention samples 10 ceramic spheres for evaluation, and the average value is set as the surface roughness value Ra.
上述表面粗糙度Ra=2~10nm陶瓷球形體進行鈦酸鋇濕式分散時，磨損量的評價結果，得知若Ra=10nm至5nm時雖平滑但磨損量亦會降低，可是若5nm以下則幾乎持平。此現象可認為因為二氧化鋯球形體受來自鈦酸鋇的切削作用，例如即使初期平滑性為2nm左右，但使用後會因切削傷導致其惡化成5nm前後的平滑性。由以上結果，關於本發明的鈦酸鋇之濕式分散用途，為能降低因陶瓷球形體造成的氧化鋯磨損量且使安定化，陶瓷球形體較佳為設為表面粗糙度Ra=2~5nm範圍。The evaluation results of the wear amount of the above-mentioned ceramic spheres with surface roughness Ra=2~10nm when barium titanate is wet dispersed show that if Ra=10nm to 5nm, although it is smooth, the wear amount will also be reduced, but if it is below 5nm, it will be almost the same. This phenomenon can be considered to be because the zirconia spheres are subjected to the cutting effect from barium titanate. For example, even if the initial smoothness is about 2nm, it will deteriorate to a smoothness of about 5nm due to cutting damage after use. From the above results, regarding the wet dispersion of barium titanate of the present invention, in order to reduce the wear amount of zirconia caused by ceramic spheres and stabilize it, the ceramic spheres are preferably set to a surface roughness of Ra=2~5nm.
以下，根據實施例針對本發明進行具體說明，惟，本發明並不僅侷限於該等實施例。The present invention is described in detail below based on the embodiments, but the present invention is not limited to the embodiments.
粒徑係依下述方法測定。利用數位式顯微鏡VHX-2000(Keyence製)，依倍率10~200倍拍攝陶瓷球形體的集合體。使用影像分析‧計測軟體WinROOF(註冊商標：三谷商事公司製)，以測定用影像的亮度為基準施行二值化。二值化影像利用最小均方施行圓形圖分離，計算出經分離的各圓之直徑，並設為各陶瓷球形體的直徑。又，將1000個陶瓷球形體的直徑數量平均值設為平均粒徑X。又，將經圓形圖分離的各圓直徑之最小值設為最小粒徑、最大值設為最大粒徑。此外，依個數比例從最小端起計數，將累積個數1%的等值直徑設為1%粒徑(D1)，將累積個數99%的等值直徑設為99%粒徑(D99)。The particle size is measured according to the following method. Using a digital microscope VHX-2000 (manufactured by Keyence), an aggregate of ceramic spheres is photographed at a magnification of 10 to 200 times. Using the image analysis and measurement software WinROOF (registered trademark: manufactured by Mitani Shoji Co., Ltd.), binarization is performed based on the brightness of the measurement image. The binarized image is separated by pie chart using the least mean square method, and the diameter of each separated circle is calculated and set as the diameter of each ceramic sphere. In addition, the number average of the diameters of 1,000 ceramic spheres is set as the average particle size X. In addition, the minimum value of the diameters of each circle separated by the pie chart is set as the minimum particle size, and the maximum value is set as the maximum particle size. In addition, count from the smallest end according to the number ratio, set the equivalent diameter of 1% of the cumulative number as the 1% particle size (D1), and set the equivalent diameter of 99% of the cumulative number as the 99% particle size (D99).
將樹脂包埋試料，施行切剖及鏡面研磨設為測定試料。將其貼附於試料支撐架上，利用廣角X射線繞射法(微小部X射線繞射)進行測定。測定條件係如下：The sample is embedded in resin, cut and mirror-polished to make a test sample. It is attached to the sample support and measured using wide-angle X-ray diffraction (micro-part X-ray diffraction). The measurement conditions are as follows:
X射線源：CuK線(使用多層膜反射鏡)X-ray source: CuK rays (using multi-layer film reflective mirror)
輸出：50kV、22mAOutput: 50kV, 22mA
狹縫系：100μm
測定範圍：2θ=23°~33°、70°~77°Measuring range: 2θ=23°~33°, 70°~77°
累計時間：3600秒/幀。Cumulative time: 3600 seconds/frame.
從測定結果，使用下式計算出二氧化鋯各結晶層的含有率。From the measurement results, the content of each crystal layer of zirconium dioxide is calculated using the following formula.
單斜晶含有率(%)=[{Im(111)+Im(1-1-1)}/{Im(111)+Im(1-1-1)+It+c(111)}]×100Monoclinic crystal content (%) = [{Im (111) + Im (1-1-1)} / {Im (111) + Im (1-1-1) + It + c (111)}] × 100
立方晶含有率(%)=[It+c(111)/{Im(111)+Im(1-1-1)+It+c(111)}]×[{Ic(400)/{Ic(400)+It(400)+It(004)}×100Cubic crystal content (%)=[It+c (111)/{Im (111)+Im (1-1-1)+It+c (111)}]×[{Ic (400)/{Ic (400)+It (400)+It (004)}×100
正方晶含有率(%)=100-單斜晶含有率-立方晶含有率Tetragonal crystal content (%) = 100-monoclinic crystal content-cubic crystal content
其中，I係表示繞射強度。下標字係m、t、c分別表示單斜晶、立方晶、正方晶。繞射強度之( )內係表示各結晶的指數。Among them, I represents the diffraction intensity. The subscripts m, t, and c represent monoclinic, cubic, and tetragonal crystals, respectively. The parentheses in the diffraction intensity represent the index of each crystal.
最大高度波浪Wz(μm)係根據JIS B 0601：2013。針對陶瓷球形體使用雷射顯微鏡VK-X-150(Keyence製)，從圖1的4所示之測定方向(圖1中的z軸方向)，就直徑成為圖1中的2所示之X/2(μm)的該球形體之截面(圖1中與z軸正交的xy平面上)、與該球形體表面的交線部(即，圖1中的3所示之處)，以未接觸的10個球形體對象，在測定長度=平均粒徑X/2×3.141(μm)、高頻成分除去用截頻值λs=2.5(μm)、低頻成分除去用λc=無的條件下，測定z軸方向的最大高度波浪Wz，計算出最大高度波浪Wz的平均值。此處，圖1中的5係本發明之最大高度波浪Wz的測定分佈例。The maximum height waviness Wz (μm) is based on JIS B 0601: 2013. For ceramic spheres, a laser microscope VK-X-150 (manufactured by Keyence) is used to measure the maximum height waviness Wz in the z-axis direction from the measurement direction shown in 4 of FIG. 1 (the z-axis direction in FIG. 1), at the cross section of the sphere whose diameter is X/2 (μm) shown in 2 of FIG. 1 (on the xy plane orthogonal to the z-axis in FIG. 1), and at the intersection with the surface of the sphere (i.e., the point shown in 3 of FIG. 1), with 10 spheres not in contact, under the conditions of measurement length = average particle diameter X/2 × 3.141 (μm), high-frequency component removal cutoff value λs = 2.5 (μm), and low-frequency component removal λc = none, and the average value of the maximum height waviness Wz is calculated. Here, 5 in Figure 1 is an example of the measured distribution of the maximum height wave Wz of the present invention.
表面粗糙度Ra(nm)係根據JIS B 0601：2013。從陶瓷球形體的集合體任意抽樣10個粒子，使用原子力顯微鏡(Bruker公司、NanoScopeV)，在陶瓷球形體之平均粒徑X的1/10四邊形大小之測定區域中，依掃描速度=0.3Hz、解析度256×256掃描球形體中心附近，再針對所獲得之影像施行平面化(Flatten)1次、平面相稱(Plane Fit)-x3次處理，獲得將曲面擬合校正為平面的影像。針對經平面校正的影像，評價表面粗糙度Ra。針對各粒子各施行3次評價，將10粒子×3次=合計30處的Ra平均值設為該陶瓷球形體的表面粗糙度值Ra。Surface roughness Ra (nm) is based on JIS B 0601: 2013. Ten particles are randomly sampled from a collection of ceramic spheres. An atomic force microscope (Bruker, NanoScopeV) is used to scan the vicinity of the center of the sphere at a scanning speed of 0.3Hz and a resolution of 256×256 in a measurement area of a quadrilateral size of 1/10 of the average particle size X of the ceramic sphere. The obtained image is then flattened once and plane fit-x3 times to obtain an image that corrects the curved surface to a flat surface. The surface roughness Ra is evaluated for the plane-corrected image. Each particle is evaluated 3 times, and the average Ra value of 10 particles × 3 times = a total of 30 locations is set as the surface roughness value Ra of the ceramic sphere.
內部缺陷率係依下述方法測定。陶瓷球形體利用研削機施行研削至球形體直徑的40~60%大小後，更利用粒徑6μm之鑽石液施行10分鐘以上的拋光研磨，獲得略截面。所獲得之樣品使用數位式顯微鏡VHX-2000(Keyence製)依倍率10~200倍觀察，計數可觀察到的龜裂數。觀察200個陶瓷球形體，從該等之中，計算出有龜裂或點缺陷的陶瓷球形體比例，設為內部缺陷率。The internal defect rate is measured by the following method. The ceramic sphere is ground to 40-60% of the sphere diameter using a grinder, and then polished for more than 10 minutes using a 6μm diamond liquid to obtain a rough cross section. The obtained sample is observed using a digital microscope VHX-2000 (Keyence) at a magnification of 10-200 times, and the number of observable cracks is counted. 200 ceramic spheres are observed, and the proportion of ceramic spheres with cracks or point defects is calculated from them, which is set as the internal defect rate.
壓碎荷重值係依下述方法測定。利用直徑20mm之二氧化鋯製圓柱狀夾具夾持陶瓷球形體，使用電子式萬能試驗機CATY-2000YD(米倉製作所製)依0.5mm/min速度施加壓縮荷重，測定破壞時的荷重值。測定係針對30個陶瓷球形體實施，數值係採用平均值。又，當陶瓷球形體暴露於高溫之水中時，強度試驗係將所獲得之陶瓷球形體在水溫90℃中靜置50小時，然後測定陶瓷球形體的壓碎荷重值，設為「水熱試驗後的壓碎荷重值」。測定係依30個球形體實施，數值係採用平均值。又，從{(水熱試驗前的壓碎荷重值)-(水熱試驗後的壓碎荷重值)}/(水熱試驗前的壓碎荷重值)×100，計算出水熱試驗後的壓碎荷重降低率。The crushing load value is measured according to the following method. The ceramic sphere is clamped by a cylindrical fixture made of zirconia with a diameter of 20mm, and a compressive load is applied at a speed of 0.5mm/min using an electronic universal testing machine CATY-2000YD (produced by Yonekura Manufacturing Co., Ltd.) to measure the load value at the time of destruction. The measurement is carried out on 30 ceramic spheres, and the value is the average value. In addition, when the ceramic sphere is exposed to high-temperature water, the strength test is to place the obtained ceramic sphere in water at a temperature of 90℃ for 50 hours, and then measure the crushing load value of the ceramic sphere, which is set as the "crushing load value after hydrothermal test". The measurement is carried out on 30 spheres, and the value is the average value. In addition, the crushing load reduction rate after the hydrothermal test was calculated from {(crushing load value before the hydrothermal test) - (crushing load value after the hydrothermal test)}/(crushing load value before the hydrothermal test) × 100.
依下述方法施行龜裂試驗。所獲得之陶瓷球形體的集合體在珠磨機裝置(HIROSHIMA METAL & MACHINERY公司製、型號UAM-015)中填充220g，使20℃純水300g進行循環，依圓周速度12m/s進行24小時攪拌。經攪拌後，取出陶瓷球形體，使用數位式顯微鏡VHX-2000(Keyence)依倍率10~200倍觀察，確認有無龜裂。確認1000個陶瓷球形體，將有出現龜裂的陶瓷球形體個數設為龜裂個數。The crack test was carried out according to the following method. 220g of the obtained ceramic spherical aggregate was filled in a bead mill device (manufactured by HIROSHIMA METAL & MACHINERY, model UAM-015), 300g of 20℃ pure water was circulated, and stirring was performed for 24 hours at a peripheral speed of 12m/s. After stirring, the ceramic spherical bodies were taken out and observed using a digital microscope VHX-2000 (Keyence) at a magnification of 10~200 times to confirm whether there were cracks. 1000 ceramic spherical bodies were confirmed, and the number of ceramic spherical bodies with cracks was set as the number of cracks.
利用下述方法施行鈦酸鋇之濕式分散時的陶瓷球形體之磨損量評價。所獲得之陶瓷球形體的集合體在珠磨機裝置(HIROSHIMA METAL & MACHINERY公司製、型號UAM-015)中填充220g，使在20℃之純水300g中摻合鈦酸鋇30g(SIGMA-ALDRICH公司、鈦(IV)酸鋇)、分散劑3g(東京化成工業(股)、十二烷基苯磺酸鈉)而製作的漿進行循環，依圓周速度12m/s實施4小時濕式分散。所獲得之漿利用熱風乾燥機施行90℃×24小時乾燥，再將已乾固的鈦酸鋇粉末使用研缽施行微粉碎後，使用螢光X射線分析裝置(理學電氣工業製ZSX PrimusII)，藉由求取鋯強度尖峰面積相對於鈦、鋇之強度尖峰面積的比率，而計算出鈦酸鋇粉末中的二氧化鋯量(陶瓷球形體磨損量)。又，實施該試驗後，依照與前述龜裂試驗同樣的手法，使用數位式顯微鏡確認陶瓷球形體的龜裂個數。The wear amount of ceramic spheres during wet dispersion of barium titanium oxide was evaluated by the following method. 220 g of the obtained ceramic sphere aggregate was filled in a bead mill (HIROSHIMA METAL & MACHINERY, model UAM-015), and a slurry prepared by mixing 30 g of barium titanium oxide (barium titanium (IV) oxide, SIGMA-ALDRICH) and 3 g of a dispersant (sodium dodecylbenzene sulfonate, Tokyo Chemical Industry Co., Ltd.) in 300 g of pure water at 20°C was circulated, and wet dispersion was performed for 4 hours at a peripheral speed of 12 m/s. The obtained slurry was dried in a hot air dryer at 90°C for 24 hours, and the dried barium titanate powder was finely pulverized in a mortar. The amount of zirconium dioxide in the barium titanate powder (amount of ceramic spherical wear) was calculated by using a fluorescent X-ray analyzer (ZSX PrimusII manufactured by Rigaku Denki Kogyo) by obtaining the ratio of the zirconium strength peak area to the strength peak area of titanium and barium. After the test, the number of ceramic spherical cracks was confirmed using a digital microscope in the same manner as the above-mentioned crack test.
在氧氯化鋯中，依所獲得之陶瓷球形體中之氧化物換算成為表1的氧化釔/二氧化鋯莫耳比所示比例之方式，添加氯化釔，依照共沉法製作原料粉末。Yttrium chloride is added to zirconium oxychloride in such a manner that the oxide in the obtained ceramic sphere is converted into the ratio shown in the molar ratio of yttrium oxide/zirconium dioxide in Table 1, and the raw material powder is prepared by the co-precipitation method.
接著，使用上述原料粉末，依滾動造粒成形法，施行造粒成形直到燒結後的平均粒徑X成為50μm前後之尺寸為止，獲得成形體。Next, the raw material powder is used to perform granulation molding according to the rolling granulation molding method until the average particle size X after sintering reaches about 50μm to obtain a molded body.
其次，所獲得之成形體降低表面波浪的步驟，係一邊依滾動造粒機內保持一定水分率之方式僅添加水，一邊施行約40小時的滾動，而降低表面波浪。Secondly, the step of reducing the surface waves of the obtained shaped body is to add water in a manner that maintains a certain moisture content in the rolling granulator while performing rolling for about 40 hours to reduce the surface waves.
將依如上所獲得之成形體施行乾燥後，依1400℃施行2小時煅燒，獲得中間燒結體(燒結步驟)。然後，對中間燒結體依1380℃、120MPa施行1.5小時的HIP處理(熱間均壓步驟)。針對所獲得之燒結體，使用滾筒研磨裝置施行表面研磨後，藉由施行篩式分級，而製作表1所示之粉碎用球形介質。After drying the molded body obtained as above, calcining was performed at 1400℃ for 2 hours to obtain an intermediate sintered body (sintering step). Then, the intermediate sintered body was subjected to HIP treatment (hot-mixing pressure equalization step) at 1380℃ and 120MPa for 1.5 hours. The obtained sintered body was surface-polished using a roller grinding device, and then screen-graded to produce the spherical media for crushing shown in Table 1.
使用實施例1的原料粉末，與實施例1同樣地，依照滾動造粒成形法造粒至燒結後之平均粒徑X成為100μm前後之尺寸之成形體，實施降低表面波浪的步驟。所獲得之成形體經乾燥除去水分後，再施行煅燒、HIP處理。針對所獲得之燒結體，使用滾筒研磨裝置施行表面研磨後，藉由施行篩式分級，而製作表1所示之粉碎用球形介質。Using the raw material powder of Example 1, the powder was granulated by the rolling granulation method until the average particle size X after sintering was about 100 μm, and the surface wave reduction step was performed. The obtained shaped body was dried to remove moisture, and then calcined and HIP treated. The obtained sintered body was surface ground using a roller grinding device, and then screen-graded to produce the spherical medium for crushing shown in Table 1.
使用實施例1的原料粉末，與實施例1同樣地，依照滾動造粒成形法造粒至燒結後之平均粒徑X成為200μm前後之尺寸之成形體，實施降低表面波浪的步驟。所獲得之成形體經乾燥除去水分後，再施行煅燒、HIP處理。針對所獲得之燒結體，使用滾筒研磨裝置施行表面研磨後，藉由施行篩式分級，而製作表1所示之粉碎用球形介質。Using the raw material powder of Example 1, the powder was granulated by the rolling granulation method until the average particle size X after sintering was about 200 μm, and the surface wave reduction step was performed. The obtained shaped body was dried to remove moisture, and then calcined and HIP treated. The obtained sintered body was surface ground using a roller grinding device, and then screen-graded to produce the spherical medium for crushing shown in Table 1.
與實施例1同樣地，依照滾動造粒成形法造粒至燒結後之平均粒徑X成為50μm前後之尺寸之成形體。除將降低表面波浪的步驟的時間縮短為10小時之外，其餘均與實施例1同樣地實施，而製作表1所示之粉碎用球形介質。Similar to Example 1, the granulation was carried out by the rolling granulation molding method until the average particle size X after sintering was about 50 μm. Except for shortening the time of the step of reducing the surface wave to 10 hours, the rest was implemented in the same way as Example 1 to produce the spherical medium for crushing shown in Table 1.
與實施例2同樣地，依照滾動造粒成形法造粒至燒結後之平均粒徑X成為100μm前後之尺寸之成形體。除將降低表面波浪的步驟的時間縮短為10小時之外，其餘均與實施例2同樣地實施，而製作表1所示之粉碎用球形介質。Similar to Example 2, the granulation was carried out by the rolling granulation molding method until the average particle size X after sintering was about 100 μm. Except for shortening the time of the step of reducing the surface wave to 10 hours, the rest was implemented in the same way as Example 2 to produce the spherical medium for crushing shown in Table 1.
與實施例3同樣地，依照滾動造粒成形法造粒至燒結後之平均粒徑X成為200μm前後之尺寸之成形體。除將降低表面波浪的步驟的時間縮短為10小時之外，其餘均與實施例3同樣地實施，而製作表1所示之粉碎用球形介質。Similar to Example 3, the granulation was carried out by the rolling granulation molding method until the average particle size X after sintering was about 200 μm. Except for shortening the time of the step of reducing the surface wave to 10 hours, the rest was implemented in the same way as Example 3 to produce the spherical medium for crushing shown in Table 1.
與實施例2同樣地，依照滾動造粒成形法造粒至燒結後之平均粒徑X成為100μm前後之尺寸之成形體。除將HIP步驟的處理溫度從1380℃變更為1300℃之外，其餘均與實施例2同樣地實施，而製作表1所示之粉碎用球形介質。Similar to Example 2, the granulation was carried out by the rolling granulation molding method until the average particle size X after sintering was about 100 μm. Except for changing the treatment temperature of the HIP step from 1380°C to 1300°C, the rest was carried out in the same way as Example 2 to produce the spherical medium for crushing shown in Table 1.
進行與實施例1同樣的製造製程直到HIP處理，但研磨步驟係使用珠磨機依如下條件進行。研磨材係使用由粒徑3μm之氧化鋁(Tipton公司(股)、Light 1A)3.0重量%、分散劑之多元羧酸鈉塩(中京油脂(股)、Serna D-305)0.5重量%調製的研磨漿，依珠磨機攪拌圓周速度=12m/s合計研磨6小時後，再利用由粒徑1μm之氧化鋁(Tipton公司(股)、Light 1A)1.0重量%、分散劑同為D-305：0.5重量%調製的研磨漿，實施4小時研磨。最後，利用僅由D-305：0.5重量%調製的漿施行2小時拋光，除去陶瓷球形體的表面殘渣，獲得表面粗糙度Ra=2nm的陶瓷球形體。之後的篩式分級係依照與實施例1同樣之手法實施。The same manufacturing process as Example 1 was carried out until the HIP treatment, but the grinding step was carried out using a bead mill under the following conditions. The grinding material was a grinding slurry prepared from 3.0% by weight of aluminum oxide (Tipton Co., Ltd., Light 1A) with a particle size of 3μm and 0.5% by weight of polycarboxylic acid sodium salt (Chujing Oil Co., Ltd., Serna D-305) as a dispersant. After grinding for a total of 6 hours at a bead mill stirring peripheral speed = 12m/s, grinding was then carried out for 4 hours using a grinding slurry prepared from 1.0% by weight of aluminum oxide (Tipton Co., Ltd., Light 1A) with a particle size of 1μm and 0.5% by weight of D-305 as a dispersant.Finally, the slurry prepared with only D-305: 0.5 wt% was used for 2 hours of polishing to remove the surface residue of the ceramic sphere, and a ceramic sphere with a surface roughness of Ra = 2nm was obtained. The subsequent screening classification was carried out in the same way as in Example 1.
進行與實施例1同樣的製造製程直到HIP處理，但研磨步驟係使用珠磨機依如下條件進行。研磨材係使用由粒徑3μm之氧化鋁(Tipton公司(股)、Light 1A)3.0重量%、分散劑之多元羧酸鈉塩(中京油脂(股)、Serna D-305)0.5重量%調製的研磨漿，依珠磨機攪拌圓周速度=12m/s合計研磨6小時後，再利用僅由D-305：0.5重量%調製的漿施行2小時拋光，除去陶瓷球形體的表面殘渣，獲得表面粗糙度Ra=5nm的陶瓷球形體。之後的篩式分級係依照與實施例1同樣之手法實施。The same manufacturing process as in Example 1 was carried out until the HIP treatment, but the grinding step was carried out using a bead mill under the following conditions. The grinding material was a grinding slurry prepared from 3.0% by weight of aluminum oxide (Light 1A, Tipton Co., Ltd.) with a particle size of 3μm and 0.5% by weight of polycarboxylic acid sodium salt (Serna D-305, Zhongjing Oil Co., Ltd.) as a dispersant. After grinding for a total of 6 hours at a bead mill stirring peripheral speed = 12m/s, the slurry was used to polish for 2 hours using only 0.5% by weight of D-305 to remove the surface residue of the ceramic sphere and obtain a ceramic sphere with a surface roughness of Ra = 5nm. The subsequent screening classification was carried out in the same manner as in Example 1.
進行與實施例1同樣的製造製程直到HIP處理，但研磨步驟係使用珠磨機依如下條件進行。研磨材係使用由粒徑3μm之氧化鋁(Tipton公司(股)、Light 1A)3.0重量%、分散劑之多元羧酸鈉塩(中京油脂(股)、Serna D-305)0.5重量%調製的研磨漿，依珠磨機攪拌圓周速度=12m/s合計研磨3小時後，再利用僅由D-305：0.5重量%調製的漿施行2小時拋光，除去陶瓷球形體的表面殘渣，獲得表面粗糙度Ra=10nm的陶瓷球形體。之後的篩式分級係依照與實施例1同樣的手法實施。The same manufacturing process as in Example 1 was carried out until the HIP treatment, but the grinding step was carried out using a bead mill under the following conditions. The grinding material was a grinding slurry prepared from 3.0% by weight of aluminum oxide (Light 1A, Tipton Co., Ltd.) with a particle size of 3μm and 0.5% by weight of polycarboxylic acid sodium salt (Serna D-305, Zhongjing Oil Co., Ltd.) as a dispersant. After grinding for a total of 3 hours at a bead mill stirring peripheral speed = 12m/s, the slurry was used to polish for 2 hours using only 0.5% by weight of D-305 to remove the surface residue of the ceramic sphere and obtain a ceramic sphere with a surface roughness of Ra = 10nm. The subsequent screening classification was carried out in the same manner as in Example 1.
與實施例1同樣地，依照滾動造粒成形法造粒至燒結後之平均粒徑X成為50μm前後之尺寸之成形體。除省略降低表面波浪的步驟之外，其餘均與實施例1同樣地實施，而製作表1所示之粉碎用球形介質。Similar to Example 1, the granulation is performed by the rolling granulation molding method until the average particle size X after sintering becomes a molded body of about 50 μm. Except for omitting the step of reducing the surface wave, the rest is implemented in the same way as Example 1 to produce the spherical medium for crushing shown in Table 1.
與實施例2同樣地，依照滾動造粒成形法造粒至燒結後之平均粒徑X成為100μm前後之尺寸之成形體。除省略降低表面波浪的步驟之外，其餘均與實施例2同樣地實施，而製作表1所示之粉碎用球形介質。Similar to Example 2, the granulation is carried out according to the rolling granulation molding method until the average particle size X after sintering becomes a molded body of about 100 μm. Except for omitting the step of reducing the surface wave, the rest is implemented in the same way as Example 2 to produce the spherical medium for crushing shown in Table 1.
與實施例3同樣地，依照滾動造粒成形法造粒至燒結後之平均粒徑X成為200μm之前後尺寸之成形體。除省略降低表面波浪的步驟之外，其餘均與實施例3同樣地實施，而製作表1所示之粉碎用球形介質。Similar to Example 3, the granulation was carried out by the rolling granulation molding method until the average particle size X after sintering became a molded body with a size of about 200 μm. Except for omitting the step of reducing the surface wave, the rest was implemented in the same way as Example 3 to produce the spherical medium for crushing shown in Table 1.
在氧氯化鋯中，依所獲得之陶瓷球形體中氧化物換算成為表1的氧化釔/二氧化鋯莫耳比所示比例之方式添加氯化釔，利用共沉法製作原料粉末。Yttrium chloride is added to zirconium oxychloride in such a manner that the oxide in the obtained ceramic sphere is converted into the ratio shown in the molar ratio of yttrium oxide/zirconium dioxide in Table 1, and the raw material powder is prepared by co-precipitation method.
其次，使用上述原料粉末，與實施例2同樣地，利用滾動造粒成形法造粒至燒結後之平均粒徑成為100μm尺寸之成形體，再實施降低表面波浪的步驟。所獲得之成形體經乾燥而除去水分後，施行煅燒、HIP處理。針對所獲得之燒結體，使用滾筒研磨裝置施行表面研磨後，藉由施行篩式分級，而製作表1所示之粉碎用球形介質。Next, the raw material powder is used to granulate the granules to an average particle size of 100 μm after sintering by the rolling granulation molding method in the same manner as in Example 2, and then the step of reducing the surface wave is performed. The obtained shaped body is dried to remove moisture, and then calcined and HIP treated. The obtained sintered body is surface ground using a roller grinding device, and then screen-graded to produce the spherical medium for crushing shown in Table 1.
進行與比較例1同樣的製法直到HIP步驟，但研磨步驟係與實施例8同樣依使用珠磨機之研磨條件實施，獲得表面粗糙度Ra=3nm的表面平滑性。篩式分級亦與實施例8同樣地實施。The same manufacturing method as in Comparative Example 1 was carried out until the HIP step, but the grinding step was carried out under the same grinding conditions as in Example 8 using a bead mill, and a surface smoothness of surface roughness Ra = 3nm was obtained. Screen grading was also carried out in the same manner as in Example 8.
評價結果如表1~2所示。The evaluation results are shown in Tables 1~2.
如實施例1~6所示，藉由降低表面波浪，便可獲得不易破損的陶瓷球形體。實施例7係藉由降低HIP溫度，而提高內部缺陷率、且龜裂個數略有増加，但仍在容許範圍內。As shown in Examples 1 to 6, by reducing the surface waves, a ceramic sphere that is not easily damaged can be obtained. Example 7 reduces the HIP temperature, thereby increasing the internal defect rate and slightly increasing the number of cracks, but it is still within the allowable range.
比較例1~3因為表面波浪較大，因而屬於較容易破損的陶瓷球形體。比較例4因為單斜晶比例較大，因而屬於較容易破損的陶瓷球形體。比較例5因為正方晶比例較大，因而水熱試驗後的壓碎荷重值降低率較大，屬於水溫上升時發生破損的可能性高的陶瓷球形體。比較例6，因為正方晶比例較小，因而屬於較容易破損的陶瓷球形體。Comparative Examples 1 to 3 are ceramic spheres that are easily damaged because of their large surface waves. Comparative Example 4 is a ceramic sphere that is easily damaged because of its large monoclinic crystal ratio. Comparative Example 5 is a ceramic sphere that has a high probability of being damaged when the water temperature rises because of its large tetragonal crystal ratio, and has a large reduction rate in the crushing load value after the hydrothermal test. Comparative Example 6 is a ceramic sphere that is easily damaged because of its small tetragonal crystal ratio.
再者，如實施例1及實施例8~10所示，若表面粗糙度Ra=5~20nm範圍，隨Ra降低，鈦酸鋇濕式分散時的二氧化鋯磨損量會降低，但5nm與2nm係呈現相同程度。又，此時的陶瓷球形體龜裂個數，實施例1、8~10均屬於零發生。又，龜裂試驗時的龜裂耐性係與實施例1同樣地，於實施例8~10中亦均為零發生。Furthermore, as shown in Examples 1 and 8-10, if the surface roughness Ra is in the range of 5-20 nm, as Ra decreases, the amount of zirconia wear during wet dispersion of barium titanate will decrease, but 5 nm and 2 nm are at the same level. In addition, the number of ceramic spherical body cracks at this time is zero in Examples 1 and 8-10. In addition, the crack resistance during the crack test is the same as in Example 1, and is also zero in Examples 8-10.
比較例7，鈦酸鋇濕式分散時的二氧化鋯磨損量雖較實施例10少，但呈現較實施例8~9高的數值。發現陶瓷球形體有龜裂產生，判斷可能係微小龜裂碎片混入鈦酸鋇分散物的影響。關於龜裂試驗時的龜裂個數亦是與比較例1無大差異，有龜裂產生。In Comparative Example 7, the wear of zirconium dioxide during wet dispersion of barium titanate is less than that of Example 10, but it is higher than that of Examples 8-9. It was found that the ceramic spheres had cracks, which may be caused by the mixing of tiny crack fragments into the barium titanate dispersion. The number of cracks during the crack test is not much different from that of Comparative Example 1, and cracks have occurred.
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