JPH10246698A - Method for analyzing ceramic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an analysis method for obtaining information regarding the amount of presence of phases easily in a ceramic body where a plurality of phases containing a common specific constituent exist. SOLUTION: In an analysis method, a ceramic body to be analyzed is in a similar constituent phase where at least two phases being included contain a common specific constituent and generates a difference in a surface roughness between parts where the presence ratio of the above similar constituent phase differs each other. By applying electron beams to the surface of the ceramic body, fluorescent X rays based on the above specific constituent are discharged and the fluorescent X rays are detected by a detector. Then, by utilizing that the intensity of fluorescent X rays to be detected changes according to the surface roughness of the ceramic body, information regarding the amount of presence of the similar constituent phase is obtained based on the intensity of fluorescent X rays to be detected in the above.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for analyzing ceramics.

[0002]

2. Description of the Related Art Conventionally, alumina (Al ₂ O ₃ ) is mainly used as a dielectric material used for electronic devices such as microwave capacitors and resonators, and a predetermined amount of titanium oxide (TiO ₂ ) and tin oxide ( Ceramics containing SnO ₂ ) are used. Such ceramics are manufactured by mixing and molding raw material powders such as Al ₂ O ₃ , TiO ₂ and SnO ₂ , and then firing them at about 1500 ° C. Here, at least a part of the blended TiO ₂ reacts with Al ₂ O ₃ during firing to form aluminum titanate (Al ₂ TiO ₅ ). The amount of this Al ₂ TiO ₅ formed And the distribution are also one of the factors governing the electrical characteristics (such as dielectric loss) of the ceramic body when used as the above device. It has an important meaning in manufacturing.

For example, when the ceramic body is cooled after firing, a part of the formed Al ₂ TiO ₅ may be decomposed into Al ₂ O ₃ and TiO ₂ . It is known that the amount of decomposition generally increases as the cooling rate decreases. At this time, if the amount of the decomposition becomes uneven in the ceramics, the dielectric loss of the ceramics body increases, leading to a problem of deteriorating the characteristics of the device. In order to prevent such inconvenience, for example, the relationship between the cooling rate of the ceramic body and the amount of decomposition of Al ₂ TiO ₅ is accurately grasped, and the necessary and sufficient cooling rate for preventing the unevenness of the decomposition amount from occurring so much. It is effective to find out each phase (Al ₂ T) in the ceramic body.
iO _5, Al ₂ O ₃ and the establishment of analytical methods information is obtained accurately for the presence of TiO _2, etc.) is essential.

[0004] Conventionally, as the analysis method, a method using X-ray diffraction (for example, a diffractometer method) or an electron probe X-ray microanalyzer (EPMA) is known. In the former method, monochromatic X-rays are incident on a powder or polycrystalline sample at various angles, and the intensity of the diffracted X-rays at each angle is detected. The relationship between the obtained X-ray diffraction intensity and the incident angle (diffraction pattern) ) Is a method of identifying each phase using the fact that the phase is unique depending on the crystal structure. On the other hand, the latter method, for example, in a scanning electron microscope,
A predetermined area of the sample surface is irradiated with a high-speed electron beam focused by an electron lens, thereby detecting and analyzing a group of fluorescent X-rays (different wavelengths and intensities depending on the contained components and contents) generated from the sample. By doing so, it is possible to obtain knowledge on the types, contents, distribution states, and the like of the elements in the sample in the above region. In general, if the phase is different, the type and content of the component will be different, so by knowing the distribution of one or more specific components by the above method,
It is possible to obtain information on the abundance ratio and distribution state of the desired phase in the sample.

[0005]

However, in the above-mentioned X-ray diffraction method, the average content ratio of the phase in the ceramic body can be relatively easily known, but information on the distribution state of each phase is obtained. Is very difficult. Specifically, a sample for diffraction is taken out from each part of one ceramic body, and X-ray diffraction is performed for each sample. However, since it is necessary to increase the number of samples to know the distribution state accurately, it is troublesome. In addition to this, if the original ceramic body is small, it becomes impossible to take out many samples.

On the other hand, in the method using EPMA, by scanning an electron beam on the sample surface, the intensity distribution of the fluorescent X-ray corresponding to a specific component on the sample surface can be displayed as an image by, for example, shading of pixels. (So-called fluorescent X-ray image), whereby the distribution of components in the sample can be easily grasped. Therefore, when the composition of the phase to be analyzed is significantly different from the other phases, the distribution state of the phase can be relatively easily known by using the above-described method. However, as mentioned above, in such a case to be identified by distinguishing the Al ₂ O ₃ and inclusions of TiO ₂ to which it and the Al ₂ TiO ₅ was Deki decomposed, Al ₂ TiO ₅ and A
Al as a common component between the l ₂ O _3, but also Al ₂
Since Ti as a common component is contained between TiO ₅ and TiO ₂ , there is a drawback that the above method is essentially difficult to determine.

An object of the present invention is to provide an analysis method which can easily obtain information on the abundance of a phase in a ceramic body in which a plurality of phases containing a common specific component are mixed. It is in.

[0008]

Means for Solving the Problems and Functions / Effects To solve the above problems, the analysis method of the present invention has the following features. That is, the ceramic body to be analyzed is
A plurality of phases are mixed, and at least two or more of the plurality of phases contain a common specific component (similar component phase), and the abundance ratios of the similar component phases are mutually different. A material that causes a difference in surface roughness between different parts is used. By irradiating the surface of such a ceramic body with an electron beam, fluorescent X-rays based on the specific component are emitted from the surface, and the fluorescent light is emitted by a detector arranged in a predetermined positional relationship with respect to the surface of the ceramic body. X-rays are detected. Then, the detected fluorescence X
Utilizing that the intensity of the line changes according to the surface roughness of the ceramic body, based on the intensity of the fluorescent X-rays from a predetermined region of the surface of the ceramic body, at least one of the above-mentioned similar component phases is used. , Information on the abundance in the area is obtained.

That is, even if two or more similar component phases containing a common specific component are mixed in the same ceramics body, the present inventors have found that the two components having different proportions of the similar component phases have different proportions. If there is a difference in the surface roughness of the ceramic body, there will be a difference in the detection intensity of the fluorescent X-ray based on the specific component emitted when the electron beam is irradiated on the surface roughness. It has been found that information on the abundance ratio of the component phases can be obtained.

Thus, when a ceramic body contains a plurality of phases having substantially the same composition and different crystal structures only (for example, a phase on the high temperature side remains as a non-equilibrium phase due to rapid cooling). Alternatively, it is difficult to obtain information on the discrimination and abundance of the high-temperature phase using conventional methods, such as when two or more phases that partially decompose and finely mix with each other are dispersed and formed with cooling of the high-temperature phase. The analysis of the analogous component phase which has been considered can be easily performed. For example, by detecting the fluorescent X-rays at a plurality of positions on the surface of the ceramic body and obtaining the distribution of the intensity values of the fluorescent X-rays on the surface of the ceramic body, the distribution of the intensity values is the distribution state of the similar component phase on the surface. Is information that reflects the When X-ray fluorescence is detected at a plurality of positions on the surface of the ceramic body, for example, a beam of an electron beam to be irradiated is one-dimensionally (ie, linear) or two-dimensionally irradiated on the surface.
A method of performing dimensional (ie, planar) scanning is effective.

In the case where a ceramic body to be analyzed uses a material whose difference in surface roughness between parts having different proportions of similar component phases is emphasized by polishing, the present invention provides The effect will be more remarkably achieved. In this case, the surface of the ceramic body
An electron beam is irradiated after polishing is performed in advance.

As a specific example of the ceramic body, at least a part of the first phase existing at a predetermined first temperature is cooled to a second temperature lower than the first phase by one or more first phases. One that undergoes a phase transformation or decomposition into two phases, and the first phase and the second phase constitute the aforementioned similar component phase. For such a ceramic body, information reflecting the distribution state of the similar component phase is often obtained particularly easily. The reason for the presumption will be described with reference to the drawings.

For the sake of simplicity, as shown in FIG. 1 (a), the ceramic bodies to be analyzed are all the main metal element components θ and σ at the first temperature (for example, the firing temperature of ceramics) T1. (B) by cooling at a predetermined cooling rate to a second temperature (eg, room temperature) assuming a single phase α (first phase) containing A part thereof is decomposed into a phase β having a common component θ with the phase α and a phase γ also having a common component σ. Since the cooling rate of the surface layer portion of the ceramic body is high, the phase β of the phase α and the phase γ
The amount of decomposition is small, and the cooling rate is relatively low in the central part, so that the amount of decomposition is large, and the region where the amount of decomposition is large (ie, the phase β and the phase γ are mainly contained) It is assumed that the area K is determined to be an outer area L having a small amount of decomposition (that is, an area mainly composed of the phase α) L. FIGS. 2A and 2B show cross sections of FIGS. 1A and 1B, respectively.

When the above-mentioned regions K and L are to be determined based on the emission intensity distribution of fluorescent X-rays from a specific component by irradiating the ceramic body with an electron beam as described above, for example, the phase α and the phase β If the fluorescent X-rays of the component σ that are not common between the components are used, the fluorescent light of the component σ is hardly detected from the phase β. However, actually, the region K where a large amount of phase β is generated
Is mixed with the phase γ containing the component σ in a dispersed manner, and the fluorescent X-rays of the component σ based on the phase γ are detected at a considerable intensity. Becomes Conversely, when the fluorescent X-rays having the component θ are used, the fluorescent X-rays are hardly detected from the phase γ, but are detected from the phase β.
As described above, it can be understood that it is extremely difficult to accurately distinguish the regions K and L from the intensity distribution of the fluorescent X-ray of the specific component, no matter what component is focused.

Here, when the surface of the above-mentioned ceramic body after cooling is polished, as shown in FIG. 2C, the crystal grains of phase β and phase γ generated by decomposition of phase α become: In some cases, the crystal grains of the phase α are more likely to fall off from the ceramic body. For example, as shown in FIG.
When the volume change during the decomposition of phase into phase β and phase γ is relatively large, since both phases are brittle ceramic phases, fine cracks are formed around the crystal grains of generated phase β and phase γ. This may cause the bonding strength of the crystal grains to the ceramic body to weaken, thereby causing grain shedding.

When the crystal grains of the phase β and the phase γ fall off by polishing, a dropout hole is formed after that, and as a result, the region K where many of the phases β and γ are formed
On the other hand, the surface roughness of the polished surface is increased due to the formation of a large number of pits, and the area L has a small number of pits due to the small amount of the phases β and γ formed. Will be exhibited. And, as shown in FIG.
By irradiating the polished surface with an electron beam, fluorescent X-rays of a predetermined component (for example, θ or σ) emitted from the surface of the ceramic body are detected by a detector arranged at a predetermined angle with respect to the surface. Upon detection, the fluorescent X-rays emitted from the region L reach the detector at an average energy level without being particularly interrupted because the polished surface is flat, as shown in FIG. I do. On the other hand, the total emission amount of the fluorescent X-rays from the region K having a large surface roughness as shown in FIG.
The following difference occurs between the distribution state of the X-ray intensity value and the region L having a small surface roughness. That is, for example, a large number of drop holes are formed in the region K. However, the fluorescent X-rays emitted from the inner surface of the drop hole hit the wall surface of the drop hole and are blocked, so that they reach the detector at a low energy level. On the other hand, the fluorescent X-rays emitted from the end of the dropout hole or the projection reach the detector at a high energy level. As a result, there is a difference in the distribution state of the detected intensity of the fluorescent X-ray between the region K and the region L, and it is possible to distinguish the two regions.

The above is summarized as follows. That is, the surface roughness of the ceramic body increases as the proportion of specific similar component phases (phase β and phase γ in the above example) increases. In the distribution of the intensity values of the fluorescent X-rays from the surface of the ceramic body, information (intensity value variation information) that reflects the degree of variation of the intensity values, such as width, variance, and standard deviation, has a large surface roughness. In the area, the degree of variation in the intensity value is larger than that in the area having a small surface roughness. In the distribution of the intensity value of the fluorescent X-ray in a predetermined area of the ceramic body, the intensity value indicated by the intensity value variation information is The greater the degree of variation, the greater the proportion of the specific similar component phase in the region.

For example, whether or not there is a difference in a specific similar component phase between a certain region and a certain region can be known by judging whether or not there is a difference in intensity value variation information in the region. For example, when the intensity distribution width represented by the difference between the maximum value and the minimum value of the intensity of the fluorescent X-rays on the surface is adopted as the intensity value variation information, the region having the large surface roughness is smaller than the region having the small surface roughness. Also, since the intensity distribution width is large, it can be determined whether or not there is a difference in the amount of the similar component phase based on whether or not there is a difference in the intensity distribution width.

Further, in the region where the surface roughness is large, the width of the intensity distribution value of the fluorescent X-ray becomes large, and the variance or the standard deviation of the intensity value also becomes large. It can also be used as an index for determination. The use of the variance or the standard deviation has an advantage that even if the maximum intensity value or the minimum intensity value suddenly increases due to the influence of noise or the like, the influence is less likely to be obtained. Further, as the width of the intensity distribution value of the fluorescent X-rays increases, the maximum value of the intensity of the fluorescent X-rays tends to increase and the minimum value also tends to decrease. In this case, the maximum value or the minimum value of the intensity of the fluorescent X-ray can be used as an index for determining the magnitude of the amount of the similar component phase as the intensity value variation information. Further, as the intensity value variation information, a first reference value is set on the high intensity side with respect to the average intensity value in the intensity distribution of the fluorescent X-ray, and a unit area of an analysis point having an intensity value higher than the first reference value per unit area. Can also be used. Conversely, a second reference value is set on the low intensity side with respect to the average intensity value in the intensity distribution of the fluorescent X-rays, and a unit area of an analysis point having an intensity value lower than the second reference value per unit area is set. Can also be used.

As a more specific example of the ceramic body, a metal titanate phase in which the first phase contains titanium and another predetermined metal as a constituent metal element (for example, aluminum titanate (Al ₂ TiO ₅ )), and the second phase is titanium oxide (T) formed by decomposition of the metal titanate phase.
iO ₂ ) phase and an oxide phase of the predetermined metal (for example, Al ₂ O)
₃ ) and those containing: For example, 70 to 90% by weight of Al ₂ O ₃ and ₂ to 20% of TiO ₂
Wt%, and the other ceramic components of SnO ₂ or the like by firing by a predetermined amount, from 10 to 80% by weight of the TiO ₂ of the total amount was formed Al ₂ TiO ₅ phase reacts with Al ₂ O ₃ These are widely used as dielectrics used in electronic devices such as microwave capacitors and resonators. In this case, the generated Al ₂ TiO ₅
Some of the phases may decompose into TiO ₂ and Al ₂ O ₃ phases upon cooling. As the ceramic body, one containing calcium titanate, strontium titanate, barium titanate or the like in addition to the one containing aluminum titanate as the metal titanate salt phase can be applied to the method of the present invention.

Next, the distribution of the detected fluorescent X-rays on the surface of the ceramic body can be visualized by various methods. For example, a predetermined analysis area is set on the surface of the ceramic body, and this is made to correspond to an output area of a predetermined output device, such as a display area of a display device or a print area of a printing device, and the intensity of the detected fluorescent X-rays. The range of values is divided by one or a plurality of thresholds, and the respective densities and / or colors of the pixels forming the output area are made to correspond one-to-one to each of the divided ranges of the intensity values. By setting the density and / or color of pixels corresponding to a plurality of predetermined positions on the analysis area to those corresponding to the intensity values of the fluorescent X-rays detected at those positions,
The distribution of the intensity values of the fluorescent X-rays in the analysis area is mapped on the output area, and the mapping result is output to an output device, thereby obtaining this as information reflecting the distribution state of the similar component phase in the analysis area. . In addition,
In order to detect X-ray fluorescence from each position in the analysis area,
What is necessary is just to scan the irradiated electron beam two-dimensionally in the analysis area.

In this way, the intensity value distribution of the fluorescent X-rays on the analysis area can be visually displayed two-dimensionally by the difference in the density and / or color of the pixels. That is, in the above example, the area where the variation in the detection intensity of the fluorescent X-ray is small due to the large surface roughness of the ceramic body, and conversely, the detection intensity of the fluorescent X-ray due to the small surface roughness Are displayed with different densities and / or color distributions, so that it is possible to distinguish at a glance a region having a large number of specific similar component phases and a region having a small number of similar component phases.

On the other hand, a virtual analysis line is set on the surface of the ceramic body, the intensity of the fluorescent X-ray is detected at a plurality of predetermined positions on the analysis line, and the detection result of the intensity value of the fluorescent X-ray is obtained. By outputting the data to the output device in a form associated with the position on the analysis line, the information can be obtained as information reflecting the distribution state of the similar component phase on the analysis line.

Also, two or more various values of the intensity value variation information of the fluorescent X-rays (that is, the above-described intensity value width, variance, standard deviation, etc.) and the existence of a specific similar component phase corresponding to each value. If a calibration curve indicating the relationship with the ratio is prepared in advance, the value of the intensity value variation information is obtained based on the distribution of the detected fluorescent X-rays, and a specific similar component phase corresponding to the value of the intensity value variation information is obtained. Can be quantitatively identified with reference to the above calibration curve. The calibration curve is for obtaining the above-mentioned intensity value variation information (or an average value thereof) due to fluorescent X-rays from the surface for each of a plurality of ceramic body samples which are considered to have different proportions of the similar component phase. Alternatively, the existence ratio of the similar component phase can be specified by the X-ray diffraction method, and can be created based on a combination of the data of the intensity value variation information and the data of the existence ratio of the similar component phase.

[0025]

Embodiments of the present invention will be described below with reference to the embodiments shown in the drawings. FIG. 5 shows that in the method for analyzing a ceramic body of the present invention, the surface of the ceramic body sample is irradiated with an electron beam to detect fluorescent X-rays from the surface of the sample, and the detection result is not displayed as visual information. FIG. 3 is a block diagram illustrating a configuration example of a device that prints out. That is, the device 1 is an existing EPMA
It has almost the same configuration as the device, and the I / O port 6
And the CPU 3, ROM 4, and RAM 5 connected thereto.
A central control unit 2 comprising a ceramic sample (not shown) set on a sample table in a vacuum chamber, an electron beam focused on a predetermined analysis surface by an electron lens. An electron beam scanning mechanism 7 for irradiating a beam and scanning the beam one-dimensionally or two-dimensionally on the analysis surface, and detecting fluorescent X-rays of various wavelengths emitted from the ceramic body upon irradiation with the electron beam. A monitor 9 for printing or displaying and outputting the detection result of the fluorescent X-ray or the analysis result based on the detection result. The detector 8 includes a spectroscopic unit for selectively extracting only a specific wavelength (that is, a component corresponding to a specific component element) of the fluorescent X-rays of various wavelengths, and an intensity of the separated fluorescent X-ray. And a detecting unit such as a scintillation counter or a proportional counter for detecting the temperature. The monitor 11 is connected to the I
/ O port 6 Further, a control program for controlling the entire apparatus 1 is stored in the ROM 4.

For example, when the surface of a ceramic body sample is polished and irradiated with an electron beam while scanning the analysis region two-dimensionally, fluorescent X-rays are emitted from each position in the analysis region. The detector 8 detects the wavelength based on the specific component element, and sends the count value to the central control unit 2 as the data of the fluorescent X-ray intensity at each position. Here, as shown in FIG. 6A, the analysis area 10 is divided in a matrix by a predetermined number of small and vertical areas 11 and, as shown in FIG. A storage area 31 corresponding to each of the small areas 11 is formed, and data of the detected intensity value of the fluorescent X-ray from each corresponding small area 11 is stored therein.

On the other hand, as shown in FIG. 6C, each of the small areas 11 is a predetermined display area set on the screen of the monitor 11 or a predetermined print area of the printer 9 (hereinafter, collectively referred to as these). , Which are referred to as output areas). Then, as shown in FIG. 6D, the range of the intensity value of the detected fluorescent X-ray is divided by one or a plurality of threshold values, and an output area is formed in each of the divided intensity values. Different colors (or densities) of the corresponding pixels are associated with each other on a one-to-one basis, and a table indicating the correspondence is stored in the ROM 4. Then, referring to the table, each small area 11
Is set to a color corresponding to the intensity value of the fluorescent X-ray detected in each of the regions 11 so that the distribution of the intensity value of the fluorescent X-ray in the analysis region is displayed on the output region. Color mapping is performed, and the result can be output as an image to the monitor 11 or printed out from the printer 9. The mapping may be performed by a single color shading display (for example, gray scale). Alternatively, only one threshold value is set, and the pixel is classified into two types of density depending on whether the detection intensity is larger than the threshold value. It may be performed by a binary output set to any one.

Hereinafter, a specific analysis example and an output example of the result will be described. The sample used for the analysis was prepared as follows. First, Al ₂ O ₃ powder (average particle size 0.5 μm)
m, purity 99.95% by weight) 82.7 g, TiO ₂ powder (average particle size 0.3 μm, purity 99.9% by weight) 7.7
g and SnO ₂ powder (average particle size 0.6 μm, purity 99.
(5% by weight), 9.7 g of water, 80 ml of water and 1.5 g of polyvinyl alcohol as a binder were mixed and mixed for a predetermined time by a ball mill, and the obtained slurry was dried to obtain a raw material powder. This is molded at a predetermined pressure into a cylindrical shape having a diameter of 19 mm and a height of 10 mm.
After sintering for 1 hour in the atmosphere of the above, it was cooled to room temperature at a predetermined speed, and the outer surface was further polished to a diameter of 15 mm and a height of 8 mm.
A cylindrical ceramic body sample was obtained. The sample is
Two types were prepared, one having an average cooling rate to room temperature of 400 ° C./hour and one having an average cooling rate of 30 ° C./hour (hereinafter, the former is referred to as a rapidly cooled sample, and the latter is referred to as a gradually cooled sample).

Next, the samples were cut at the center in the height direction in a direction perpendicular to the axis, and the cut surfaces were mirror-polished using a diamond paste. Then, for each of the outer portion and the central portion of the polished surface, JISB-0601
After measuring the surface roughness by the method shown in the above, the surface roughness was set in an existing EPMA apparatus, and the polished surface was irradiated with an electron beam while scanning it two-dimensionally. (Hereinafter referred to as Ti fluorescent X-rays), and the distribution of the detected intensity was color-mapped according to the method described above. In this embodiment, the fluorescent X-ray detection intensity range is divided into 18 levels, and the detection intensity corresponding to each range is displayed in different colors. Further, for each of the above parts, X by the diffractometry method
The line diffraction pattern was also measured. For comparison, a sample not subjected to mirror polishing was separately prepared, and the same analysis was performed.

FIG. 7 shows the measurement results of the surface roughness of the outer portion ((a)) and the center portion ((b)) of the polished surface of the quenched sample, and the latter (Rmax = 0.58 μm). It can be seen that the surface is rougher than the former (Rmax = 0.20 μm). 8A and 8B show scanning electron micrographs of the outer portion and the center portion, respectively, in which FIG. 8A shows a relatively flat surface state in the former, while polishing is being performed in the latter in the latter. In this case, a large number of irregularities are formed, which are considered to be caused by dropping of the crystal grains.

FIG. 9 (a) shows a color mapping output showing the distribution of the detected intensity of Ti fluorescent X-rays from the polished surface of the quenched sample. In the figure, an area K surrounded by a solid line near the center of the sample has a large intensity value width of about 208 cps in the detected intensity value distribution, and many color spots corresponding to the intensity width are mixed. However, visually, for example, red and purple spots are conspicuous and appear slightly darker as a whole.
On the other hand, in the area L outside the area K, the width of the intensity value is 3
Since it is as small as about 5 cps, the number of colors covering the intensity range is small, and visually, particularly, yellow spots and green spots are conspicuous, and the whole area is displayed whitish. The width of the region K in the intensity distribution of the Ti fluorescent X-rays is about six times larger than the width of the region L outside the region K.

FIGS. 10 (a) and 10 (b) show the X-ray diffraction patterns of the former on the outer side of the sample and the latter on the center. In (a), the diffraction peak (indicated by O) of the Al ₂ TiO ₅ phase, which is considered to have been formed by the reaction between Al ₂ O ₃ and TiO ₂ during firing, is relatively large, and TiO ₂ Almost no phase diffraction peak appears. On the other hand, in (b), Al ₂ Ti
While the diffraction peak of the O ₅ phase is considerably smaller than that of (a), the diffraction peak of the rutile type TiO ₂ phase (indicated by R in the figure) appears relatively large. This means that the outer part of the sample has a relatively high cooling rate after firing, so that most of the Al ₂ TiO ₅ phase formed at the firing temperature remains in a supercooled state, This indicates that most of the Al ₂ TiO ₅ phase has been decomposed into a TiO ₂ phase and an Al ₂ O ₃ phase because the cooling rate is low in the inner part of.

As a result, in the color mapping output of FIG. 9A, the area K where red spots and purple spots mainly exist has a higher content ratio of the Al ₂ TiO ₅ phase than the outer area L. It can be seen that this indicates a region reduced by the decomposition. In the case of the sample which was not subjected to mirror polishing, the surface roughness was almost the same between the outer portion and the center portion of the sample, and there was almost no difference between the two portions in the corresponding color mapping output.

In the above-described region K, as shown in FIGS. 7 and 8, the surface roughness of the polished surface is larger than that of the outer region L due to the drop of crystal grains. The cause is that the Al ₂ TiO ₅ phase is TiO ₂ phase and Al ₂ O
_Since the volume change when decomposed into _three phases is relatively large, many fine cracks are generated around the crystal grains of the TiO ₂ phase and Al ₂ O ₃ phase generated by the decomposition, and the This is probably due to the tendency of the grains to fall off. In the region K, as shown schematically in FIG. 4B, for example, the Ti fluorescent X-rays emitted from the inner surface of the dropout hole are weak, and those emitted from the end projections are weak. Since it is detected strongly, it is assumed that the value of the width of the intensity value in the intensity value distribution has increased.

As described above, in the color mapping data, the width of the detected Ti fluorescence X-rays from the region L is about 35 cps in the detected intensity distribution, and the Ti fluorescent X-rays from the region K are also the same. Range of intensity values is 2
It can be calculated that it is about 08 cps. On the other hand, FIG.
From the results of X-ray diffraction shown in FIG. ₅ , the content of the Al ₂ TiO ₅ phase in the portion corresponding to the region L is about 17.5% by weight, considering that almost 100% of TiO ₂ has reacted with Al ₂ O _3. %
And Al ₂ Ti in a portion corresponding to the region K.
The content of the O ₅ phase is considered to be about 2.7% by weight from the peak area ratio of the (020) plane and the (023) plane of the Al ₂ TiO ₅ phase indicated by the arrow in the figure. Therefore, as shown in FIG. 11, the thus obtained Al ₂ Ti
The content of the O ₅ phase is plotted against the average detection intensity of the Ti fluorescent X-rays, and a straight line or a curve regression is applied thereto.
i A calibration curve for determining the content of the Al ₂ TiO ₅ phase can be obtained from the detected intensity of the fluorescent X-ray, and the
it is possible to identify the amount of l ₂ TiO ₅ phase.

On the other hand, FIG. 9B shows a color mapping output when the same analysis is performed on the slowly cooled sample. Regarding this sample, even when mirror polishing was performed, there was almost no difference in surface roughness between the outer portion and the central portion (the former was Rmax = 0.59 μm, and the latter was Rmax = 0.58 μm).
m), many of the crystal grains were dropped out. In the color mapping output, the width in the intensity distribution of the Ti fluorescent X-rays is large over the entire polished surface, and a number of color spots corresponding to the intensity width are mixed. This is presumably because the sample was gradually cooled, so that the decomposition of the Al ₂ TiO ₅ phase progressed over the entire sample.

In the embodiment described above, the electron beam is two-dimensionally scanned on the sample surface,
Although the method of two-dimensionally mapping the detection intensity of the fluorescent X-rays to the output area has been described, a method of performing a so-called line analysis by using this as one-dimensional scanning is also possible.
That is, as shown in FIG. 12A, a virtual analysis line is set on the polished surface, the intensity of the fluorescent X-ray is detected along the analysis line, and as shown in FIG. The detection result of the detected intensity value of the fluorescent X-ray can be output to the monitor 11 or the printer 9 in FIG. 5 in a form associated with the position on the analysis line.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing the structure of a ceramic body.

FIG. 2 is an explanatory diagram showing a state in which crystal grains drop off in a ceramic body due to decomposition of a phase.

FIG. 3 is a schematic diagram for explaining the reason why crystal grains are likely to drop due to phase decomposition.

FIG. 4 is a schematic diagram showing a difference in a detection state of fluorescent X-rays between a flat polished surface and a polished surface having a large surface roughness due to dropping of crystal grains.

FIG. 5 is a block diagram showing an example of a device configuration for performing the analysis method of the present invention.

FIG. 6 is an explanatory diagram showing a relationship between a small area set on an analysis surface, a memory area and pixels of an output device, and a fluorescent X
FIG. 4 is a conceptual diagram of a table for giving a relationship between a line detection intensity range and a pixel output state.

FIG. 7 is a diagram illustrating an example of a measurement result of a surface roughness of a polished surface of a sample in an analysis example.

FIG. 8 is a scanning electron micrograph of a polished surface of a sample.

FIG. 9 is a diagram showing an analysis example of two-dimensional color mapping of the intensity distribution of fluorescent X-rays.

FIG. 10 is a diagram showing an example of an X-ray diffraction pattern of a sample.

FIG. 11 is a diagram showing an example of a calibration curve for determining the content ratio of a specific phase from the intensity of fluorescent X-rays.

FIG. 12 is an explanatory diagram of a method of measuring the intensity distribution of fluorescent X-rays along an analysis line and a conceptual diagram of an analysis profile obtained by the method.

[Explanation of symbols]

 8 Detector 9 Printer (output device) 11 Monitor (output device) 21 pixels

Claims (10)

[Claims] 1. A ceramic comprising a plurality of different phases mixed with each other, wherein at least two or more of the plurality of phases contain a common specific component (hereinafter referred to as a similar component phase). A method for analyzing a body, wherein the ceramic body has a difference in surface roughness between portions where the proportions of the similar component phases are different from each other, and irradiating the surface of the ceramic body with an electron beam. The fluorescent X-rays based on the specific component are emitted from the surface, and the fluorescent X-rays are detected by a detector arranged in a predetermined positional relationship with respect to the surface of the ceramic body, and the fluorescent light is detected. Utilizing that the intensity of X-rays changes according to the surface roughness of the ceramic body, the fluorescent X-rays from a predetermined region on the surface of the ceramic body are used. Based on output intensity, the similar component phases of at least one thing, the analysis method of the ceramic, characterized in that to obtain the information about the abundance in the region. 2. A distribution of intensity values of the fluorescent X-rays on the surface of the ceramic body by detecting the fluorescent X-rays at a plurality of positions on the surface of the ceramic body, and calculating the distribution of the intensity components of the X-rays on the surface of the ceramic body. 2. The method for analyzing ceramics according to claim 1, wherein the information is obtained as information reflecting a phase distribution state. 3. The ceramic body has a difference in surface roughness between portions having different proportions of the similar component phase.
3. The method for analyzing ceramics according to claim 1, wherein a material emphasized by polishing is used, and the surface of the ceramic body is irradiated with the electron beam after being subjected to polishing in advance. 4. The surface roughness of the ceramic body increases as the proportion of a specific similar component phase increases, and the distribution of the intensity values of the fluorescent X-rays from the ceramic body surface has a width. (Hereinafter referred to as “intensity value variation information”) that reflects the degree of variation of the intensity values such as variance, standard deviation, etc. In the distribution of the intensity values of the fluorescent X-rays in a predetermined region of the ceramic body, the greater the degree of variation in the intensity values indicated by the intensity value variation information, the greater the degree of the identification in the region. The method for analyzing ceramics according to any one of claims 1 to 3, wherein a similar component phase is present in a large proportion. 5. The intensity value variation information is an intensity distribution width represented by a difference between a maximum value and a minimum value of the intensity of the fluorescent X-rays on the surface, and the surface roughness in a region where the surface roughness is large. 5. The method for analyzing ceramics according to claim 4, wherein the intensity distribution width is larger than a region having a smaller value. 6. The ceramic body according to claim 1, wherein at least a part of the first phase existing at a predetermined first temperature is cooled to a second temperature lower than the first phase. The first phase and the second phase constitute the similar component phase, and the surface roughness of the ceramic body changes according to the abundance ratio of the second phase. The method for analyzing ceramics according to claim 4, wherein: 7. The first phase is a metal titanate salt phase comprising titanium and a specific metal other than titanium as a constituent metal element,
The ceramic analysis method according to claim 6, wherein the second phase includes a titanium oxide phase generated by decomposition of the metal titanate salt phase and an oxide phase of the specific metal. 8. A predetermined analysis area is set on the surface of the ceramic body, and is set to correspond to an output area of a predetermined output device such as a display area of a display device or a print area of a printing device. The range of the intensity value of the fluorescent X-ray is divided by one or a plurality of threshold values, and the different densities and / or colors of the pixels forming the output area correspond one-to-one with each of the divided intensity values. By setting the density and / or color of pixels corresponding to a plurality of predetermined positions on the analysis area to those corresponding to the intensity values of the fluorescent X-rays detected at the respective positions, the analysis area Mapping the distribution of the intensity values of the fluorescent X-rays on the output area, and outputting the mapping result to the output device, so that the result of the mapping is obtained before the analysis area. The analysis method of the ceramic according to any one of claims 2 to obtain as information reflecting the distribution of similarity component phases 7. 9. A virtual analysis line is set on the surface of the ceramic body, the intensity of the fluorescent X-ray is detected at a plurality of positions on the analysis line, and the detection result of the intensity value of the fluorescent X-ray is obtained. 8. The method according to claim 2, wherein the information is output to an output device in a form associated with the position on the analysis line, thereby obtaining the information reflecting the distribution state of the similar component phase on the analysis line. Analysis method of the described ceramics. 10. A calibration curve indicating in advance the relationship between two or more various values of the intensity value variation information and the abundance ratio of the specific similar component phase corresponding to each value, and detects the detected fluorescence. The value of the intensity value variation information is obtained based on the distribution of X-rays, and the existence ratio of the specific similar component phase corresponding to the value of the intensity value variation information is quantitatively identified with reference to the calibration curve. The method for analyzing ceramics according to any one of claims 1 to 9, wherein: