JP2006046979A - Sample manufacturing substrate, liquid sample building-up method, sample manufacturing method and manufacturing method of sample manufacturing substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sample manufacturing substrate suitable for mixing multiple kinds of liquid raw materials by a combinatorial technique to independently build up many kinds of liquid samples different in mixing ratio on one substrate or obtaining dried or sintered samples by drying or sintering the built-up liquid samples, and its manufacturing method. <P>SOLUTION: The sample manufacturing substrate is constituted by providing a plurality of mutually parallel first recesses and a plurality of the mutually parallel second recesses crossing them to the surface of a substrate. The liquid sample building-up method is constituted by building up the liquid samples on a plurality of the crossing points of the first and second recesses of the sample manufacturing substrate. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

In the present invention, for example, by using a combinatorial method, a plurality of types of liquid raw materials are mixed, and various types of liquid samples having different mixing ratios are separately placed on a single substrate, or the mounted liquid samples are dried. The present invention relates to a sample preparation substrate, a liquid sample assembling method, a sample manufacturing method, and a sample preparation substrate manufacturing method suitable for obtaining dry samples and sintered samples obtained by sintering them.

2. Description of the Related Art Conventionally, as a sample preparation substrate for independently mounting a large number of liquid samples on a single substrate, a microplate in which a large number of wells, which are concave portions for storing samples, are formed is known. For example, a well having a circular planar shape or a rectangular shape is known (Patent Document 1). As the microplate, a synthetic resin manufactured using a mold is known, and can be mass-produced at a low cost.
JP-A-9-68532

However, even if only a small number of sample preparation substrates are manufactured, it is necessary to manufacture an expensive mold, which is not suitable for manufacturing a small lot. In the case of manufacturing a small lot, the manufacturing method for processing the substrate surface in order to form a large number of wells having a circular shape or a square shape in plan view requires a large number of steps.

In addition, when a liquid sample is heat-treated at a high temperature, the sample preparation substrate needs to have heat resistance.
For example, when a compound is produced as a sample on a sample preparation substrate using a plurality of types of liquid inorganic material samples as starting materials, a plurality of types of liquid inorganic material samples are mixed, placed on the sample preparation substrate, dried and sintered. It will be necessary. Therefore, heat resistance is required for the sample preparation substrate. In particular, when a metal oxide is a target, a sample may be reacted at a high heat exceeding 1000 ° C., and a sample preparation substrate that can withstand that temperature is required.

As materials having such heat resistance and chemically stable even at high temperatures, ceramics such as alumina and zirconia, and platinum are known. It is generally difficult to accurately mold these materials using a mold. For example, if the ceramic material is fired after being molded by a method such as using a mold before firing, it is difficult to accurately form a sample preparation substrate due to ceramic shrinkage. Therefore, processing is generally performed after firing the ceramic. However, forming a large number of wells having a circular or square planar shape by processing after firing the ceramic requires a large number of man-hours and is very expensive.

The reason why accuracy is required for the sample preparation substrate is as follows. That is, when a plurality of samples are formed on the sample preparation substrate and each sample is automatically analyzed by, for example, X-rays, the X-rays are sampled if the sample is not formed at an accurate position on the sample preparation substrate. Therefore, it is impossible to irradiate a predetermined position, and accurate X-ray analysis becomes impossible. Also, for example, in measurement using contact between a sample and a terminal, such as measurement of electrical conductivity, it is difficult to evaluate the correct physical properties unless the terminal and the sample are in accurate contact. There is no change in the need for accuracy.

The present invention has been made to solve the above-described problems, and is suitable for the production of small lots. In addition, a large number of liquid samples are individually arranged on a single sample preparation substrate. After that, a sample preparation substrate suitable for obtaining a dried sample obtained by volatilizing the solvent and drying and a sintered sample obtained by sintering them at a high temperature, and a liquid sample assembling method and sample using the sample preparation substrate And a method for manufacturing a sample preparation substrate are provided.

The present invention provides a sample preparation substrate capable of independently placing a large number of liquid samples on a single substrate by simply providing a plurality of concave strips intersecting each other on the substrate surface, and the sample preparation substrate The present invention relates to a liquid sample assembling method, a sample manufacturing method, and a sample manufacturing substrate manufacturing method.

In addition, as the liquid sample of the present invention, one that is heat-treated after being placed can be suitably employed, and particularly a liquid inorganic material sample that is heat-treated at a high temperature can be suitably employed. The number of liquid samples placed on one substrate is preferably 9 or more in order to widen the range of target samples that can be analyzed at one time and increase research efficiency, but if it is 36 or more, the effect is great. Further, the relationship between the concentration of the liquid sample and the amount to be arranged is determined by the required amount of the sample obtained as a result of drying or sintering the liquid sample. The concentration of the liquid sample is not generally determined due to solubility, etc.
In order to secure a certain number or more of the number of plates on a single substrate, it is preferable that the number is about 5 to 30 microliters.

That is, the present invention is characterized in that (1) a plurality of mutually parallel first recesses and a plurality of mutually parallel second recesses intersecting with each other are provided on the surface of the substrate. A sample preparation substrate.

The first and second concave portions can be molded using a mold, but can be produced by small-lot production by molding by mechanical processing such as polishing or cutting, blasting or laser processing. In addition, if it is molded before firing like ceramic, a material that is difficult to obtain with high accuracy due to shrinkage after firing can be processed easily and accurately.

The outer shape of the sample preparation substrate is not particularly limited, but it is preferably a flat plate having a square shape in plan view because it is easy to manufacture and easy to handle. The material for the sample preparation substrate is not particularly limited, and may be synthetic resin, metal, ceramic, or the like. In particular, when heat resistance is required, it is preferable to use ceramic such as alumina, zirconia, or silicon, or platinum. The first groove portion or the second groove portion may be provided up to the side end of the sample preparation substrate, or may be provided only in the central portion while leaving the side end portion.

The present invention also provides (2) a substrate for preparing a sample in which a plurality of first parallel concave portions and a plurality of parallel second concave portions intersecting each other are provided on the surface of a base material. A liquid sample assembling method, characterized in that a liquid sample is arranged at a plurality of intersections of the first concave stripe portion and the second concave stripe portion.

When a liquid sample is arranged at a plurality of intersections, the liquid sample is held at the intersections in the form of droplets by surface tension. In particular, it is effective if the sample preparation substrate has no affinity for the liquid. Specifically, the contact angle with the liquid is preferably 60 ° or more, and more preferably 105 ° or more. As described above, as a means for making the sample preparation substrate incompatible with the liquid, a method of applying a liquid-repellent chemical substance to the surface is simple and preferable.

The present invention also provides (3) a substrate for sample preparation in which a plurality of first parallel strips and a plurality of second parallel strips intersecting each other are provided on the surface of the substrate. A liquid sample assembling method, wherein a liquid sample is placed on a plurality of convex portions formed by the first concave stripe portion and the second concave stripe portion.

When a liquid sample is placed on a plurality of protrusions, the liquid sample is held in the protrusions in the form of droplets by surface tension. In particular, it is effective if the sample preparation substrate has no affinity for the liquid. Specifically, the contact angle with the liquid is preferably 60 ° or more, and more preferably 105 ° or more. The sample obtained by drying and sintering the placed liquid sample is deposited on the convex part of the sample preparation substrate, so that the range of the incident angle with respect to the sample is increased in the case of measurement by electromagnetic waves such as X-rays. Can do.

In addition, the present invention is (4) a method for producing a sample, characterized by volatilizing a solvent of a liquid sample placed by any of the liquid sample placement methods (2) or (3) above.

In addition, the present invention provides (5) Sample production characterized by volatilizing the solvent of the liquid sample placed by the liquid sample placement method of either (2) or (3) above and further sintering it. Method.

In addition, the present invention provides (6) a plurality of first concave ridges parallel to each other by processing the surface of a flat substrate, and a plurality of second parallel ridges intersecting each other. A method for manufacturing a sample preparation substrate, comprising: forming a sample preparation substrate.

The processing method of the surface of the flat substrate is not particularly limited, but a known method such as blasting or laser processing can be employed in addition to mechanical processing such as polishing and cutting.

The sample preparation substrate of the present invention is a sample preparation substrate simply by providing a plurality of mutually parallel first recesses and a plurality of mutually parallel second recesses intersecting them on the surface of the substrate. Therefore, it is easy to manufacture without using a mold. That is, it is suitable for manufacturing a small lot. Moreover, even if it is a ceramic etc. which are difficult to manufacture accurately with a forming die, a highly accurate sample preparation substrate can be manufactured by processing. Therefore, the liquid sample can be placed at an accurate position of the sample preparation substrate, and therefore, a sample obtained by drying and sintering the liquid sample can be deposited at an accurate position of the sample preparation substrate.

Thus, since the sample preparation substrate is manufactured with high accuracy, the sample preparation substrate can be accurately positioned with respect to the analysis apparatus and the measurement apparatus. Further, if the sample is deposited at an accurate position of the sample preparation substrate, the sample can be moved to an accurate position where analysis or measurement is performed. Conversely, analysis points and measurement points can be moved with respect to the sample.
As a result, accurate analysis and measurement of physical properties are possible.

(Embodiment 1)
Embodiment 1 of the present invention will be described below with reference to the drawings. FIG. 1 is a plan view showing Embodiment 1 of the sample preparation substrate of the present invention, and FIG. 2 is a cross-sectional view taken along line AA of FIG.

As shown in FIG. 1 and FIG. 2, six parallel first recesses 5, 5,.
.. And six parallel second concave strips 6, 6... Orthogonal to them are provided to form the sample preparation substrate 1. The first groove 5, 5, ... and the second groove 6, 6,
.. Each has a rectangular cross section up to the side edge of the sample preparation substrate 1.

The cross-sectional shapes of the first groove 5 and the second groove 6 are not limited to a rectangle, but may be a square or a semicircle that opens upward, or only a bottom surface that is a semicircle that opens upward. It may be. Moreover, the depth and cross-sectional shape of the 1st groove part 5 and the 2nd groove part 6 may be the same, and may differ.

Moreover, the 1st groove part 5 and the 2nd groove part 6 may be orthogonal, and may cross | intersect by the predetermined | prescribed angle. In addition, the number of the first groove portions 5 and the second groove portions 6 varies depending on the planar dimensions of the sample preparation substrate 1, but a large number of liquid samples are arranged, samples are simultaneously manufactured, and measurement and evaluation are performed. Are preferably 4 or more each, more preferably 6 or more each. Moreover, the number of the 1st groove part 5 and the 2nd groove part 6 does not need to be the same number, and can be arbitrarily set according to a sample manufacturing apparatus or a measurement / evaluation apparatus.

36 of the first concave strips 5, 5,... Of the sample preparation substrate 1 formed in this way and the second concave strips 6, 6,. .. Can be used as a sample forming portion which is a place where a liquid sample is placed.

The distance between the adjacent groove 5 and the center line of the groove 5 is 1.5 times the width of the groove 5 or more.
If the distance between the center of the recess 6 and the recess 6 adjacent to each other is not less than 0 times, and the width of the recess 6 is not less than 1.5 times and not more than 10 times the liquid sample, Intersections 3, 3,.
It is preferable because liquid samples that are in the form of droplets due to surface tension can be placed without contact with each other. That is, since the liquid sample can be arranged as droplets having a horizontal projection area larger than the area of the sample forming portion (intersection 3), the amount of the dried sample deposited by volatilizing the solvent of the liquid sample can be increased.

(Embodiment 2)
Next, another embodiment of the present invention will be described with reference to the drawings. FIG. 3 is a plan view showing Embodiment 2 of the sample preparation substrate of the present invention.

As shown in FIG. 3, six parallel first recesses 51, 51,.
.. And six parallel second recesses 61, 61... Perpendicular to them are provided to form the sample preparation substrate 11. The first groove portions 51, 51,... And the second groove portions 61, 61,... Have a rectangular cross section up to the side edge of the sample preparation substrate 11, respectively.

Here, the 1st groove part 51 and the 2nd groove part 61 may be orthogonally crossed, and may cross | intersect by the predetermined | prescribed angle. In addition, the number of the first groove portions 51 and the second groove portions 61 varies depending on the planar dimensions of the sample preparation substrate 11, but a large number of liquid samples are arranged and the samples are simultaneously manufactured for measurement and evaluation. In order to efficiently carry out the above, there is no particular limitation, but it is preferably 4 or more, more preferably 6 or more. Moreover, the number of the 1st groove part 51 and the 2nd groove part 61 does not need to be the same number, and can be arbitrarily set according to a sample manufacturing apparatus or a measurement / evaluation apparatus.

The first concave strips 51, 51,... And the second concave strips 61, 61,. The parts 4, 4,... Can be sample forming parts for placing a liquid sample.

The distance between the centers of the convex portions 4 adjacent to each other is not less than 1.5 times the diameter of the circle circumscribing the convex portion 4.
If it is less than double, when the liquid sample is placed on the projections 4, 4,... That are the sample forming part, the liquid samples that are in the form of droplets due to surface tension can be placed without contacting each other. This is preferable because it is possible. That is, since the liquid sample can be arranged as a droplet having a horizontal projection area larger than the area of the convex portion 4 as the sample and the forming portion, the amount of the dry sample deposited by volatilizing the solvent of the liquid sample can be increased. .

A first embodiment of the present invention will be described with reference to FIGS. In this example, sample preparation was performed in order to clarify what crystalline phase can be obtained in which range on the composition diagram by mixing ternary inorganic substances at different ratios and sintering at high temperature. The crystal phase was analyzed. As the material for the sample preparation substrate 1, alumina having a purity of 99.9% was employed. The first concave strips 5, 5,... Having a width of 2 mm and a depth of 0.5 mm were polished on the surface of an alumina plate having a plane dimension of 35 mm × 35 mm and a thickness of 5 mm. Also, the first concave strips 5, 5,
The second concave strips 6, 6,... Having a width of 2 mm and a depth of 0.5 mm are formed by polishing so as to be orthogonal to.

The distance between the first concave stripes 5 adjacent to each other and the center line of the concave stripes 5 is 5 mm, which is 2.5 times the width of the concave stripes 5, and similarly, the second concave stripes 6 adjacent to each other. The distance between the centers of the groove portions 6 was 5 mm, which is 2.5 times the width of the groove portions 6. In addition, the first concave strips 5, 5,... And the second concave strip 6,
36 intersections 3, 6,... Are set as sample forming portions as liquid sample placement locations.

As a liquid sample, (1) 0.5 mol / l of chromium acetate (Cr (OCOCH ₃ ) ₃ )
Mixing of aqueous solution, (2) 1.0 mol / l aqueous solution of lithium hydroxide hydrate (LiOH.H ₂ O) and (3) titanium oxide (TiO ₂ ) slurry concentration 1.0 mol / l with water as dispersion medium What changed ratio was mix | blended with the different mixing container, and what was stirred and mixed was used.

20 μl of the above liquid sample was weighed from the mixing container with a dispensing pipette and placed at intersections 3, 3,. The placed liquid sample was held at the intersection 3 to form a slightly flat droplet. Adjacent droplets were not in contact with each other.

Next, the sample preparation substrate 1 on which the liquid sample was placed was placed on a hot plate heated to 90 ° C., and water as a solvent was volatilized to obtain a dry sample. All the dried samples could be deposited on the sample forming part (intersection 3).

Furthermore, the dried sample was calcined at 1173 degrees, 1273 degrees, and 1373 degrees at an absolute temperature for 3 hours to obtain a calcined sample. All sintered samples could be deposited on the sample forming part (intersection 3). When these samples were analyzed by X-ray, a ramsdellite type crystal phase was observed.

Another embodiment of the present invention will be described with reference to FIG. The material of the substrate 11 for sample preparation is purity 9
9.5% alumina (machinable ceramic) was used. Plane dimension is 35mm x 35mm,
On the surface of an alumina plate having a thickness of 5 mm, six first concave strips 51, 51,... Having a width of 3.5 mm and a depth of 0.5 mm were formed by cutting. Also, the first concave strips 51, 5
1 and .. 2nd concave-line part 6 parallel to each other of width 3.5mm and depth 0.5mm so as to be orthogonal to
1, 61,... Were formed by cutting.

Further, the 25 convex portions 4 formed by the first concave stripe portions 51, 51,... And the second concave stripe portions 61, 61,. . Sample forming part (convex part 4
) Was set to 2 mm × 2 mm.

As a liquid sample, (1) 0.5 mol / l of chromium acetate (Cr (OCOCH ₃ ) ₃ )
Mixing of aqueous solution, (2) 1.0 mol / l aqueous solution of lithium hydroxide hydrate (LiOH.H ₂ O) and (3) titanium oxide (TiO ₂ ) slurry concentration 1.0 mol / l with water as dispersion medium What changed ratio was mix | blended with the different mixing container, and what was stirred and mixed was used.

10 μl of the above liquid sample was weighed from the mixing container with a dispensing pipette and placed on the sample forming part (convex parts 4, 4,...). The placed liquid sample was held in the sample forming part (convex part 4) by surface tension, and a slightly flat liquid droplet was formed. Adjacent droplets did not contact each other.

Next, the sample preparation substrate 11 on which the liquid sample was placed was placed on a hot plate heated to 90 ° C., and water as a solvent was volatilized to obtain a dry sample. All the dried samples could be deposited on the sample forming part (convex part 4).

Furthermore, the dried sample was calcined at 1173 degrees, 1273 degrees, and 1373 degrees at an absolute temperature for 3 hours to obtain a calcined sample. All of the sintered samples could be deposited on the sample forming part (convex part 4). When these samples were analyzed by X-ray, the same ramsdellite type crystal phase as in Example 1 was observed.

Although the embodiments of the present invention have been described with reference to the drawings, the specific configuration of the present invention is not limited to these embodiments, and the present invention can be changed even if there is a design change or the like without departing from the gist of the present invention. include.

For example, the sample preparation substrate does not need to be square, and may be rectangular or circular. The material for the sample preparation substrate does not need to be a single material. For example, platinum is deposited on the surface of a sample preparation substrate made of ceramic such as alumina or zirconia to reduce the reactivity with the liquid sample, Conductivity can be imparted to the surface of the manufacturing substrate.

Since various sample preparation substrates can be manufactured in a small lot, it is possible to design and manufacture a sample preparation substrate optimal for the experiment contents. As a result, the efficiency of research and development can be improved. In addition, since the material for the sample preparation substrate is not limited, a wide variety of liquid samples can be arranged on the premise of various processes such as a subsequent heat treatment. That is, combinatorial techniques for analyzing various samples and synthesizing new substances can be efficiently performed.

It is a top view which shows Embodiment 1 of the board | substrate for sample preparation of this invention. It is the sectional view on the AA line of FIG. It is a top view which shows Embodiment 2 of the board | substrate for sample preparation of this invention.

Explanation of symbols

1,11 Sample preparation substrate
2 Substrate surface
3 Intersection (sample formation part)
4 Convex part (sample forming part)
5,51 First groove 6,61 Second groove

Claims (6)

A substrate for preparing a sample, wherein a plurality of mutually parallel first recesses and a plurality of mutually parallel second recesses intersecting with each other are provided on the surface of the substrate. The first concave portion of the sample preparation substrate, wherein a plurality of first parallel concave portions and a plurality of parallel second concave portions intersecting each other are provided on the surface of the substrate. A liquid sample assembling method, wherein a liquid sample is arranged at a plurality of intersections between the first concave groove portion and the second concave stripe portion. The first concave portion of the sample preparation substrate, wherein a plurality of first parallel concave portions and a plurality of parallel second concave portions intersecting each other are provided on the surface of the substrate. A liquid sample assembling method, comprising: placing a liquid sample on a plurality of convex portions formed by the second concave portion and the second concave portion. A method for producing a sample, comprising volatilizing a solvent of the liquid sample placed by the liquid sample placing method according to claim 2. A method for producing a sample, comprising: volatilizing a solvent of the liquid sample placed by the liquid sample placing method according to claim 2 or 3 and further sintering the solvent. Sample preparation characterized by forming a plurality of mutually parallel first concave ridges and a plurality of mutually parallel second concave ridges intersecting with each other by processing the surface of a flat substrate Manufacturing method for industrial use.

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