JP5871736B2 - Etching solution processing mechanism and etching solution coating method - Google Patents

Description

  The present invention relates to an etching solution processing mechanism and an etching solution application method. More specifically, the present invention enables pretreatment of an etching solution to enable a more complicated etching process in a technique for reconstructing a sequential etching structure image used when acquiring a three-dimensional material structure image. The present invention relates to an etching solution processing mechanism and an etching solution application method.

  In structural metal materials such as steel, aluminum, and magnesium, materials with low energy loss and materials excellent in environmental resistance are required. For the development of such materials, the three-dimensional data of the material organization has begun to be utilized along with the advancement of nanotechnology and science and technology. Many metal materials are polycrystalline materials composed of a plurality of crystals, and variations in the size of crystal grains constituting the metal material may affect mechanical properties such as strength or ductility of the metal material. Many. In addition, the crystal grains of the metal material have a three-dimensional irregular shape, and the crystal grain size and grain size distribution obtained from observation with an optical microscope, which is two-dimensional cross-sectional structure observation, are accurate. It's hard to be a thing. Furthermore, in material design using computer simulation based on a physical model, it is necessary to use highly accurate three-dimensional distribution data of crystal grain size as input data, and there is a demand for acquiring measured values of three-dimensional data of material structures. There is.

  Two methods for three-dimensional observation of the material structure are known. The first method is a non-destructive method using X-rays. An example of a non-destructive method is a tomography method in which an X-ray image transmitted through a material is reconstructed to obtain a three-dimensional image. The tomography method has a problem in that an X-ray source that emits strong radiation is required because the X-ray transmission ability with respect to a metal material is small. Furthermore, even when an X-ray source that emits strong synchrotron radiation is used, in order to obtain a three-dimensional image of the steel material, it is necessary to reduce the thickness of the sample to about 0.5 mm. For this reason, it is not easy to apply the tomography method to a structural member in which a steel plate having a thickness of several mm or more is used.

  The second method is a serial sectioning method. In the serial sectioning method, a microscope image obtained by performing mechanical polishing (hereinafter also referred to as mechanical polishing or simply polishing), chemical etching (hereinafter also simply referred to as etching), and microscope observation step by step is reproduced. It is constructed to obtain a three-dimensional image. In the serial sectioning method, the surface of a material is mechanically polished, and then a material structure obtained by chemical etching is observed with a microscope. Next, a predetermined amount is further polished and the operation of microscopic observation after etching is continuously repeated, and the observed microscopic image is reconstructed to obtain a three-dimensional image.

  In the serial sectioning method, a two-dimensional image can be acquired at a certain depth by mechanical polishing. Moreover, the structure of the material structure | tissue of the surface of the grind | polished sample can be clarified by slightly corroding the metal surface by chemical etching and giving fine unevenness and coloring.

  The name of the serial sectioning method is derived from obtaining thin layer tissue images (also referred to as sectioning images) continuously. In the serial sectioning method, acquired thin tissue images are stacked using a computer and reconstructed as a stereoscopic image. An example of the thin layer structure is a surface structure obtained by polishing several hundreds of nanometers per time. A thin layer structure can be treated as having the same structure when reconstructed as a stereoscopic image.

  In the serial sectioning method, the material structure image of the most suitable size from several tens of microns to mm size can be obtained by using optical microscope observation, so various materials that occur during deformation, destruction, and material manufacturing process Organization information can be known. Such information cannot be obtained with a three-dimensional reconstructed image in a minute region of micron size or less where a transmission electron microscope image or a scanning electron microscope image is used.

  In the serial sectioning method, it is necessary to polish a sample every time a sectioning image is acquired. However, since the polishing and etching operations are performed manually, there is a problem that it takes about one week to obtain several hundred sectioning images from one target sample (Non-patent Document 1). reference). For this reason, there has been a strong need to fully automatically acquire a three-dimensional tissue image of several tens of microns to mm size.

  One way to solve this problem is to use a device called “Robo-Met.3D” jointly developed by the US Air Force Research Institute and Carnegi Mellon University. This method is a technique for performing a predetermined treatment by moving a sample with a robot arm in each of the processing steps of mechanical polishing, chemical etching, and optical microscope observation, and commercialization is progressing in the United States.

  The problem of this technique using a robot arm is that the sample is moved to a predetermined position by the robot arm, so that it is not easy to place the sample at the sample position without deviation on the order of submicrons. In the serial sectioning method, if a displacement occurs during processing, a huge amount of post-processing for correcting the position of the sectioning image is required when reconstructing the three-dimensional image. Furthermore, when observing a material structure in the order of μm or sub-μm, it may be difficult to obtain sufficient resolution. For this reason, it is required that the observation surface position of the sample does not rotate or shift in the surface.

  A device called “Genus — 3D” has solved this problem. In “Genus — 3D”, the sample is arranged in a vertical position and is moved in a straight line in the vertical direction, so there is no need to move the sample three-dimensionally by a robot arm or the like. “Genus — 3D” was developed by one of the inventors of the present invention.

  “Genus — 3D” has a vertical drive mechanism that moves the sample position up and down. When the sample is placed above, the image is taken with an optical microscope, and when it moves downward, the polishing disk moves from the horizontal direction and the sample is moved. To polish. Next, after cleaning the sample, the surface of the sample is etched with a single etching solution sprayed from a cleaning nozzle or an etching nozzle. In “Genus — 3D”, a series of these processes is automated by computer control, so that a sectioning image can be acquired without misalignment even in a material structure of μm order or sub-μm order. With the introduction of “Genus — 3D”, a three-dimensional distribution image of the crystal grain size of a steel material consisting of a single ferrite phase can be easily obtained, and the grain size of the ferritic steel that has a great influence on the strength and ductility of the ferritic steel It became possible to measure the distribution of.

  On the other hand, instead of carbon steel made of a ferrite single phase having low strength, high strength steel plate having high strength has been used. Hi-Ten has a steel plate structure in which various hard material structures other than ferrite such as pearlite, bainite and martensite are mixed. When verifying a steel material structure by optical microscopy, it is known to color each steel material structure by a characteristic etching method. For example, Patent Document 1 describes a technique for discriminating a ferrite phase from a bainite phase by a color etching method. Patent Document 2 describes a technique for color-etching an austenite phase by utilizing a complicated mixed etching solution. By applying these coloring techniques to fully automatic serial sectioning microscopy, it is possible to generate data for mechanical image processing for material structure measurement from images acquired by optical microscope observation. Tissue measurement is possible.

  As the range in which a fully automatic serial sectioning microscope using an optical microscope is used is expanded, it is desired to reconstruct a three-dimensional material structure image for a more complicated material structure. In order to reconstruct a three-dimensional material structure image, there is a need to use a color etching solution in which a plurality of etching solutions are mixed, instead of a single etching solution such as nital or chromic acid.

  However, in the fully automatic serial sectioning microscope, priority is given to automating each element of polishing, etching, cleaning and observation, and only a structure in which a single type of etching solution is sprayed from each nozzle and applied to the sample. Was known.

JP 59-219473 A JP-A-5-163590

Masato Enomoto et al., “Iron and Steel”, Volume 90 (2004), p. 183

  On the other hand, the structure which sprayed and apply | coated the etching liquid stored by mixing a some etching liquid from a single nozzle was examined. However, the surface texture etching of a metal material needs to control the mixing ratio, flow rate, concentration, etc. of the etching solution, and is not suitable for use as a plurality of mixed etching solutions. This is because the mixing ratio of the etching solutions changes due to a chemical reaction between the etching solutions of the plurality of stored etching solutions.

  An object of the present invention is to solve the above problems and establish a technique for mixing a plurality of etching solutions.

  In order to achieve the above object, the present inventor has intensively studied the form and configuration of an etching solution processing mechanism that can be attached to and detached from the fully automatic serial sectioning microscope apparatus. Has led to the development of the etching solution processing mechanism and the etching coating method.

(1) In a fully automatic serial sectioning microscope apparatus that polishes the surface of the sample, etches the surface of the polished sample, and automatically repeats a series of processes for imaging the surface of the etched sample. An etching solution processing mechanism for applying a mixed etching solution in which a first etching solution and a second etching solution different from the first etching solution are mixed to the surface of the polished sample;
A first etchant container containing the first etchant;
A second etchant container containing the second etchant;
An etching liquid mixing container for mixing and generating a mixed etching liquid by mixing the first and second etching liquids;
A first etching solution supply unit configured to supply a predetermined amount of the first etching solution from the first etching solution container to the etching solution mixing container when it is determined that the surface of the sample is polished ;
A second etching solution supply unit configured to supply a predetermined amount of the second etching solution from the second etching solution container to the etching solution mixing container when it is determined that the surface of the sample is polished ;
A cleaning liquid supply unit for supplying a cleaning liquid to the etching liquid mixing container after the mixed etching liquid is sprayed;
A mixed etching solution spraying unit that sprays and applies a predetermined amount of mixed etching solution from the etching solution mixing container onto the surface of the polished sample ;
After authenticating that the sample has moved to a position where the liquid ejected from the mixed etching liquid ejecting section does not reach the sample, the cleaning liquid contained in the etching liquid mixing container is ejected from the mixed etching liquid ejecting section. Etching solution processing mechanism for fully automatic serial sectioning microscope.

(2) a third etching solution container for containing a third etching solution different from the first and second etching solutions;
After a mixed etching solution obtained by mixing the first etching solution and the second etching solution is injected and the cleaning solution is injected, a predetermined amount of the third etching solution is transferred from the third etching solution container to the etching solution mixing container. A third etching solution supply unit for supplying
Further comprising
The mixed etching solution spraying unit sprays and applies the third etching solution from the etching solution mixing container onto the surface of the polished sample,
The cleaning liquid supply unit according to (1), wherein the cleaning liquid supply unit supplies the cleaning liquid to the etching liquid mixing container after the third etching liquid is sprayed .

(3) The etchant processing mechanism for a fully automatic serial sectioning microscope according to (2) , wherein each of the first to third etchant supply units has a metering pump .

(4) The etching solution processing mechanism for a fully automatic serial sectioning microscope according to any one of (1) to (3), wherein the etching solution processing mechanism further includes a stirrer disposed inside the etching solution mixing container .

(5) The etching solution processing mechanism for a fully automatic serial sectioning microscope according to any one of (1) to (4), which is detachably connected to the fully automatic serial sectioning microscope apparatus.

(6) In a fully automatic serial sectioning process in which a series of processes for polishing the surface of the sample, etching the surface of the polished sample, and imaging the surface of the etched sample is continuously automatically performed, A processing mechanism is a method of applying a mixed etching liquid to a sample, and the etching liquid processing mechanism is
When it is determined that the surface of the sample is polished, a mixed etching solution generated by mixing at least two different etching solutions at a predetermined ratio is contained in an etching solution mixing container,
Authenticate that the sample is placed at the etching position where the sample is etched,
After authenticating that the sample has moved to the etching position, the mixed etching solution is applied from the etching solution mixing container to the sample via a mixed etching solution spraying unit,
Supplying a cleaning liquid to the etching liquid mixing container,
Authenticates that the sample has moved to a cleaning retreat position where the liquid ejected from the mixed etching solution ejecting unit does not reach the sample;
After authenticating that the sample has moved to the cleaning retreat position, the cleaning liquid is sprayed through a mixed etching liquid spraying unit.
A method comprising steps.

  According to the present invention, it becomes possible to inject a mixed etching solution into a material structure such as a metal having a complicated structure to perform etching, and developed according to a wide range of needs such as a high-strength steel sheet. It is possible to reconstruct a three-dimensional material structure image for a multiphase steel material.

It is a see-through | perspective perspective view of the conventional fully automatic serial sectioning microscope apparatus. It is a schematic block diagram of the conventional fully automatic serial sectioning microscope apparatus. (A) shows the 1st state of the fully automatic serial sectioning microscope apparatus shown in FIG. 2, (b) shows the 2nd state of the fully automatic serial sectioning microscope apparatus shown in FIG. 2, (c) shows FIG. FIG. 4 shows a third state of the fully automatic serial sectioning microscope apparatus shown in FIG. 3, and FIG. 4D is a view showing a fourth state of the fully automatic serial sectioning microscope apparatus shown in FIG. 2. (A) is a schematic front view of the fully automatic serial sectioning microscope apparatus which concerns on this invention, (b) is a schematic plan view of the fully automatic serial sectioning microscope apparatus which concerns on this invention, (c) concerns on this invention It is a schematic side view of a fully automatic serial sectioning microscope apparatus. It is a schematic block diagram of the fully automatic serial sectioning microscope apparatus which concerns on this invention. It is a schematic block diagram of an example of the etching liquid processing mechanism which concerns on this invention. It is a figure which shows the processing flow of the etching liquid processing mechanism of FIG. It is a schematic block diagram of the other example of the etching liquid processing mechanism which concerns on this invention. It is a figure which shows the processing flow of the etching liquid processing mechanism of FIG. It is an optical micrograph of a finely dispersed martensite phase that has been subjected to repeller etching.

  Exemplary embodiments of the present invention will be described below in detail with reference to the accompanying drawings. In addition, in this specification and drawing, about the component which has the substantially same function structure, duplication description is abbreviate | omitted by attaching | subjecting the same code | symbol.

  First, the basic configuration of a fully automatic serial sectioning microscope to which the present invention is applied will be described.

  FIG. 1 is a perspective view of a fully automatic serial sectioning microscope apparatus 100. FIG. 2 is a schematic configuration diagram of the fully automatic serial sectioning microscope apparatus 100.

  The fully automatic serial sectioning microscope apparatus 100 that is “Genus — 3D” includes an optical microscope observation mechanism 10, a surface polishing apparatus mechanism 20, an etching solution processing mechanism 30, a cleaning processing mechanism 40, and a drying processing mechanism 50. The fully automatic serial sectioning microscope apparatus 100 further includes a control unit 60, a sample stage 70 on which the sample 110 is disposed, and a liquid receiving unit 80. The fully automatic serial sectioning microscope apparatus 100 is connected to a cleaning liquid source 140, an air compressor 150, and a general-purpose computer 160.

  The optical microscope observation mechanism 10 includes an objective lens 11, an eyepiece lens 12, an imaging unit 13, a lens barrel unit 14, and an illumination unit 15, and an etched metal surface structure of the sample 110 on the sample stage 70. Is taken as a digital image. The objective lens 11 is a lens arranged close to the sample 110 when the sample 110 is imaged. The eyepiece 12 is used when an operator (not shown) observes the metal surface structure of the sample 110 with the naked eye. The imaging unit 13 is a color camera with 5 million pixels. The lens barrel part 14 is a housing of the optical microscope observation mechanism 10 and forms an optical path between the eyepiece 12 and the imaging part 13. The illumination unit 15 provides moderate brightness to the optical path formed by the lens barrel unit 14.

  The surface polishing apparatus mechanism 20 includes a polishing plate 21, a polishing plate driving unit 22, first and second polishing liquid containers 23 and 24, and a laser polishing amount meter 25. The polishing plate 21 is a disc type polishing unit that polishes a thin layer structure in the depth direction by wet polishing. The polishing disk drive unit 22 has a motor and rotates the polishing disk 21 connected via a belt. The first and second polishing liquid containers 23 and 24 are each formed of polypropylene and store different kinds of polishing liquids. The laser polishing meter 25 measures the depth of the sample 110 polished by the polishing board 21.

  The surface polishing apparatus mechanism 20 can move the polishing plate 21 in the horizontal direction between a standby position and a polishing position where the polishing plate 21 polishes the sample 110 by a horizontal drive mechanism 26 indicated by a broken line arrow in FIG. it can. The horizontal drive mechanism 26 has a stepping motor, and the control unit 60 calculates the position of the polishing board 21 based on the pulse signal output from the stepping motor. When the polishing process is performed, the surface polishing apparatus mechanism 20 moves from the standby position to the polishing position to place the polishing board 21 on the surface of the sample 110. The surface polishing apparatus mechanism 20 moves the polishing board 21 to the polishing position while rotating the polishing board 21 and then lowers the polishing board 21 to the surface of the sample 110 to mechanically polish the surface of the sample 110. After the mechanical polishing is completed, the surface polishing apparatus mechanism 20 raises the polishing board 21 and separates it from the surface position of the sample 110. Next, the surface polishing apparatus mechanism 20 returns the polishing board 21 to the standby position.

  The etching solution processing mechanism 30 includes an etching solution container 31, an etching solution nozzle 32, and an etching solution pressing valve 33, and suitably etches the surface of the sample 110 after polishing. The etchant container 31 is made of polypropylene and contains a single etchant such as nital. The etchant nozzle 32 is formed of SUS304. When the etching solution pressing valve 33 is opened, the etching solution is pushed out of the etching solution container 31 and injected from the etching solution nozzle 32 by the pressure of the compressed air supplied from the air compressor 150.

  The cleaning processing mechanism 40 includes a cleaning liquid valve 41 connected to a cleaning liquid source 140 for supplying a cleaning liquid and a cleaning liquid nozzle 42, and cleans the sample surface after etching. When the cleaning liquid valve 41 is opened, the cleaning liquid is sprayed from the cleaning liquid nozzle 42 by the water pressure applied to the cleaning liquid source 140 that is a faucet in one example.

  The drying processing mechanism 50 includes an air regulator 51 connected to an air compressor 150 that supplies compressed air, a compressed air valve 52, and a compressed air injector 53, and performs a drying process on the sample surface after etching.

  In the fully automatic serial sectioning microscope apparatus 100, since the sample 110 is cleaned and dried by the cleaning processing mechanism 40 and the drying processing mechanism 50, the sample 110 is not likely to corrode after etching.

  The control unit 60 includes a calculation unit 61 and a memory 62, and controls the operation of the fully automatic serial sectioning microscope apparatus 100 according to a computer program stored in the memory 62. The control unit 60 includes an optical microscope observation mechanism 10, a surface polishing apparatus mechanism 20, an etching solution processing mechanism 30, a cleaning processing mechanism 40, and a drying processing mechanism 50 in order for the fully automatic serial sectioning microscope apparatus 100 to execute a series of fully automatic processes. The calculation unit 61 controls each of the above. The computing unit 61 has a CPU (Central Processing Unit). The memory 62 stores a sequence program for a series of fully automatic processes. The control unit 60 is connected to a general-purpose computer 160 having dedicated control software via a communication line. An operator (not shown) inputs processing conditions such as the depth of mechanical polishing and the number of imaging operations to the memory 62 of the control unit 60 via the general-purpose computer 160. The general-purpose computer 160 constructs a cross-sectional tissue image captured by the optical microscope observation mechanism 10 into a three-dimensional image.

  An emergency stop button 63, a power button 64, and an illumination button 65 are disposed on the casing of the fully automatic serial sectioning microscope apparatus 100. When the emergency stop button 63 is pressed, the control unit 60 performs the emergency stop of the fully automatic serial sectioning microscope apparatus 100 regardless of the operation state of the fully automatic serial sectioning microscope apparatus 100. The control unit 60 turns on and off the power supply of the fully automatic serial sectioning microscope apparatus 100 when the power button 64 is pressed. The control unit 60 turns on and off the illumination unit 15 by pressing the illumination button 65.

  The sample stage 70 is made of a corrosion-resistant metal, and fixes the sample 110 on a horizontal plane. The sample stage 70 is moved in the vertical direction from an etching position positioned below to an imaging position positioned above by a vertical drive mechanism 71 indicated by a broken line arrow. The etching position is a position where the sample is polished, etched, washed and dried. The imaging position is a position where the sample is imaged. The vertical drive mechanism 71 has a stepping motor, and the control unit 60 calculates the position of the sample stage 70 based on the pulse signal output from the stepping motor. The sample stage 70 is moved to the imaging position by the vertical drive mechanism 71 after the surface polishing and etching process of the sample 110 at the etching position, and the surface of the sample 110 placed on the sample stage 70 is moved to the optical microscope observation mechanism 10. Is imaged.

  The liquid receiving unit 80 is disposed below the sample stage 70, receives the etching solution and cleaning solution overflowing from the sample stage 70, and drains the drained unit 81 to the drain tank 82.

  Sample 110 is a metal sample having a pre-mirror polished surface.

  Next, the operation of the fully automatic serial sectioning microscope apparatus 100 will be described.

  FIGS. 3A to 3D are views showing first to fourth states of the fully automatic serial sectioning microscope apparatus 100, respectively.

  First, as shown in FIG. 3A, the fully automatic serial sectioning microscope apparatus 100 moves the polishing plate 21 onto the surface of the sample 110 placed on the sample stage 70, and the polishing plate 21 moves the sample 110. Polish the surface. Next, as shown in FIG. 3B, the fully automatic serial sectioning microscope apparatus 100 sprays and applies an etching solution 39 to the surface of the polished sample 110. Next, as shown in FIG. 3 (c), the fully automatic serial sectioning microscope apparatus 100 injects the cleaning liquid 43 onto the surface of the sample 110 after the etching, then opens the compressed air valve 52 and opens the compressed air 54. Dry the surface. As shown in FIG. 3D, the fully automatic serial sectioning microscope apparatus 100 moves the sample stage 70 to the imaging position and images the surface of the sample 110 placed on the sample stage 70.

  In the fully automatic serial sectioning microscope apparatus 100, the sample stage 70 does not move in the horizontal direction but moves only in the vertical direction. For this reason, in the fully automatic serial sectioning microscope apparatus 100, the observation surface of the surface texture observation image of the sample 110 is not likely to be displaced in principle. Further, in the fully automatic serial sectioning microscope apparatus 100, all processes of polishing, etching, cleaning and drying and imaging are automatically continuously performed for several days, and 100 or more continuous optical microscope tissue images are acquired. Can do.

  Heretofore, the fully automatic serial sectioning microscope apparatus 100 has been described.

  The fully automatic serial sectioning microscope apparatus 100 is a fully automated serial sectioning microscope method including an etching operation that often depends on manual operations, but has a problem that a plurality of etching solutions cannot be mixed and used. In etching that slightly corrodes the surface of the sample to give fine irregularities and coloring, the control of the mixing ratio of the etching solution and the amount of the etching solution becomes very delicate. Since the mixing ratio of the etching solution changes, it is not preferable to store a plurality of etching solutions in one etching solution container. Moreover, since the ratio of the etching solution varies on the surface of the sample, it is not preferable to apply the etching solution by spraying the etching solution from a plurality of etching solution containers onto the sample. Thus, the fully automatic serial sectioning microscope apparatus 100 cannot use a plurality of etching solutions.

  The present invention solves such a problem of the fully automatic serial sectioning microscope apparatus 100.

  4A is a front view of the fully automatic serial sectioning microscope system 200, FIG. 4B is a plan view of the fully automatic serial sectioning microscope system 200, and FIG. 4C is a fully automatic serial section. 1 is a side view of a sectioning microscope system 200. FIG.

  The fully automatic serial sectioning microscope system 200 includes a fully automatic serial sectioning microscope apparatus 101 mounted on a first apparatus base 121, a general-purpose computer 160 and a general-purpose computer display apparatus 161 mounted on a second apparatus base 122. Have.

  The fully automatic serial sectioning microscope apparatus 101 includes a main body having the same structure as the above-described fully automatic serial sectioning microscope apparatus 100 and the etching solution processing mechanism 1. Etching solution processing mechanism 1 is detachably connected to the main body.

  FIG. 5 is a schematic configuration diagram of the fully automatic serial sectioning microscope apparatus 101.

  The fully automatic serial sectioning microscope apparatus 101 is different from the above-described fully automatic serial sectioning microscope apparatus 100 in that the etching solution processing mechanism 1 is detachably arranged instead of the etching solution processing mechanism 30. .

  FIG. 6 is a schematic configuration diagram of the etching solution processing mechanism 1.

  The etching liquid processing mechanism 1 includes an etching liquid nozzle 32, an etching liquid pressing valve 33, an etching liquid mixing container 34, first and second etching liquid containers 35a and 35b, first and second etching liquid pumps 36a, 36b. Further, the etching solution processing mechanism 1 includes a stirrer 37, a mixing container cleaning valve 38, and an etching control unit 360 connected to the general-purpose computer 160.

  The etching liquid mixing container 34 is a container formed of PEEK (polyetheretherketone) resin, and a stirring bar 37 is disposed on the bottom surface.

  The amount of etching solution sprayed from the etching solution nozzle 32 is the amount of etching solution sprayed from the etching solution nozzle 32 per unit time and the time when the etching solution pressing valve 33 is open. Calculated by multiplying by time. The etching solution injection amount per unit time is determined based on the passage resistance of the orifice arranged inside the etching solution nozzle 32 and the pressure of the compressed air set by the air regulator 51. A unit injection amount calculation table showing the relationship among the etching solution injection amount per unit time, the passage resistance of the orifice, and the pressure of compressed air is stored in the etching storage unit 362 inside the etching control unit 360. When the operator inputs an injection amount of the etching solution, the etching calculation unit 361 of the etching control unit 360 sets the etching solution pressing valve opening time based on the input injection amount of the etching solution and the unit injection amount calculation table. Calculate. The calculated etching solution pressing valve opening time is stored in the etching storage unit 362 inside the etching control unit 360.

  The first and second etching liquid containers 35a and 35b are each formed of polypropylene and store different first and second etching liquids, respectively.

  Each of the first and second etchant pumps 36a and 36b has a metering tube pump having a stepping motor. The first and second etchant pumps 36a and 36b each adjust the supply amount by setting the rotation angle of the tube pump. The rotation angles of the tube pumps that determine the supply amounts of the first and second etchant pumps 36a and 36b are stored in the etching storage unit 362, respectively. The rotation angle stored in the etching storage unit 362 can be changed by the operator via the general-purpose computer 160.

  The stirrer 37 is a magnetic stirrer formed of a fluororesin and driven by a stirrer motor (not shown) that rotates a magnet. The driving of the stirrer 37 is stored in the etching storage unit 362. The driving time stored in the etching storage unit 362 can be changed by the operator via the general-purpose computer 160.

  The mixing container cleaning valve 38 is connected to the cleaning liquid source 140, and the opening and closing of the mixing container cleaning valve 38 is controlled by the etching control unit 360. The mixing container cleaning valve open time, which is the time during which the mixing container cleaning valve 38 is open, is stored in the etching storage unit 362 inside the etching control unit 360. The mixing container cleaning valve opening time stored in the etching storage unit 362 can be changed by the operator via the general-purpose computer 160.

  The cleaning liquid supplied to the etching liquid mixing container 34 via the mixing container cleaning valve 38 is ejected from the etching liquid nozzle 32 by compressed air supplied to the etching liquid mixing container 34 via the etching liquid pressing valve 33. Is done. In order to prevent the discharged cleaning liquid from hitting the sample 110 placed on the sample stage 70, the cleaning liquid is jetted and discharged after the sample stage 70 has moved from the etching position to the cleaning retreat position. The cleaning retreat position is an intermediate point between the etching position and the imaging position. For this reason, the cleaning liquid sprayed from the etching liquid nozzle 32 does not reach the sample 110 disposed on the sample stage 70. The cleaning liquid injection valve opening time, which is the time during which the etching liquid pressing valve 33 is opened to discharge the cleaning liquid, is stored in the etching storage unit 362 inside the etching control unit 360.

  Next, the operation of the etching solution processing mechanism 1 will be described.

  FIG. 7 is a diagram showing a processing flow of the etching solution processing mechanism 1.

  First, in step S101, the etching controller 360 transfers the first and second etching liquid containers 35a and 35b from the first and second etching liquid pumps 36a and 36b to the etching liquid mixing container 34 via the first and second etching liquid pumps 36a and 36b. Each etchant is supplied. The supply amounts of the first and second etching liquids to be supplied are determined based on the rotation angles of the first and second etching liquid pumps 36a and 36b stored in the etching storage unit 362, respectively.

  Next, in step S102, the etching control unit 360 detects the activation of the first and second etching liquid pumps 36a and 36b, and then drives the stirrer motor 37 by driving the stirrer motor.

  Next, in step S103, the control unit 60 moves the sample stage 70 to the etching position after detecting the stop of the first and second etchant pumps 36a and 36b. Next, the control unit 60 transmits a stage etching position signal indicating that the sample stage 70 has moved to the etching position to the etching control unit 360. Next, the etching control unit 360 receives the stage etching position signal and authenticates that the sample stage 70 has moved to the etching position.

  Next, in step S <b> 104, the etching control unit 360 opens the etching solution pressing valve 33, sprays the etching solution from the etching solution nozzle 32, and applies it to the sample 110. The etching solution pressing valve opening time is stored in the etching storage unit 362.

  Next, in step S105, the control unit 60 moves the sample stage 70 to the cleaning retreat position after detecting the closing of the etching solution pressing valve 33. Next, the control unit 60 transmits a stage cleaning retreat position signal indicating that the sample stage 70 has moved to the cleaning retreat position to the etching control unit 360. Next, the etching control unit 360 receives the stage cleaning retract position signal and authenticates that the sample stage 70 has moved to the cleaning retract position.

  Next, in step S <b> 106, the etching control unit 360 opens the mixing container cleaning valve 38 to supply the cleaning liquid to the etching liquid mixing container 34 and drives the stirrer 37 to clean the etching liquid mixing container 34. When the etching liquid mixing container 34 is cleaned, the stirrer 37 is driven to enable faster cleaning. The mixing container cleaning valve opening time is stored in the etching storage unit 362.

  Next, in step S107, the etching control unit 360 opens the etching solution pressing valve 33, and ejects the cleaning solution in the etching solution mixing container 34 from the etching solution nozzle 32 to be discharged. The cleaning liquid injection valve opening time is stored in the etching storage unit 362.

  In step S108, the etching control unit 360 determines whether the sample 110 is polished again. If it is determined that the sample 110 is polished again, the process returns to step S101. If it is determined that there is no processing for polishing the sample 110, the processing ends.

  The etching solution processing mechanism 1 has been described above.

  Next, a second embodiment of the etching solution processing mechanism will be described with reference to FIGS.

  FIG. 8 is a schematic configuration diagram of the etching solution processing mechanism 2.

  The etching solution processing mechanism 2 is different from the etching solution processing mechanism 1 in that it further includes a third etching solution container 35c in which a third etching solution is accommodated and a third etching solution pump 36c.

  The third etching solution container 35c is formed of polypropylene in the same manner as the first and second etching solution containers 35a and 35b.

  The third etchant pump 36c has a metering tube pump including a stepping motor, like the first and second etchant pumps 36a and 36b, and the supply amount is adjusted by setting the rotation angle of the tube pump.

  The etching solution processing mechanism 2 applies an etching solution obtained by mixing the first and second etching solutions to the sample 110 and then applies an etching solution obtained by mixing the first and third etching solutions to the sample 110. Since two etching liquids having different components are mixed in a single etching liquid mixing container 34, the etching liquid processing mechanism 2 cleans the etching liquid mixing container 34 every time the etching liquid is mixed.

  Next, the operation of the etching solution processing mechanism 2 will be described.

  FIG. 9 is a diagram showing a processing flow of the etching solution processing mechanism 2.

  Steps S201 to S207 are processing steps in which the etchant mixed container 34 is washed by applying an etchant obtained by mixing the first and second etchants to the sample 110. Steps S <b> 208 to S <b> 214 are processing steps in which the etching liquid mixed with the first and third etching liquids is applied to the sample 110 to clean the etching liquid mixing container 34.

  In steps S206 and S213, the controller 60 supplies the cleaning liquid to the etching liquid mixing container 34 to clean the etching liquid mixing container 34. For this reason, there is no possibility that the etching liquid obtained by mixing the first and second etching liquids and the first and third etching liquids react in the etching liquid mixing container 34 to change the components of the etching liquid.

  The etching solution processing mechanism 2 has been described above.

  Next, another embodiment will be described.

  The etching solution processing mechanism 1 mixes two etching solutions to generate one mixed etching solution, and the etching solution processing mechanism 2 mixes three etching solutions to generate two mixed etching solutions. However, the etching solution processing mechanism according to the present invention may generate one or a plurality of mixed etching solutions by mixing four or more kinds of etching solutions.

  In addition, although the etching solution processing mechanisms 1 and 2 have the single etching solution mixing container 34, they may have a plurality of etching solution mixing containers. Moreover, you may use in combination with the system which apply | coats a single etching liquid.

  In the etching solution processing mechanisms 1 and 2, pressure is applied to the etching solution mixing container 34 by compressed air, but pressure is applied to the etching solution mixing vessel 34 using a high-pressure inert gas such as high-pressure argon gas. May be.

  In the etching solution processing mechanisms 1 and 2, the first and second etching solution pumps 36 a and 36 b each have a metering tube pump, but as a second etching solution supply unit that supplies a predetermined amount to the etching solution mixing container. Other pumps may be used as long as they function.

  The etchant nozzle 32 is a nozzle having an orifice. However, other structures such as a metering pump may be adopted as long as the etchant nozzle 32 functions as a mixed etchant injection unit that applies a predetermined amount of the mixed etchant to the surface of the sample 110. .

  In the etching solution processing mechanisms 1 and 2, the cleaning retreat position is an intermediate point between the etching position and the imaging position, but may be a position where the liquid ejected from the etching liquid nozzle 32 does not reach the sample 110. For example, the cleaning retract position may be the same position as the imaging position. In the etching solution processing mechanisms 1 and 2, the polishing, etching, cleaning, and drying processes are performed at the etching position, but each process may be performed by moving the sample stage 70 in the vertical direction.

  In the etching solution processing mechanisms 1 and 2, a magnetic stirrer is employed as the stirrer 37, but an induction magnetic stirrer may be employed as the stirrer.

  Further, in the etching solution processing mechanisms 1 and 2, a metal is used as the sample 110, but ceramics or a semiconductor material may be used as the sample.

  As described so far, the etching solution processing mechanism 1 has the etching solution mixing container 34 for mixing the first and second etching solutions, so that the etching solution mixed at a desired ratio can be generated.

  In addition, since the etching solution processing mechanism 1 includes the mixing container cleaning valve 38 that supplies the cleaning solution to the etching solution mixing container 34, the etching solution mixing container 34 can be cleaned after the etching process. For this reason, there is no possibility that the etching solution generated during the previous etching process will remain in the etching solution mixing vessel 34, and the mixture is mixed at a ratio of the first and second etching solutions supplied from the first and second etching solution containers. An etchant can be generated.

  Further, since the cleaning liquid that has cleaned the etching liquid mixing container 34 is ejected and discharged from the etching liquid nozzle, the etching liquid processing mechanism 1 does not need to have a separate discharge mechanism for discharging the cleaning liquid. When the cleaning liquid that has cleaned the etching liquid mixing container 34 is discharged from the etching liquid nozzle, the cleaning liquid that has cleaned the etching liquid mixing container 34 is not likely to be sprayed onto the sample because the sample is retracted to the cleaning retreat position.

  In addition, since the etching solution processing mechanism 1 has the stirrer 37 inside the etching solution mixing vessel 34, even when any of the first and second etching solutions contains moisture and a hydrophobic liquid, the first and second etching solutions are used. Etching solution can be mixed.

  In addition, since the first and second etchant pumps 36a and 36b have a metering pump, the etchant processing mechanism 1 can supply a predetermined amount of etchant.

Examples of the etching solution processing mechanism of the present invention will be described below.
Example 1
In this example, the etching solution processing mechanism 1 was used to mix an etching solution corresponding to a typical repeller reagent as a color etching solution for a martensite phase or the like. The sample was a carbon steel plate containing a finely dispersed martensite phase. The surface of the sample used was mirror-finished by general mechanical polishing.

  In this example, “4 g picric acid + 100 ml ethanol” was used as the first etching liquid, and “1 g sodium pyrosulfite + 100 ml water” was used as the second etching liquid.

  The supply amount of the first and second etching solutions and the injection amount of the mixed etching solution were changed for each sample. Since the first and second etching solutions are ethanol-based and water-based mixed etching solutions, the mixing operation is important. Therefore, the stirrer 37 was always rotated.

  The surface of the sample was polished by alumina polishing and buffing with a polishing plate 21 to make a mirror surface.

  When jetting the mixed etching liquid onto the sample, pressure was applied to the etching liquid mixing container 34 by Ar gas.

  The etched sample was washed with washing water and dried with dry air.

  The sample surface was imaged as a digital image with an optical microscope equipped with an automatic focus correction device.

  Table 1 shows the quality of the martensitic phase photograph that accompanies changes in the mixing ratio of the first and second etching solutions and the jetting time of the etching solution.

  A relatively good etching material structure is obtained under the condition that the first etching solution is excessively applied to the second etching solution (see sample numbers 2, 4, 5, and 6). However, even under conditions where the first etching solution is applied excessively, the contrast is weak when the spray time is short (see sample number 1). On the other hand, when the spray time was long under the condition that the first etching solution was applied excessively, the etching was excessive (see Sample Nos. 3 and 7). Even when the amount of the first and second etching liquids was equal, if the injection time was long, it was excessive etching (see sample number 11).

  Under the condition that the second etching solution was applied excessively with respect to the first etching solution, the etching process could not be performed sufficiently (see sample numbers 12 to 17).

  In addition, when the first and second etching solutions were applied to the sample alone without mixing, the etching could not be performed at all (see sample numbers 18 and 19). When the first etching solution was applied to the sample alone, the grain boundaries were etched to some extent, but the martensite phase could not be etched, which was insufficient as an etching solution for material structure images. When the second etching solution was applied to the sample alone, etching unevenness was generated as a whole, which was insufficient as an etching solution for material structure images.

  In the fully automatic serial sectioning microscope apparatus 100, two etching solution containers 31 and two etching solution nozzles 32 were used to irradiate the sample with the first and second etching solutions at the same time, but almost no etching effect was observed ( Sample number 20).

  FIG. 10 is an optical micrograph of an example in which a good etching process was performed. In FIG. 10, the white portion on the photograph is a martensite phase dispersed, and the periphery is a ferrite phase.

  In this embodiment, the first etching solution is mixed excessively or in the same amount as the second etching solution, and the injection time for injecting the mixed etching solution is set to an appropriate time, so that the automatic serial sectioning can be performed. Usable 3D material texture images could be obtained.

(Example 2)
In this example, a mixed etching solution was applied to carbon steel having ferrite and bainite. Carbon steel having a ferrite and a bainite system has been difficult to capture images necessary for reconstructing several hundreds of continuous photographs by the conventionally used nital etching.

  In this example, “picric acid 3 g + ethanol 100 ml” was used as the first etching liquid, and “sodium thiosulfate 5 g + citric acid 3 g + water 100 ml” was used as the second etching liquid. Furthermore, in this example, nitric acid 2 ml + ethanol 100 ml (2% nital) was used as the third etching solution, and nitric acid 5 ml + ethanol 100 ml (5% nital) was used as the fourth etching solution.

  The supply amount of the first to fourth etching solutions and the injection amount of the mixed etching solution were changed for each sample. The first to third etching solutions were mixed in the etching solution mixing vessel 34 and sprayed onto the sample. Thereafter, the etching solution mixing vessel 34 was washed with the washing solution, the fourth etching solution was supplied to the cleaned etching solution mixing vessel 34, and the supplied fourth etching solution was sprayed onto the sample.

  When spraying the mixed etching liquid onto the sample, pressure was applied to the etching liquid mixing container 34 by an inert gas.

  The surface of the sample was polished by alumina polishing and buffing with a polishing board 21 to be mirror-finished.

  In spraying the mixed etching liquid onto the sample, pressure was applied to the etching liquid mixing container 34 by Ar gas.

  The etched sample was washed with methyl alcohol and dried with dry air.

  The material structure image of the sample surface was taken as a digital image by an optical microscope equipped with an automatic focus correction device.

  Table 1 determines the quality of the image according to the change in the mixing ratio of the first to fourth etching solutions and the change in the jetting time of the etching solution.

  When there was much 1st etching liquid, coloring progressed and the uniform contrast was not acquired (refer sample number 2 and 3).

  When there was much 2nd etching liquid, etching did not fully advance and sufficient contrast was not acquired (refer sample numbers 13-15).

  When the etching solution mixing vessel 34 was not washed, the etching solution was mixed in the etching solution mixing vessel 34, which hindered the etching action.

  As mentioned above, although preferred embodiment of this invention was described referring an accompanying drawing, it cannot be overemphasized that this invention is not limited to the example which concerns. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the claims, and these are naturally within the technical scope of the present invention. Understood.

DESCRIPTION OF SYMBOLS 1, 2 Etching liquid processing mechanism 10 Optical microscope observation mechanism 20 Surface polishing apparatus mechanism 30 Etching liquid processing mechanism 31 Etching liquid container 32 Etching liquid nozzle 33 Etching liquid pressing valve 34 Etching liquid mixing container 35a First etching liquid container 35b Second etching Liquid container 35c Third etching liquid container 36a First etching liquid pump 36b Second etching liquid pump 36c Third etching liquid pump 37 Stirrer 38 Mixing container cleaning valve 40 Cleaning processing mechanism 50 Drying processing mechanism 60 Control unit 70 Sample stage 80 Liquid Receiving part 110 Sample

Claims (6)

In a fully automatic serial sectioning microscope apparatus for automatically operating a series of processes of polishing a sample surface, etching the polished sample surface, and imaging the etched sample surface continuously, An etching solution processing mechanism for applying a mixed etching solution in which an etching solution and a second etching solution different from the first etching solution are mixed to the surface of the polished sample;
A first etchant container containing the first etchant;
A second etchant container containing the second etchant;
An etching liquid mixing container for mixing and generating a mixed etching liquid by mixing the first and second etching liquids;
A first etching solution supply unit configured to supply a predetermined amount of the first etching solution from the first etching solution container to the etching solution mixing container when it is determined that the surface of the sample is polished ;
A second etching solution supply unit configured to supply a predetermined amount of the second etching solution from the second etching solution container to the etching solution mixing container when it is determined that the surface of the sample is polished ;
A cleaning liquid supply unit for supplying a cleaning liquid to the etching liquid mixing container after the mixed etching liquid is sprayed;
A mixed etching solution spraying unit that sprays and applies a predetermined amount of mixed etching solution from the etching solution mixing container onto the surface of the polished sample ;
After authenticating that the sample has moved to a position where the liquid ejected from the mixed etching liquid ejecting section does not reach the sample, the cleaning liquid contained in the etching liquid mixing container is ejected from the mixed etching liquid ejecting section. Etching solution processing mechanism for fully automatic serial sectioning microscope. A third etchant container containing a third etchant different from the first and second etchants;
After a mixed etching solution obtained by mixing the first etching solution and the second etching solution is injected and the cleaning solution is injected , a predetermined amount of the third etching solution is transferred from the third etching solution container to the etching solution mixing container. A third etching solution supply unit for supplying
Further comprising
The mixed etching solution spraying unit sprays and applies the third etching solution from the etching solution mixing container onto the surface of the polished sample,
The etching liquid processing mechanism for a fully automatic serial sectioning microscope according to claim 1 , wherein the cleaning liquid supply unit supplies the cleaning liquid to the etching liquid mixing container after the third etching liquid is sprayed . The etching liquid processing mechanism for a fully automatic serial sectioning microscope according to claim 2 , wherein each of the first to third etching liquid supply units has a metering pump. The etching solution processing mechanism for a fully automatic serial sectioning microscope according to any one of claims 1 to 3 , wherein the etching solution processing mechanism further includes a stirrer disposed inside the etching solution mixing container. The etching solution processing mechanism for a fully automatic serial sectioning microscope according to any one of claims 1 to 4 , which is detachably connected to the fully automatic serial sectioning microscope apparatus. In a fully automatic serial sectioning process that continuously and automatically operates a series of processes for polishing the surface of the sample, etching the surface of the polished sample, and imaging the surface of the etched sample, an etching solution processing mechanism includes: A method of applying a mixed etching solution to a sample, wherein the etching solution processing mechanism comprises:
When it is determined that the surface of the sample is polished, a mixed etching solution generated by mixing at least two different etching solutions at a predetermined ratio is contained in an etching solution mixing container,
Authenticate that the sample is placed at the etching position where the sample is etched,
After authenticating that the sample has moved to the etching position, the mixed etching solution is applied from the etching solution mixing container to the sample via a mixed etching solution spraying unit,
Supplying a cleaning liquid to the etching liquid mixing container,
Authenticates that the sample has moved to a cleaning retreat position where the liquid ejected from the mixed etching solution ejecting unit does not reach the sample;
After authenticating that the sample has moved to the cleaning retreat position, the cleaning liquid is sprayed through a mixed etching liquid spraying unit.
A method comprising steps.