JP2019090779A - Method of preparing resin embedded with analysis sample - Google Patents

Abstract

To provide a method of preparing a resin embedded with an analysis sample, which allows for sufficiently preventing particle aggregation of a granular sample within a resin material to improve dispersion of the granular sample in the resin material when preparing a resin embedded with a sample from the granular sample and granular resin material.SOLUTION: There is provided a method of preparing a resin embedded with a sample, comprising a granular sample immobilized in a resin material, obtained by embedding a target granular sample, comprising particles having non-uniform diameters and containing a plurality of types of single molecules and/or compounds, in the resin material. The method comprises steps of; pouring a granular sample 2 into a container 1 together with a granular resin material 3; rotating the container 4 having the granular sample 2 and the granular resin material 3 therein and, at the same time, revolving the same in a direction that is the same as or opposite to a rotating direction using a planetary centrifugal mixer, thereby mixing the granular sample 2 with the granular resin material 3 in the container 4; pressuring and heating the granular sample 2 and the granular resin material 3 in the container 4 to melt the granular resin material 3; and curing the melted granular resin material.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a sample embedding resin for analysis by embedding and fixing a fine particulate sample to be analyzed into a resin material prior to analysis, and in particular, to a method in a resin material A technique for improving the dispersibility of particulate samples is proposed.

  For example, measure and analyze the elemental content, particle size distribution, single substance separation degree, etc. of granular samples consisting of particles of non-uniform composition and particle size such as ore, slag, sludge, dust or recycled raw materials such as electric and electronic equipment Because the particles that make up the particulate sample are so small, it is common practice to embed and fix the particulate sample in a resin material to obtain a sample-embedded resin before setting it in the analyzer. ing. As an example of such an analyzer, a mineral analysis system (Mineral Liberation Analyzer, MLA) analyzes ore particles based on SEM-EDS, and is used particularly in the field of mineral resources.

In such a sample-embedded resin, in order to improve analysis accuracy, it is required that the particulate sample be sufficiently dispersed in the resin material and have a representative composition free from separation and segregation.
Therefore, conventionally, when preparing a sample embedding resin, first, a granular sample is mixed with a liquid resin material, and the resulting mixture is manually stirred or in a container with an ultrasonic stirrer. The mixture was heated in the air to cure the liquid resin material contained therein.

  Here, when the particulate sample is particularly composed of ore particles, the particle size of the particle is nonuniform, and various particulate metals, compounds thereof and the like are included. When the liquid resin material is used in step (d), a difference occurs in the sedimentation speed of each particle of the granular sample which settles in the liquid resin material until the curing of the liquid resin material is completed. And this has the problem that the dispersibility of the granular sample in a resin material is reduced after hardening of a liquid resin material, and the separation segregation of the granular sample in sample embedding resin arises.

  In order to solve this problem, Patent Document 1 describes “A method of preparing a resin-embedded sample in which a granular sample is embedded in a resin, and solidifying the mixture of the granular sample and the resin for pelletizing the pellet, A method for producing a resin-embedded sample, comprising: a solidification step for obtaining a pellet molded body; and a melt solidification step for solidifying the resin for pellet contained in the pellet molded body to obtain solidified pellets. Is proposed. And, according to this, “when preparing a sample, it is possible to reduce the burden of analysis such as increase in the number of analysis samples, without causing a bias of the existence state of minerals due to the specific gravity difference of ore particles contained in the sample). It can be said that the resin-embedded sample and the method for producing the same can be provided.

JP, 2016-50918, A

By the way, as another factor that the dispersibility of the particulate sample in the resin material is lowered, there is aggregation of particles which can be generated by the fine particles of the particulate sample. When the granular sample is fixed in the resin material without sufficient removal of particle aggregation, the analysis accuracy caused by the analysis device misidentifying the aggregated particles as one particle when this is analyzed by the analysis device I can not deny the decline of
According to the method described in Patent Document 1, although it is possible to prevent the decrease in dispersibility due to the difference in sedimentation velocity of each particle when using a liquid resin material, such aggregation of particles can not be suppressed. Therefore, it can be said that there is room for further improvement from the viewpoint of improving the dispersibility.

  An object of the present invention is to address such problems in the prior art, and it is an object of the present invention to manufacture a sample embedding resin from a granular sample and a granular resin material. It is an object of the present invention to provide a method for producing a sample embedding resin for analysis which can sufficiently suppress the aggregation of particles of a sample and improve the dispersibility of a particulate sample.

  As a result of intensive investigations, the inventor decided to use a rotation-revolution stirrer for stirring the granular sample and the granular resin material, and after the stirring, pressurizing and heating the granular sample and the granular resin material, the aggregation of the particles was effective. It has been found that the dispersibility of the granular sample in the resin material can be effectively improved, and a representative composition free from segregation and segregation can be obtained. This is because the granular sample and the particles of the granular resin material are kneaded by the rotation and revolution stirrer and the particles adhere to the surface of the particles of the granular sample by revolving the container into which the granular sample and the granular resin material are charged while rotating. It is considered that the particles of P. are exfoliated, etc., but the present invention is not limited to such theory.

  Based on such findings, the method for producing a sample embedding resin for analysis of the present invention comprises embedding a particulate sample to be analyzed consisting of particles having nonuniform particle sizes and containing plural kinds of single substances and / or compounds in a resin material. A method for producing a sample-embedded resin in which the particulate sample is fixed in the resin material, wherein the particulate sample and the particulate resin material are charged into a container, and the container containing the particulate sample and the particulate resin material is prepared. The granular sample and the granular resin material in the container are agitated by revolving in a rotation direction opposite to the rotation while rotating with a rotation-revolution stirrer, and then the granular sample and the granular resin material in the container are pressurized Heating and melting and then curing the particulate resin material.

  Further, according to the method for producing a sample embedding resin for analysis of the present invention, a particulate sample to be analyzed which is composed of particles having nonuniform particle sizes and which contains plural kinds of single substances and / or compounds is embedded in a resin material A method for producing a sample-embedded resin in which the particulate sample is fixed in a material, wherein the particulate sample and the particulate resin material are charged into a container, and the container containing the particulate sample and the particulate resin material is The granular sample and the granular resin material in the container are agitated by revolving in the same rotational direction as the rotation while rotating with a stirrer, and then the granular sample and the granular resin material in the container are pressurized and heated, It is to cure after melting the granular resin material.

  It is preferable that the revolution speed at the time of stirring by a rotation revolution stirrer be 400 rpm to 2000 rpm.

In the method for producing a sample embedding resin for analysis of the present invention, it is preferable to perform at least the final stage of stirring by the rotation and revolution stirrer in a vacuum atmosphere.
Further, in the method for producing a sample embedding resin for analysis of the present invention, it is preferable to carry out the initial stage of stirring by the rotation and revolution stirrer in an air atmosphere.

  It is effective to set the stirring time by the rotation revolution stirrer to 1 minute to 30 minutes.

Incidentally, in the method for producing a sample embedding resin for analysis of the present invention, it is possible to simultaneously press and heat the particulate sample and the particulate resin material.
In this case, it is preferable to set the pressure and heating time of the particulate sample and the particulate resin material to 10 minutes to 20 minutes.

In the method for producing a sample embedding resin for analysis of the present invention, when pressing the particulate sample and the particulate resin material, the pressure applied to the particulate sample and the particulate resin material is preferably 7 MPa to 35 MPa, particularly 20 MPa to 30 MPa .
Further, in the method for producing a sample embedding resin for analysis of the present invention, when heating the particulate sample and the particulate resin material, the temperature of the particulate sample and the particulate resin material is 50 ° C to 220 ° C, particularly 100 ° C to 200 ° C. It is preferable to raise it.

  In the method for producing a sample embedding resin for analysis of the present invention, particles constituting the particulate sample can be used as ore particles.

  In the method for producing a sample embedding resin for analysis of the present invention, as the container to be rotated by a rotation and revolution stirrer, a container in which a plurality of containers each containing a granular sample and a granular resin material are disposed can be used.

  According to the method of preparing the sample embedding resin for analysis of the present invention, the container containing the granular sample and the granular resin material is revolved and stirred while being rotated by the rotation revolution stirrer, and then the granular sample and the particles in the container are stirred. By pressing and heating the resin material and melting and curing the particulate resin material, the aggregation of the particles of the particulate sample in the resin material is sufficiently suppressed, whereby the dispersibility of the particulate sample in the resin material is achieved. Can be improved.

It is a perspective view which shows typically a mode at the time of making it revolve, rotating a container containing a granular sample and a granular resin material by one Embodiment of this invention. It is a perspective view which shows typically a mode at the time of making it revolve, rotating a container containing a granular sample and a granular resin material by other embodiment. It is a perspective view which shows typically a mode at the time of making it revolve, rotating the container which arrange | positioned two or more containers containing a granular sample and a granular resin material by other embodiment.

Hereinafter, embodiments of the present invention will be described in detail.
In the method of preparing a sample embedding resin for analysis according to one embodiment of the present invention, a particulate sample to be analyzed which is composed of particles having nonuniform particle sizes and which contains plural kinds of single substances and / or compounds is embedded in a resin material. In preparing the sample embedding resin in which the particulate sample is fixed in the resin material, the particulate sample is charged together with the particulate resin material into a container, and then the container containing the particulate sample and the particulate resin material The granular sample and the granular resin material in the container are agitated by causing the granular sample and the granular resin material in the container to revolve in the opposite rotation direction to the rotation or the same rotation direction while rotating the rotation with the rotation revolution stirrer. The particulate sample and the particulate resin material are pressurized and heated to melt and then cure the particulate resin material.

(Granular sample)
Particulate samples to be analyzed shall be relatively small particles by subjecting ore, slag, sludge, dust or their recycled materials including electric and electronic equipment to predetermined treatment etc. Can. Such granular samples are usually composed of many kinds of nonuniform particles having different compositions and different particle sizes, since intentional equalization of composition and particle size is not performed.

  Among them, when targeting granular samples consisting of ore particles, such ore particles may include copper ore, and examples of such ore particles include copper ore, copper ore, chalcopyrite, copper ore, arsenopyrite, etc. Broshan copper ore may be included. Besides copper ore, pyrite, magnetite, silicate mineral, molybdenite, gold particles and the like may be included. Examples of silicate minerals include orthoclase, albite, plagioclase, muscovite, biotite and quartz.

When targeting granular samples made of slag, the slag itself has a complicated composition including SiO ₂ , CaO, Al ₂ O ₃ , FeO, Fe ₃ O _{4 and the} like, and further contains matte particles and metal particles in the slag. There is a case.
In the case of a granular sample composed of an electric and electronic device, particles having various compositions such as a resin part contained in a substrate, a metal part constituting a circuit, and a flame retardant part are present.
In the case of sludge and dust, it is unlikely that they have a single composition.

  The particle size of the particles constituting the particulate sample is relatively uniformly distributed and nonuniform, for example, in the range of 1 μm to 700 μm, typically 20 μm to 200 μm. In addition, although the particle size which can be measured with a particle size distribution analyzer may be 0.243 micrometers-2000 micrometers, for example, the particle size of the above-mentioned granular sample is distributed unevenly in this range.

(Resin material)
As the resin material for embedding and fixing the above-mentioned granular sample, various materials can be used if they can be maintained in granular form at the time of charging into a container to be described later and at stirring, and can be cured by pressure and heating thereafter. Although a thing can be used, a phenol resin, an epoxy resin, an acrylic resin etc. can be mentioned, for example. Among them, a phenol resin is preferable because it has no filler.
The particle size of the particulate resin material is, for example, several μm to several hundreds μm.

(Preparation method of sample embedding resin for analysis)
In order to produce a sample-embedded resin for analysis using the above-mentioned granular sample and resin material, first, the granular sample 2 is granulated in a predetermined container 1 such as a bottomed cylindrical shape as illustrated in FIGS. Charge with resin material 3 In this embodiment, only the granular sample 2 and the granular resin material 3 can be charged into the container 1, and it is not necessary to further charge the graphite or the like. This is because the aggregation of the particles of the granular sample 2 can be sufficiently effectively removed in the granular resin material 3 by the rotation and revolution stirrer as described later. However, in other embodiments, materials such as graphite other than the particulate sample 2 and the particulate resin material 3 may be introduced.

  Next, the container 4 containing the granular sample and the granular resin material is set in a predetermined rotation revolution stirrer, and based on the function of the rotation revolution stirrer, as shown by the arrows in each of FIGS. The rotation and revolution of the container 4 containing the granular resin material are simultaneously performed to stir the granular sample 2 and the granular resin material 3 in the container 1. More specifically, the bottom portion of the bottomed cylindrical container 1 is disposed obliquely downward with its central axis inclined, and the central axis is the rotation axis of the container 4 containing the granular sample and the granular resin material. At the same time, the revolution axis is set so that the rotation axis is inclined at a predetermined angle θ at a distance from the container 1, and the container 4 containing the particulate sample and the particulate resin material is revolved around the revolution axis.

  As a result, the particles of the particulate sample 2 and the particulate resin material 3 are kneaded, and the other particles adhering to the surface of the aggregated particles of the particulate sample 2 are peeled off, so that the particles of the particulate sample 2 are aggregated. It can be removed effectively. At this time, since the particulate sample 2 and the particulate resin material 3 are sufficiently mixed, the deviation of the particulate sample 2 in the container 1 is eliminated. As a result, the dispersibility of the particulate sample 2 in the particulate resin material 3 in the sample embedding resin to be produced can be greatly enhanced.

  In addition to the stirring by the rotation / revolution stirrer, it is also possible to perform stirring by, for example, manual work before or after that, but from the viewpoint of reduction of work man-hours and shortening of work time, It is preferable not to perform stirring other than the rotation revolution stirrer. In many cases, the dispersibility can be sufficiently improved by stirring with a rotation revolution stirrer.

  As the revolution-revolution stirrer, for example, known ones can be used without particular limitation as long as they can perform such rotation and revolution of the container 4 containing the granular sample and the granular resin material. The revolution and rotation in the rotation revolution stirrer can be in mutually opposite rotational directions as shown in FIG. 1 or can be in the same rotational direction as shown in FIG. That is, the relative rotational direction of revolution and rotation is not particularly limited, and can be appropriately set according to the rotation revolution stirrer used, the state of the granular sample 2 to the granular resin material 3, and the like.

  Further, as shown in FIG. 3, it is also possible to rotate and revolve a container 4a in which a plurality of containers 4 containing granular samples and granular resin materials are disposed. This container 4a, which may also be referred to as a table by means of a rotation-revolution stirrer, can also be regarded as a container containing a granular sample and a granular resin material. In this case, the container 4a is rotated with the central axis of the container 4a as the rotation axis, and the revolution axis is set so that the rotation axis is inclined at a predetermined angle θ, and the container 4a is revolved around the revolution axis. In the example shown in FIG. 3, four containers 4 containing the granular sample and the granular resin material are arranged at equal intervals from one another around the central axis of the container 4a. However, the granular sample and the granular resin material in the container 4a are The arrangement aspect and the number of containers 4 are not limited to this. Thus, by rotating and revolving the container 4a in which a plurality of containers 4 containing granular samples and granular resin materials are arranged, the plural granular samples and the granular samples 2 of the container 4 containing granular resin materials are dispersed at one time The work efficiency can be greatly improved.

Here, it is preferable to set the revolution speed at the time of stirring by the rotation revolution stirrer to 400 rpm to 2000 rpm. If the revolution speed is too slow, there is a concern that agglomerated particles may be formed, and on the other hand, if the revolution speed is too fast, there is a risk that the grains will be worn due to friction. Although it depends on the particle size of the granular sample 2 and the granular resin material 3, as described later, the revolution speed is relatively slow in the first air atmosphere, and after the granular sample 2 and the granular resin material 3 are mixed to some extent, Under a vacuum atmosphere, it is preferable to make the revolution speed faster than that. From this point of view, it is effective to set the revolution speed in the range of 400 rpm to 2000 rpm at first, and thereafter set the revolution speed in the range of 1000 rpm to 2000 rpm on the premise that the revolution speed is higher than the first revolution speed.
Here, it is preferable that the rotation speed at the time of stirring by the rotation revolution stirrer be 0.4 to 0.6 times the revolution speed. If the rotation speed is too slow, it is considered that agglomerated particles are present. On the other hand, if the rotation speed is too fast, there is a concern that the particles may be worn away and differ from the original particle size.
In addition, the revolution speed and rotation speed which were mentioned above can be set with a rotation revolution stirrer.

  The angle θ of the rotation axis during stirring by the rotation rotation stirrer is preferably 30 ° to 60 °, more preferably 40 ° to 50 °, and the rotation axis is inclined from the rotation axis to perform stirring Can. If the inclination angle θ of the rotation shaft is small, the one with a large specific gravity is likely to settle to the bottom of the container, and if the inclination angle θ is large, the resin may spill out of the container and a necessary resin amount can not be filled There is sex. The inclination angle θ can be appropriately set in accordance with the property of the material.

  By the way, it is preferable to perform the above-mentioned stirring by the rotation / revolution stirrer with the atmosphere around the container 4 containing the granular sample and the granular resin material as a vacuum atmosphere in that the gap between the particles can be reduced.

However, if the atmosphere around the container 4 containing the granular sample and the granular resin material in the rotation and revolution stirrer is set to a vacuum atmosphere from the initial stage of stirring, the granular sample 2 existing near the surface of the opening of the container 1 may be scattered I am concerned. In order to prevent this, in the initial stage of stirring, it is preferable to perform stirring under the action of gravity as an air atmosphere, and then switch to a vacuum atmosphere and further stir. That is, it is preferable that the initial stage of stirring be in the air, and at least the final stage thereafter be in the vacuum.
Here, the initial stage of the stirring can be from when the stirring by the rotation and revolution stirrer starts to when 30 seconds to 60 seconds have elapsed. The time for which a vacuum atmosphere is subsequently applied can be 60 seconds to 30 minutes.

  As described above, when switching from the atmospheric atmosphere to a vacuum atmosphere during the stirring time by the revolution revolution stirrer, the total time of those is preferably 1 minute to 30 minutes, more preferably 5 minutes to 15 minutes. Can. If the stirring time is short, there is a concern that the dispersion of the granular sample 2 in the granular resin material 3 will be insufficient. On the other hand, if the stirring time is too long, the granular sample 2 is Destruction of the particles may occur due to the particles colliding with one another.

  Thereafter, the particulate sample 2 and the particulate resin material 3 in the container 1 are pressurized and heated, and the particulate resin material is melted while being molded and then cured. At this time, although it is necessary to take out the granular sample 2 and the granular resin material 3 from the container 1 in order to pressurize and heat, it is preferable to introduce the granular sample 2 and the granular resin material 3 while maintaining the mixed state as much as possible. In the container 1 set in the stirrer, a sheet of polyvinylidene chloride or the like is spread in advance before putting the granular sample 2 or the granular resin material 3 and the granular sample 2 and the granular resin material 3 are put thereon You may make it mix by a rotation revolution stirrer. Then, after mixing, the sheet can be wrapped in a sheet of polyvinylidene chloride or the like, taken out, and set as it is in the pressure heating apparatus.

Here, for example, a known hot embedding device can be used. In this case, generally, pressurization and heating of the granular sample 2 and the granular resin material 3 are performed simultaneously, and the time from the start to the end of the heating and pressurization is preferably 1 minute to 30 minutes, Preferably, it is 10 minutes to 20 minutes. If this pressure / heating time is too long, there is a concern that different speeds of the particles of the granular sample 2 may be caused during melting before the granular resin material 3 is cured, while the pressure / heating time is If the length is too short, the sample may be peeled off during planar polishing.
However, for example, cold forming and heating may be performed in this order or in the reverse order to separate pressurization and heating.

  When the granular sample 2 and the granular resin material 3 are pressurized, the pressure applied to the granular sample 2 and the granular resin material 3 is preferably 7 MPa to 35 MPa, and more preferably 20 MPa to 30 MPa. If the pressing force at this time is too small, the resin material may not be molded sufficiently, and there is a concern that the sample embedding resin can not be produced or is broken at the time of subsequent handling or analysis. On the other hand, if the pressing force is too large, there is a possibility that the particles of the particulate sample 2 may be damaged.

When heating the granular sample 2 and the granular resin material 3, it is preferable to set the granular sample 2 and the granular resin material 3 to 50 ° C. to 220 ° C., and more preferably 100 ° C. to 200 ° C. If the maximum temperature reached is too low, melting and curing of the particulate resin material 3 may not be effectively performed, and if too high, the properties of the sample may change.
In addition, when raising the temperature of the granular sample 2 and the granular resin material 3, it is desirable to make fine adjustments such that the temperature is raised every 1 ° C. In general, the temperature rising rate and the cooling rate are changed according to the type and volume of the particulate sample 2 and the particulate resin material 3.

In the sample embedding resin produced as described above, the particle size distribution of the particles of the granular sample dispersed in the resin material in the sample embedding resin is substantially the same as the particle size distribution of the granular sample before embedding, that is, substantially The same tendency is preferable from the viewpoint of suppressing aggregation of particles.
And such a sample embedding resin can be used for analysis of the element content of a granular sample, particle size distribution, single separation degree, etc. using various analyzers. In particular, here, when particles constituting the particulate sample are ore particles, the sample embedding resin can be effectively used for analysis by a mineral analysis system (Mineral Liberation Analyzer, MLA).

1 container 2 granular sample 3 granular resin material 4, 4a container containing granular sample and granular resin material θ inclination angle of rotation axis with respect to revolution axis θ

Claims (12)

A particulate sample to be analyzed which is composed of particles having nonuniform particle sizes and which contains plural kinds of single particles and / or compounds is embedded in a resin material to prepare a sample embedding resin in which the particulate sample is fixed in the resin material. Method,
The above-mentioned granular sample is put into a container together with a granular resin material, and the container containing the granular sample and the granular resin material is made to rotate in a rotation direction opposite to the rotation while rotating the rotation container with the rotation revolution stirrer. The particulate sample and the particulate resin material in the container are stirred, and then, the particulate sample and the particulate resin material in the container are pressurized and heated to melt and then cure the particulate resin material. Method. A particulate sample to be analyzed which is composed of particles having nonuniform particle sizes and which contains plural kinds of single particles and / or compounds is embedded in a resin material to prepare a sample embedding resin in which the particulate sample is fixed in the resin material. Method,
In the container, the granular sample is charged together with the granular resin material, and the container containing the granular sample and the granular resin material is rotated in the same rotation direction as the rotation while rotating by the rotation revolution stirrer. A method for producing a sample embedding resin for analysis, which comprises stirring a granular sample and a granular resin material and thereafter pressing and heating the granular sample and the granular resin material in a container to melt and then harden the granular resin material.   The manufacturing method of the sample embedding resin for analysis of Claim 1 or 2 which sets the revolution speed at the time of stirring by a rotation revolution stirrer to 400 rpm-2000 rpm.   The manufacturing method of the sample embedding resin for analysis as described in any one of Claims 1-3 which performs a vacuum atmosphere at least the final stage of the stirring by a rotation revolution stirrer.   The preparation method of the sample embedding resin for analysis as described in any one of Claims 1-4 which performs the initial stage of the stirring by a rotation revolution stirrer in air | atmosphere atmosphere.   The manufacturing method of the sample embedding resin for analysis as described in any one of Claims 1-5 which makes stirring time by a rotation revolution stirrer 1 minute-30 minutes.   The manufacturing method of the sample embedding resin for analysis as described in any one of Claims 1-6 which pressurize and heat a granular sample and a granular resin material simultaneously.   The method for producing a sample embedding resin for analysis according to claim 7, wherein pressing and heating times of the particulate sample and the particulate resin material are 10 minutes to 20 minutes.   The preparation of the sample embedding resin for analysis according to any one of claims 1 to 8, wherein the pressure applied to the particulate sample and the particulate resin material is 20 MPa to 30 MPa when the particulate sample and the particulate resin material are pressurized. Method.   The sample embedding resin for analysis according to any one of claims 1 to 9, wherein the temperatures of the particulate sample and the particulate resin material are raised to 100 ° C to 200 ° C when the particulate sample and the particulate resin material are heated. How to make   The method for producing a sample embedding resin for analysis according to any one of claims 1 to 10, wherein particles constituting the particulate sample are ore particles.   The sample embedding resin for analysis according to any one of claims 1 to 11, wherein a container in which a plurality of containers containing a granular sample and a granular resin material are disposed is used as the container to be rotated by the rotation revolution stirrer. How to make it.