JP2011214978A - Device and method for measuring coefficient of cubic expansion of solid organic polymer material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a device and method for measuring a coefficient of cubic expansion of a solid organic polymer material, which measures a coefficient of cubic expansion of, for example, a synthetic resin or synthetic rubber having properties of swelling within a high-pressure fluid, such as a subcritical fluid or supercritical fluid, or measures a coefficient of cubic expansion of a rubber product, such as a packing or O-ring, abutting on a high-temperature/high-pressure atmosphere fluid in a chemical process.SOLUTION: The measuring device of a coefficient of cubic expansion of a solid organic polymer material is equipped with: a measuring vessel capable of housing fluid, a solid sample made of a solid organic polymer material having properties of swelling by the fluid, and a fluid medium flowing within the fluid by swelling of the solid sample; a piston provided within the measuring vessel so that the piston can be elevated and lowered freely by swelling of the solid sample and flow of the fluid medium within the fluid; and a detection means of detecting a distance where the piston has risen to measure the coefficient of cubic expansion of the solid sample.

Description

  The present invention relates to an apparatus and a method for measuring the volume expansion coefficient of a solid organic polymer material, and more specifically, a synthetic resin or synthetic rubber having a property of swelling in a high-pressure fluid such as a subcritical fluid or a supercritical fluid. Of solid organic polymer materials that can measure the volume expansion coefficient of rubber products such as packing or O-rings that are in contact with high temperature and high pressure atmospheric fluid in chemical processes The present invention relates to a volume expansion coefficient measuring device and a measuring method thereof.

  Since supercritical fluids have excellent penetrating power to substances, functional substances are injected into solids made of various materials to give desired properties to the solids, or impurities are removed from the solids, etc. Various technologies have been developed. Especially in the case of carbon dioxide, since the critical temperature and critical pressure are relatively low, supercritical carbon dioxide is a solid organic polymer such as a synthetic resin represented by general-purpose plastics, general-purpose engineering plastics, and special engineering plastics. Various techniques for contacting and processing materials have been developed.

  By the way, when processing a solid organic polymer material such as a synthetic resin or a synthetic rubber at a predetermined temperature, the physical properties of the solid organic polymer material, such as a glass transition point (Tg), are grasped in advance. In doing so, the temperature setting of the apparatus for that purpose can be easily performed in performing the processing. For this reason, the glass transition point (Tg) is estimated, and the weight transition (ΔW), volume change (ΔV), and volume change (ΔV) of the solid organic polymer material are added to the formula for estimating the glass transition point (Tg). Since changes in density (Δρ) and the like are included, these are measured, and the measured values are substituted into the above estimation formula to estimate the glass transition point (Tg).

  Further, not only the glass transition point (Tg) but also an estimation formula may be used for physical quantities such as specific heat (constant pressure specific heat Cp, constant volume specific heat Cv) and melting point (Tm), for example. Similar to the transition point (Tg), a change in weight (ΔW), a change in volume (ΔV), and the like are included.

  And, when the supercritical carbon dioxide as described above is brought into contact with the solid organic polymer material, the solid organic polymer material absorbs the supercritical carbon dioxide and swells to change its weight and volume. Naturally, such supercritical fluids are handled at high temperatures and pressures. Therefore, especially when measuring volumes, volume errors due to high temperatures and high pressures compared to standard volumes of materials at normal temperatures and in air are considered. In addition, volume errors due to the absorption of supercritical carbon dioxide in solid organic polymer materials must be taken into account, making it difficult to measure volume changes under such conditions. It was.

  Therefore, in such a case, conventionally, a sample of a solid organic polymer material formed into a film is placed in a cell under high temperature and high pressure, and the area is measured by taking a photograph or the like in that state. The volume change was calculated from the area change. Specifically, the volume change has been sought by approximating the area change ΔS≈ΔV by reducing the thickness of the sample of the solid organic polymer material as much as possible.

  However, in such an approximation method, if the film-like sample has irregularities, the measurement error may increase. In addition, since the sample is in the form of a film, the sample is warped, entrained, twisted, and the like at high temperature and high pressure, and in this case, measurement error may be increased.

  In order to prevent warping, the sample was sandwiched from above and below with a glass plate or the like, but in this case, supercritical carbon dioxide was sampled from the solid organic polymer material due to the presence of the glass plate. Since it becomes difficult to make contact over the entire surface and supercritical carbon dioxide comes into contact with the sample only from the side of the thin side, the original measurement is performed under special conditions in a supercritical carbon dioxide atmosphere. When the measurement that matches the purpose cannot be performed and the measured value of the volume change is substituted into the formula for estimating the physical quantity such as the glass transition point (Tg) and specific heat under the same temperature and pressure conditions, That physical quantity is not accurately calculated. In addition, the interaction between the glass plate and the solid organic polymer material is ignored, and the error increases.

  Therefore, in order to solve such problems, patent applications such as the following Patent Document 1 have been filed. As described in claim 1 of Patent Document 1, the invention according to Patent Document 1 is “a three-dimensional shape having a property of being swollen by a high-pressure fluid in a high-pressure vessel and having a rotationally symmetric axis. After the solid made of the formed organic polymer material is fixed and accommodated, a high-pressure fluid is allowed to flow into the high-pressure vessel part to swell the solid, and after the swollen state has reached an equilibrium state, The solid images of the stationary state fixed in (3) are photographed with a digital camera, and sequentially photographed at stationary positions rotated by the same angle, and the images photographed at each stationary position have a three-dimensional shape by a predetermined calculation method. A solid volume measuring method characterized in that the volume of the solid is measured by approximately calculating the volume of the solid.

  In the invention according to Patent Document 1, since it is applied to a solid sample made of a solid organic polymer material having a property of swelling by a high-pressure fluid, and such a solid sample is accommodated in a high-pressure vessel portion, a high-pressure fluid atmosphere is generally used. The effect of easily measuring the volume of the swellable solid, which has been difficult underneath, is achieved. In addition, the accuracy of the numerical calculation of the volume change (ΔV) can be dramatically improved, and the numerical value of the volume change (ΔV) calculated in this way is a target to be processed in a supercritical carbon dioxide atmosphere. Estimates of physical quantities such as glass transition point (Tg), melting point (Tm), specific heat (Cp), (Cv) under high pressure of solid organic polymer materials such as various synthetic resins, especially under supercritical fluid atmosphere The error in the case of substitution is also an epoch-making method that did not exist in the prior art because it has the effect of being significantly less than the conventional calculation method.

  However, although the accuracy of numerical calculation of volume change (ΔV) in the atmosphere of the supercritical fluid in the high-pressure vessel part as described above can be improved, this technique is applied to the solid organic high Easy to apply to the measurement of the volume expansion coefficient of molecular materials, such as packing or O-rings that come into contact with high-temperature and high-pressure atmospheric fluid (generally high-temperature and high-pressure liquid or slurry fluid) in the chemical process is not. That is, in an actual chemical engineering process, packing and O-rings are in contact with a high-temperature and high-pressure atmospheric fluid. To measure the volume expansion coefficient of such packings and O-rings, It is necessary to leave the packing and O-ring exposed to the ambient fluid as in the actual chemical engineering process.

  On the other hand, in the measurement method of Patent Document 1, a volume of a solid sample made of a solid organic polymer material formed in a three-dimensional shape is measured based on an image obtained by rotating the solid sample by a predetermined angle about a rotational symmetry axis. Since it is a method of calculating the expansion coefficient approximately, the rotation shaft portion that is the shaft central portion that rotates the solid sample is inserted into a part of the casing that houses the solid sample to be measured. Thus, by inserting the rotating shaft portion into a part of the casing, a hole to be inserted must be formed in the casing. Such a hole is not affected by providing a certain degree of sealing performance when measuring the volume expansion coefficient in the supercritical fluid atmosphere as described above. It is difficult to store the liquid such as the packing and the O-ring exposed to the atmospheric liquid such as the oil. That is, the fluid such as oil leaks to the outside of the casing from the hole drilled through the rotating shaft portion.

  Furthermore, in the invention according to Patent Document 1, since the solid sample to be measured needs to have a three-dimensional shape that is symmetric about the rotational symmetry axis, the shape is a cone obtained by rotating a trapezoid. A special shape such as a trapezoidal shape is required, and a solid sample to be measured has to be processed into such a special shape.

  Furthermore, in the method described in the above-mentioned Patent Document 1, since the measurement is performed in a state where the solid sample is merely placed on the gantry, a fluid having a density lower than that of the solid sample is introduced into the casing, such as a supercritical fluid. However, if the ambient fluid density is about the same as or higher than that of the solid sample, the solid sample may inadvertently move on the gantry. Yes, measurement may be inaccurate.

  Furthermore, in the method described in Patent Document 1, since the solid sample in the casing is imaged from the visible window by image capturing means such as a digital camera, the image cannot be captured when the atmospheric fluid is opaque. As a result, measurement becomes impossible.

Japanese Patent No. 4225808

  The present invention has been made to solve such problems, and the volume expansion coefficient of a synthetic resin or synthetic rubber having a property of swelling in a high-pressure fluid such as a subcritical fluid or a supercritical fluid. For measuring the volume expansion coefficient of solid organic polymer materials that can measure the volume expansion coefficient of rubber products such as packings or O-rings that come into contact with high-temperature and high-pressure atmospheric fluids in chemical processes And providing a measuring method thereof.

  In order to solve such problems, the present invention provides a fluid, a solid sample made of a solid organic polymer material having a property of swelling by the fluid, and a flow that flows in the fluid by swelling the solid sample. A measurement container capable of containing a medium, a piston provided so as to be movable up and down in the measurement container when the solid sample swells and a fluid medium flows in the fluid, and a volume expansion coefficient of the solid sample. In order to make a measurement, the present invention provides a measuring device for the volume expansion coefficient of a solid organic polymer material, characterized by comprising a detecting means for detecting the distance that the piston has moved up.

  Further, the present invention accommodates a solid sample made of a solid organic polymer material having a property of swelling by a fluid in a measurement container that can contain the fluid, and the solid sample swells in the fluid. The measuring container is filled with a fluid medium to flow, and a piston is provided in the measuring container so that the solid sample swells and the fluid medium flows to allow the fluid to move up and down. The solid sample is swelled to flow, the piston is raised by flowing the fluid medium in the fluid, and the detection means for detecting the distance that the piston is raised detects the distance the piston is raised. The present invention provides a method for measuring the volume expansion coefficient of a solid organic polymer material, characterized by measuring the volume expansion coefficient of a solid sample.

  As a detection means for detecting the distance that the piston has moved up, a part of the piston is exposed outside the measurement container, and the measurement container is housed in another high-pressure container together with the exposed piston, and the tip of the piston A permanent magnet is attached to the part, and the float sucked by the permanent magnet is arranged on the outer periphery of the high-pressure vessel so that it can roll on the outer peripheral surface side of the high-pressure vessel corresponding to the position of the tip of the piston to which the permanent magnet is attached. It is possible to employ a means that is provided on the surface and detects the distance that the piston has moved up by the movement distance of the float.

  In addition, a permanent magnet is attached to the tip of the piston, and the float attracted by the permanent magnet so that it can roll on the outer peripheral surface side of the measurement container corresponding to the position of the tip of the piston to which the permanent magnet is attached. It is also possible to employ means that is provided on the outer peripheral surface of the measurement container and detects the distance that the piston has moved up by the distance of movement of the float.

  Further, as a detecting means for detecting the distance that the piston has moved up, a part of the piston is exposed outside the measurement container, and a scale is provided on the tip side of the piston, and the scale of the piston rising outside the measurement container It is also possible to adopt means for detecting the distance that the piston has moved up.

  As the fluid medium, a material such as an aggregate of a large number of spherical bodies having a surface excellent in slidability can be used.

  In the present invention, as described above, a solid sample made of a solid organic polymer material having the property of being swollen by the fluid is contained in a measurement container that can contain the fluid, and the solid sample is swollen. The measurement container is provided with a piston that is filled with a fluid medium that flows in the fluid and that can be moved up and down as the solid sample swells and the fluid medium flows. The distance by which the piston is raised by the detecting means for detecting the distance by which the piston is lifted by flowing the fluid into the fluid and causing the solid sample to swell and by causing the fluid medium to flow in the fluid. Therefore, the volume expansion rate of the solid sample is measured, and the expanded volume of the solid sample is favored by the piston through the flow of the flow medium and the movement of the fluid. Is transmitted to the distance the piston is raised is detected by said detecting means capable of measuring the volume expansion coefficient of the solid sample.

  In this way, the volume expansion coefficient of the solid sample can be measured by detecting the rising distance of the piston transmitted through the flow of the expansion fluid medium and the movement of the fluid by the detection means as described above. Regardless of physical properties such as density and transparency of the fluid that flows into the solid, it is possible to suitably measure the expanded volume of the solid sample. As a result, the solid organic polymer material in the fluid such as a supercritical fluid In addition to measuring the volume expansion coefficient, solids such as packing and O-rings in an atmospheric fluid used in an actual chemical process, which is difficult to measure with the technique described in Patent Document 1 above, are used. There is an effect that the volume expansion coefficient of the organic polymer material can be measured.

The schematic sectional drawing of the measuring apparatus of the volume expansion coefficient of the solid organic polymer material as one Embodiment. The schematic block diagram which shows the distribution system of the supercritical fluid incorporating the same measuring apparatus. The schematic sectional drawing of the measuring apparatus of the volume expansion coefficient which shows the state which the piston raised. The schematic sectional drawing of the measuring apparatus of the volume expansion coefficient of the solid organic polymer material as other embodiment. AA line sectional view of Drawing 4. The schematic sectional drawing which shows the state which the piston of the apparatus raised. Furthermore, the schematic sectional drawing of the measuring apparatus of the volume expansion coefficient of the solid organic polymer material as other embodiment. The schematic sectional drawing which shows the state which the piston of the apparatus raised.

  Hereinafter, embodiments of the present invention will be described.

  An apparatus for measuring a volume expansion coefficient of a solid organic polymer material according to the present invention includes a fluid, a solid sample composed of a solid organic polymer material having a property of being swollen by the fluid, and the solid sample being swollen in the fluid. A measurement container capable of containing a flowing fluid medium; a piston provided so as to be movable up and down in the measurement container when the solid sample swells and the fluid medium flows in the fluid; and the piston is raised Detecting means for detecting the distance and measuring the volume expansion coefficient of the solid sample.

  Moreover, the method for measuring the volume expansion coefficient of the solid organic polymer material of the present invention accommodates a solid sample made of a solid organic polymer material having the property of being swollen by the fluid in a measurement container capable of accommodating the fluid. A piston that fills the measurement container with a fluid medium that flows in the fluid as the solid sample swells, and that can move up and down as the solid sample swells and the fluid medium flows. Provided in the measurement container, the fluid flows into the measurement container to swell the solid sample, and the fluid medium is flowed in the fluid to raise the piston and detect the distance the piston has moved up. The detection means detects the distance that the piston is raised and measures the volume expansion coefficient of the solid sample.

  As a detection means for detecting the distance that the piston has moved up, a part of the piston is exposed outside the measurement container, and the measurement container is housed in another high-pressure container together with the exposed piston, and the tip of the piston A permanent magnet is attached to the part, and the float sucked by the permanent magnet is arranged on the outer periphery of the high-pressure vessel so that it can roll on the outer peripheral surface side of the high-pressure vessel corresponding to the position of the tip of the piston to which the permanent magnet is attached. It is possible to employ a means that is provided on the surface and detects the distance that the piston has moved up by the movement distance of the float.

  In addition, a permanent magnet is attached to the tip of the piston, and a float sucked by the permanent magnet is attached so that it can roll on the outer peripheral surface side of the measurement container corresponding to the position of the tip of the piston to which the permanent magnet is attached. A means that is provided on the outer peripheral surface of the measurement container and detects the distance by which the piston is lifted by the movement distance of the float can also be adopted.

  As described above, the float attracted by the permanent magnet is provided on the outer peripheral surface of the measurement container or high-pressure vessel so that it can roll on the outer peripheral surface side of the measurement container or high-pressure vessel corresponding to the position of the tip of the piston. In this case, it is possible to provide the measurement container or the high-pressure container so as to be in direct contact with the outer peripheral surface of the measurement container or the high-pressure container. It is also possible to install and store the float in its casing. Even in this case, as the permanent magnet attached to the tip of the piston moves, the float in the casing also moves while rolling, so the inside of the measurement vessel or high-pressure vessel cannot be seen through from the outside. However, the distance that the piston has risen can be detected.

  In addition, as a permanent magnet, although a ferrite magnet, a metal magnet, a bond magnet, etc. can be applied, the solid-state ferrite magnet and metal magnet which are comprised with an inorganic component are preferable. Furthermore, a metal magnet having a strong magnetic force is more preferable. The metal magnet includes an alnico magnet and a rare earth magnet, and a neodymium magnet among the rare earth magnets is more preferable. The float is preferably a metal that is attracted to a permanent magnet. Furthermore, in order to strengthen the attractive force between the permanent magnet and the float and make the interlocking smooth, it is more preferable that the material of the float is also a permanent magnet.

  Further, as a detecting means for detecting the distance that the piston has moved up, a part of the piston is exposed outside the measurement container, and a scale is provided on the tip side of the piston, and the scale of the piston rising outside the measurement container It is also possible to adopt means for detecting the distance that the piston has moved up.

  Moreover, as an expansion | swelling fluid medium, what consists of many spherical granular materials in which the surface was formed in the smooth surface can be used. For example, glass beads, stainless steel, and other metals can be used. However, it is desirable to use glass beads from the viewpoint of the smoothness of the surface, the easiness of the work of forming into a spherical shape, and the production cost.

  When such a large number of spherical particles are used, the particle size of the particles is preferably about 0.5 to 2 mm. If it is less than 0.5 mm, when the piston moves up and down, the granular material enters the gap formed between the lower part of the piston and the inner peripheral surface of the measurement container or the high-pressure container, and between the lower part of the piston and the inner peripheral surface of the container. This is because there is a possibility that the piston may not move due to inadvertently sandwiching the granular material.

  On the other hand, if the solid sample exceeds 2 mm, if the solid sample is indeterminate, there is a possibility that a gap may be inadvertently formed between the solid sample and the granular material when the solid sample comes into contact with the solid sample. This is because the measured volume may not be accurately transmitted to the expanding fluid medium, and the measurement of the volume expansion rate may be inaccurate.

  As the fluid, for example, a supercritical fluid can be used. In this case, for example, carbon dioxide (critical temperature: 31.1 ° C., critical pressure: 7.38 MPa) can be used. In addition to carbon dioxide, nitrous oxide (critical temperature: 36.4 ° C., critical pressure: 7.24 MPa), trifluoromethane (critical temperature: 25.9 ° C., critical pressure: 4.84 MPa), nitrogen (critical temperature: (-147 ° C., critical pressure: 3.39 MPa) can also be used. Moreover, not only a supercritical fluid but a subcritical fluid can also be used.

  Furthermore, the fluid is not limited to the supercritical fluid, and for example, liquid such as warm water, hot water, and oil can be used.

  As the solid sample made of an organic polymer material, various organic polymer materials such as synthetic resins and synthetic rubbers can be used. Examples of synthetic resins include polypropylene (PP), high density polyethylene (HDPE), low density polyethylene (LDPE), polyvinyl chloride (PVC), polystyrene (PS), ABS resin (ABS), and polymethyl methacrylate (PMMA). General purpose plastics such as polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), polyethylene terephthalate (PET), polyamide, polyacetal (POM), polycarbonate (PC), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), etc. In addition to general-purpose engineer plastics, polysulfone (PSU), polyethersulfone (PES), polyphenylene sulfide (PPS), polyarylate (PAR), polyamideimide (PAI), polyester Special engineering plastics such as terimide (PEI), polyetheretherketone (PEEK), polyimide (PI), fluororesin (PTFE, PCTFE, PVDF, etc.) can be used, and blend polymers that are a mixture of these Can also be used.

  Further, as the synthetic rubber, nitrile rubber, butyl rubber, EPDM, EPM, polybutadiene rubber, isoprene rubber, silicon rubber, styrene / butadiene copolymer rubber, epichlorohydrin rubber, allyl rubber, and the like can be used.

  Hereinafter, more specific embodiments of the present invention will be described with reference to the drawings.

(Embodiment 1)
FIG. 1 is a schematic cross-sectional view of an apparatus for measuring the volume expansion coefficient of a solid organic polymer material as one embodiment, and FIG. 2 is a volume expansion of the solid organic polymer material by a supercritical fluid incorporating the measurement apparatus. It is a schematic block diagram which shows a rate measurement system. As shown in FIG. 1, the measuring device 22 for measuring the volume expansion coefficient of the solid organic polymer material of the present embodiment houses the measuring container 1 for measuring the volume expansion coefficient of the solid organic polymer material in a high-pressure container 13. It consists of a structure. Both the measurement container 1 and the high-pressure container 13 are made of stainless steel. As the material of stainless steel, it is desirable to use a non-magnetic material generally called 300 series stainless steel (not attracted by a magnet). In this embodiment, SUS316 is used.

  As shown in FIG. 1, the measurement container 1 includes a substantially cylindrical container body 2, an upper lid body 4 that closes the opening 3 at the top of the container body 2, and an opening 5 at the bottom of the container body 2. The bottom cover body 6 is closed, and the piston 7 is provided in the container main body 2 so as to be movable up and down.

  The container body 2 is composed of a stainless precision cylindrical pipe. The upper lid 4 is formed of a cap nut, and the upper lid 4 is provided with a gas vent hole 8 as shown in FIG. Further, the bottom cover 6 is configured to include a cap nut 6a, and an interposer 9 is interposed between the cap nut 6a and the outer peripheral surface of the container body 2, and the interposer 9 and the cap nut 6a are interposed. A mesh 10 is interposed between the bottoms of the two. Further, a hole 11 is formed in the bottom portion of the cap nut 6a so that fluid can flow into the container body 2 from the hole 11 through the mesh 10.

  The piston 7 is composed of a rod portion 7a and a piston portion 7b attached to the lower end portion of the rod portion 7a, and a neodymium magnet 12 is attached to the upper end portion of the rod portion 7a as shown in FIG. ing. Since the carbon dioxide can flow through the clearance between the piston 7 and the upper lid 4, the gas vent hole 8, the clearance between the piston portion 7 b and the measurement container 1, and the gaps of the mesh 10, It has a structure that can fill carbon dioxide in all spaces.

  The measurement container 1 is housed in the high-pressure container 13 as described above, and the high-pressure container 13 includes a bottomed cylindrical container body 14 and a lid that closes the upper opening 15 of the container body 14. 16. A dome 18 capable of containing the piston 7 is attached to the lid 16, and the flange portion 17 of the container body 14 and the lid 16 are faced to each other and joined with a bolt so that the opening 15 at the top of the container body 14 is joined. Is closed.

  As shown in FIG. 1, the space in the dome 18 is formed relatively long so that the piston 7 can move up and down. A transparent long and narrow casing 19 with a scale is installed on one side of the side surface of the dome body 18, and the casing 19 is attached to the upper end of the rod portion 7 a of the piston 7. A neodymium float 20 is housed so that the neodymium magnet 12 can move while rolling.

  Furthermore, a gantry 21 is interposed between the bottom of the high-pressure vessel 13 and the bottom of the bottom lid 6 of the measurement vessel 1 as shown in FIG. By interposing such a gantry 21, a space is formed between the bottom of the measurement vessel 1 and the bottom of the high-pressure vessel 13, and the space becomes a fluid flow path from the hole 11 as described above. The fluid can flow into the container body 2 of the measurement container 1.

  The volume expansion coefficient measuring device 22 of the solid organic polymer material having such a configuration is used by being incorporated in a volume expansion coefficient measurement system for a solid organic polymer material using a supercritical fluid as shown in FIG. 2, for example. That is, in such a supercritical fluid distribution system, in addition to the volume expansion coefficient measuring device 22 of the solid organic polymer material as described above, a cylinder 23, a high-pressure pump 24, a pressure gauge 25, and a back pressure valve. 26.

  The cylinder 23 is a cylinder for storing a fluid that forms a supercritical fluid or a subcritical fluid. As the fluid, for example, carbon dioxide is used. The high-pressure pump 24 is a pump for supplying the fluid in the cylinder 23 to the volume expansion rate measuring device 22, and the pressure of the high-pressure pump 24 is measured by the pressure gauge 25. The back pressure valve 26 can be opened and closed with a predetermined pressure, and is for keeping the operating pressure constant at a predetermined value. Furthermore, the supercritical fluid is depressurized and separated from the measuring device 22 by completely opening the back pressure valve 26 and reducing the pressure.

  Next, an embodiment of a method for measuring the volume expansion coefficient of a solid organic polymer material by the measuring device 22 incorporated in the volume expansion coefficient measurement system of the solid organic polymer material using the supercritical fluid as described above will be described. .

  First, a general-purpose plastic solid sample 27 made of a solid organic polymer material to be measured and an aggregate of a large number of granular spherical bodies 28 as a fluid medium are placed in a measurement container 1 as shown in FIG. Accommodate. In this case, the solid sample 27 is arranged and filled into the measurement container 1 so that the aggregate of a large number of spherical bodies 28 is in close contact with the entire periphery of the solid sample 27. In the present embodiment, the solid sample 27 is made of synthetic resin, and the spherical body 28 is glass beads.

  Next, after supplying carbon dioxide from the cylinder 23 to the high-pressure vessel 13 and purging residual air in the high-pressure vessel 13, the carbon dioxide is supplied to the high-pressure vessel 13 using the high-pressure pump 24, and the temperature and pressure are adjusted. To do. The temperature is controlled by a temperature controller (not shown), and the pressure is controlled by a high pressure pump 24.

  The temperature and pressure may be any conditions as long as the high-pressure fluid to be used becomes a subcritical fluid or a supercritical fluid. In the present embodiment, carbon dioxide (critical temperature: 31.1 ° C., critical pressure: 7.38 MPa) is used as the high-pressure fluid. Therefore, the temperature range is preferably 25 ° C. to 200 ° C., and the pressure is preferably 6 MPa to 50 MPa.

  After reaching the predetermined temperature and pressure conditions, the high-pressure pump 24 is stopped. The supercritical fluid of carbon dioxide flows into the high-pressure vessel 13 as described above, but the supercritical carbon dioxide that has flowed into the high-pressure vessel 13 is further measured through the mesh 10 from the hole 11 at the bottom of the measurement vessel 1. It flows into the container 1. Then, when the supercritical carbon dioxide that has flowed into the measurement container 1 comes into contact with the solid sample 27 through the gaps between the many spherical bodies 28 that form an aggregate, the carbon dioxide penetrates into the solid sample 27. Therefore, the solid sample 27 swells and the volume increases.

  When the solid sample 27 swells and increases in volume in this way, a large number of spherical bodies 28 flow as the volume of the solid sample 27 increases, and as a result, as shown in FIG. As a result, the piston portion 7b below the piston 7 is pushed up by the volume expansion of the solid sample 27, and the piston 7 is raised. When the piston 7 moves up, the neodymium magnet 12 attached to the upper end of the rod portion 7a of the piston 7 moves upward, and is accordingly housed in a transparent glass casing 19 with a uniform scale. Move up the float 20.

  Then, the position of the float 20 in the frame 19 before the supercritical carbon dioxide flows into the measurement container 1 is detected in advance, and the piston 7 after the supercritical carbon dioxide flows into the measurement container 1 is detected. The amount of movement, and thus the amount of movement of the float 20 accompanying the movement of the neodymium magnet 12 attached to the upper end of the rod portion 7a is read. Since the inner diameter of the cylindrical body of the measurement container 1 is known in advance, the volume of the solid sample 27 that is swollen and increased can be calculated by calculating the product of the amount of movement and the inner diameter of the measurement container 1. it can. Furthermore, the volume expansion coefficient can be calculated from the value of the initial volume of the solid sample 27 measured in advance before processing.

  As described above, in the present embodiment, the solid sample 27 to be measured and the aggregate made up of a large number of spherical bodies 28 as a fluid medium are accommodated in the measurement container 1, and supercritical carbon dioxide is contained in the measurement container 1. The increase in the volume of the solid sample 27 in which the supercritical carbon dioxide permeates and swells by being introduced into the inside can be measured by detecting the movement amount of the piston by the neodymium magnet as described above.

  In this case, the high-pressure vessel 13 made of stainless steel is hermetically sealed so that the inside of the high-pressure vessel 13 cannot be seen through from the outside. Therefore, the rising distance of the piston 7 cannot be directly detected from the outside, A neodymium magnet 12 is attached to the upper end of the rod portion 7 a of the piston 7, and a transparent frame body 19 is installed on the outer surface of the high-pressure vessel 13. A neodymium magnet float 20 is placed in the frame body 19. Since it is housed so as to move with the neodymium magnet 12, the volume expansion coefficient of the swollen solid sample 27 can be easily measured even if the inside of the high-pressure vessel 13 cannot be directly visualized.

(Embodiment 2)
This embodiment is another embodiment of the measuring device for the volume expansion coefficient of the solid organic polymer material. FIG. 4 is a schematic cross-sectional view of the volume expansion coefficient measuring device of the solid organic polymer material, and FIG. 5 is a cross-sectional view taken along the line AA of FIG. As shown in the figure, the measuring apparatus 1 of the volume expansion coefficient of the present embodiment is configured by the high-pressure container itself, and in this respect, the measuring container 1 and the high-pressure container 13 are formed separately, This is different from the first embodiment in which the measurement container 1 is housed in the high-pressure container 13.

  The measurement container 1 is made of stainless steel as in the first embodiment, and uses a non-magnetic stainless steel called 300 series stainless steel, specifically SUS316. As shown in FIG. 4, the measurement container 1 includes a bottomed cylindrical container body 2 and a lid 4 that closes the opening 3 at the top of the container body 2. Further, the lid body 4 is configured by a flange portion 29 and a dome portion 30 erected from the flange portion 29 so that the piston 7 can be included. The space part in the dome part 30 is formed comparatively long so that the piston 7 can move up and down as shown in FIG. Further, although not shown in the drawing, the top of the lid 4 is configured so that fluid can flow out.

  A piston 7 is provided in the container body 2 so as to be movable up and down. The piston 7 includes a rod portion 7a and a piston portion 7b attached to the lower end portion of the rod portion 7a, and a neodymium magnet 12 is attached to the upper end portion of the rod portion 7a as shown in FIG. ing. The piston portion 7b is made of a sintered material made of stainless steel having a nominal aperture diameter of about 100 μm.

  As shown in FIGS. 4 and 5, a scaled casing 19 is installed on one side of the side surface portion of the dome portion 30, and the rod portion 7 a of the piston 7 is placed in the frame body 19. A float 20 of neodymium magnet is housed so that it can move while rolling as the neodymium magnet 12 attached to the upper end moves. Although not shown, the bottom of the container body 2 is configured to allow fluid to flow in.

  Similarly to the measurement device 22 of the first embodiment, the measurement device 22 for the volume expansion coefficient of the solid organic polymer material of the present embodiment is also incorporated into a solid volume expansion coefficient measurement system using a supercritical fluid as shown in FIG. Used in. The configuration of the solid volume expansion coefficient measurement system using the supercritical fluid is the same as that of the first embodiment, and thus detailed description thereof is omitted.

  The point that the solid sample 27 to be measured and the aggregate 28 as a fluid medium are accommodated in the measurement container 1 are the same as in the first embodiment. In this case, the solid sample 27 is arranged and the measurement container 1 is filled with the aggregate so that the aggregate consisting of a large number of spherical bodies 28 comes into close contact with the entire periphery of the solid sample 27, and the solid Similar to the first embodiment, a general-purpose plastic made of a solid organic polymer material is used as the sample 27, and glass beads are used as the spherical body 28.

  Also in this embodiment, when supercritical carbon dioxide flows into the measurement container 1 via the inflow portion at the bottom of the container body 2, the gap between the spherical bodies 28 that form the aggregate is formed by the supercritical carbon dioxide that has flowed. The carbon dioxide permeates into the solid sample 27 and the solid sample 27 swells, and the volume increases as shown in FIG. As the volume of the solid sample 27 is increased due to the swelling, the aggregate made up of a large number of spherical bodies 28 flows, and the aggregate pushes up the piston portion 7b below the piston 7 only by the volume expansion of the solid sample 27. This also raises the piston 7 in the same manner as in the first embodiment.

  However, in the present embodiment, the measurement container 1 and the high-pressure container 13 are separately provided as in the first embodiment, and the measurement container 1 is not housed in the high-pressure container 13 but the measurement container 1 itself. Is configured to be used also as a high-pressure vessel, so that supercritical carbon dioxide must be discharged from the measurement vessel 1. Therefore, the piston part 7b is comprised with the mesh. Since the piston part 7b is made of a sintered material made of stainless steel, the supercritical carbon dioxide flowing from the bottom of the measurement container 1 flows to the upper part of the measurement container 1 via the piston part 7b, and the lid 4 It is discharged outside through the outflow part of the top of the head. Further, the opening of the sintered material is much smaller than the diameter of the spherical body 28, and the spherical body 28 does not inadvertently move and close the gap of the sintered material. Note that supercritical carbon dioxide can flow upward only from the clearance between the measurement container 1 and the piston portion 7b, but by using the sintered material, more preferable flow is possible.

  Further, as the piston 7 moves up, the neodymium magnet 12 attached to the upper end of the rod portion 7a moves upward as shown in FIG. 6, and accordingly, in the casing 19 made of transparent glass with a uniform scale. It is the same as that of the first embodiment in that it moves above the stored float 20.

  Then, the position of the float 20 in the casing 19 before the supercritical carbon dioxide flows into the measurement container 1 is detected in advance, and the piston 7 moves after the supercritical carbon dioxide flows into the measurement container 1. The amount, and thus the amount of movement of the float 20 accompanying the movement of the neodymium magnet 12 attached to the upper end of the rod portion 7a is read. Since the inner diameter of the cylindrical body of the measurement container 1 is known in advance, the volume of the solid sample 27 that is swollen and increased can be calculated by calculating the product of the amount of movement and the inner diameter of the measurement container 1. it can. Furthermore, the point that the volume expansion coefficient can be calculated from the volume value of the initial state of the solid sample 27 measured in advance before processing is the same as in the first embodiment.

  Also in the present embodiment, the solid sample 27 to be measured and the aggregate 28 as a fluid medium are accommodated in the measurement container 1, and supercritical carbon dioxide flows into the measurement container 1 to allow the supercritical dioxide to flow. The increase in the volume of the solid sample 27 in which carbon permeates and swells can be measured by detecting the movement amount of the piston by the neodymium magnet as described above.

  The neodymium magnet 12 is attached to the upper end portion of the rod portion 7a of the piston 7 even though the measurement vessel 1 is hermetically sealed and cannot be seen through the high-pressure vessel 13 from the outside. In addition, a transparent casing 19 is installed on the outer surface of the high-pressure vessel 13, and a neodymium float 20 is accommodated in the casing 19 so as to be able to move with the neodymium magnet 12. The point that the volume expansion coefficient of the sample 27 can be easily measured is the same as in the first embodiment.

(Embodiment 3)
This embodiment is still another embodiment of the measuring device for the volume expansion coefficient of the solid organic polymer material. FIG. 6 is a schematic cross-sectional view of an apparatus for measuring the volume expansion coefficient of the solid organic polymer material. The volume expansion coefficient measuring apparatus of the present embodiment has the same configuration as that of the measuring container 1 of the first embodiment, and the measuring apparatus is configured only by the measuring container 1, and a high-pressure container like that of the first embodiment is used. Not.

  That is, in this embodiment, a liquid such as oil is used as the fluid instead of the supercritical fluid as in Embodiment 1. And in this embodiment, the thing made from synthetic rubber used as packing, an O-ring, etc. is used as a measuring object.

  Moreover, in this embodiment, as shown in FIG. 7, the said measurement container 1 is installed in the thermostat 31 for accommodating liquids, such as oil.

  The configuration of the measurement container 1 is the same as that of the first embodiment as described above. As shown in FIG. 7, the precision cylindrical container body 2 and the upper lid for closing the opening 3 at the top of the container body 2 are used. A body 4, a bottom lid body 6 that closes the opening 5 at the bottom of the container body 2, and a piston 7 that can be moved up and down in the container body 2 are provided.

  The upper lid body 4 is composed of a cap nut, the bottom lid body 6 is composed of a cap nut 6a, and an interposer 9 is interposed between the cap nut 6a and the outer peripheral surface of the container main body 2, The mesh 10 is interposed between the bottom of the body 9 and the cap nut 6a, and the hole 11 is formed in the bottom of the cap nut 6a.

  The point that the piston 7 is composed of the rod portion 7a and the piston portion 7b is the same as that of the first embodiment. However, in the first embodiment, the rod portion 7a is graduated, and the graduated fluid allows the fluid to flow. It is comprised so that the dimension which piston 7 raised by the inflow into the container main body 2 can be detected. Therefore, in this embodiment, the neodymium magnet 12 like Embodiments 1 and 2 is not attached to the rod part 7a, and is different from Embodiment 1 in that respect.

  In this embodiment, as shown in FIG. 6, oil 32 is accommodated in the thermostat 31, and the measurement container 1 constituting the measuring device 22 is accommodated in the thermostat 31 and immersed in the oil 32. It is in a state.

  The oil 32 in the thermostat 31 flows into the measurement container 1 through the mesh 10 from the hole 11 at the bottom of the measurement container 1. When the oil 32 that has flowed into the measurement container 1 comes into contact with the solid sample 27 made of synthetic rubber through the gaps between the spherical bodies 28 that form an aggregate composed of a large number of spherical bodies 28, Oil 32 penetrates. Therefore, the solid sample 27 made of synthetic rubber swells and increases in volume.

  When the solid sample 27 swells and its volume increases in this way, an aggregate composed of a large number of spherical bodies 28 flows as the volume of the solid sample 27 increases, and as a result, as shown in FIG. A thing pushes up the piston part 7b of the lower part of the piston 7 only for the volume expansion of the solid sample 27, and thereby the piston 7 rises. The oil 32 flows upward from the clearance between the measurement container 1 and the piston portion 7 b, and the air existing in the space above the piston portion 7 b is the clearance between the piston 7 and the upper lid body 4. And released from the vent hole 8 into the atmosphere. As a result, it becomes the same height as the interface of the oil 32 accommodated in the thermostat 31. In addition, by applying the sintered body used in the second embodiment to the piston portion 7b, the measurement container 1 can be more preferably filled with a fluid having a high viscosity such as oil.

  Then, after the oil 32 flows into the measurement container 1, the position of the scale of the rod portion 7a of the piston 7 in the vicinity of the upper lid 4 before the oil 32 flows into the measurement container 1 is detected in advance. The amount of movement of the piston 7 is read. Since the inner diameter of the cylindrical body of the measurement container 1 is known in advance, the volume of the solid sample 27 that is swollen and increased can be calculated by calculating the product of the amount of movement and the inner diameter of the measurement container 1. it can. Furthermore, the volume expansion coefficient can be calculated from the value of the initial volume of the solid sample 27 measured in advance before processing.

  As described above, also in this embodiment, the solid sample 27 to be measured and the aggregate made up of a large number of spherical bodies 28 as a fluid medium are accommodated in the measurement container 1, and the oil 32 is contained in the measurement container 1. The increase in the volume of the solid sample 27 in which the oil 32 permeates and swells by being introduced can be measured by detecting the movement amount of the piston as described above.

  In this case, since the stainless steel measurement container 1 is hermetically sealed and cannot be seen through from the outside, the rising distance of the piston 7 cannot be directly detected from the outside. Since the scale is attached to the part 7a, the volume expansion coefficient of the swollen solid sample 27 can be easily measured by reading the position of the scale even if the inside of the measurement container 1 cannot be directly visualized. is there.

  Examples of the present invention will be described below.

(Example)
In this example, the apparatus related to the first embodiment was used. As a main part, a SUS316 short tube having an outer diameter of 1 inch, an inner diameter of 19.4 mm, and a height of 175 mm was used as the main body of the measurement container. As the spherical body, BZ-2 type glass beads having an outer diameter of 2.0 mm manufactured by As One Co., Ltd. were used. A spherical neodymium magnet having a diameter of 1 mm was used as the float. As a high-pressure vessel, a microreactor MMJ-500 pressure vessel manufactured by OM Labotech was used.

  Using this apparatus, isoprene rubber was charged as a solid sample, carbon dioxide was circulated under conditions of a temperature of 50 ° C., a pressure of 20 MPa, and a treatment time of 4 hours, and carbon dioxide was brought into contact with the isoprene rubber. As a result of the experiment, it was possible to detect the rise of the float and measure the volume expansion of isoprene rubber.

Claims (10)

  A measurement container (a fluid, a solid sample (27) made of a solid organic polymer material having a property of swelling by the fluid, and a fluid medium flowing in the fluid as the solid sample (27) swells) 1), a piston (7) provided in the measurement container (1) so as to be movable up and down as the solid sample (27) swells and a fluid medium flows in the fluid, and the solid sample ( 27) A device for measuring the volume expansion coefficient of a solid organic polymer material, comprising a detecting means for detecting the distance that the piston (7) has moved up, in order to measure the volume expansion coefficient of 27).   The detection means for detecting the distance the piston (7) has moved up causes a part of the piston (7) to be bare outside the measurement container (1), and the measurement container (1) together with the bare piston (7). In a separate high-pressure vessel (13), a permanent magnet (12) is attached to the tip of the piston (7), and the piston (7) is attached to the tip of the piston (7). A float (20) attracted by the permanent magnet (12) is provided on the outer peripheral surface of the high-pressure vessel (13) so that it can roll on the outer peripheral surface side of the corresponding high-pressure vessel (13), and the float (20) The apparatus for measuring a volume expansion coefficient of a solid organic polymer material according to claim 1, which is a means for detecting the distance by which the piston (7) is lifted by the moving distance of the solid organic polymer material.   The detection means for detecting the distance the piston (7) has moved up attaches the permanent magnet (12) to the tip of the piston (7), and the tip of the piston (7) to which the permanent magnet (12) is attached. A float (20) attracted by the permanent magnet (12) is provided on the outer peripheral surface of the measurement container (1) so that it can roll on the outer peripheral surface side of the measurement container (1) corresponding to the position. The apparatus for measuring the volume expansion coefficient of a solid organic polymer material according to claim 1, which is a means for detecting the distance by which the piston (7) is lifted by the moving distance of 20).   The detection means for detecting the distance the piston (7) has moved up causes a part of the piston (7) to be bare outside the measurement container (1), and a scale is provided on the tip side of the piston (7), The apparatus for measuring the volume expansion coefficient of a solid organic polymer material according to claim 1, which is means for detecting the distance by which the piston (7) has risen by the scale of the piston (7) rising outside the measurement container (1).   The apparatus for measuring the volume expansion coefficient of a solid organic polymer material according to any one of claims 1 to 4, wherein the fluid medium comprises an aggregate of a large number of spherical bodies (28) having a surface excellent in slidability.   In the measurement container (1) that can contain the fluid, the solid sample (27) made of the solid organic polymer material having the property of being swollen by the fluid is housed, and the solid sample (27) is swollen so as to swell. The measurement is performed on the piston (7) that is filled with the fluid medium flowing in the fluid into the measurement container (1) and can be moved up and down as the solid sample (27) swells and the fluid medium flows. Provided in the container (1), the fluid flows into the measurement container (1) to swell the solid sample (27) and raise the piston (7) by flowing the fluid medium in the fluid. The volume of the solid sample (27) is measured by detecting the distance by which the piston (7) is raised by the detecting means for detecting the distance by which the piston (7) is raised. molecule Method of measuring the volume expansion rate of the fee.   The detection means for detecting the distance the piston (7) has moved up causes a part of the piston (7) to be bare outside the measurement container (1), and the measurement container (1) together with the bare piston (7). In a separate high-pressure vessel (13), a permanent magnet (12) is attached to the tip of the piston (7), and the piston (7) is attached to the tip of the piston (7). A float (20) attracted by the permanent magnet (12) is provided on the outer peripheral surface of the high-pressure vessel (13) so that it can roll on the outer peripheral surface side of the corresponding high-pressure vessel (13), and the float (20) The method for measuring the volume expansion coefficient of a solid organic polymer material according to claim 6, which is a means for detecting the distance by which the piston (7) is lifted by the moving distance of the solid organic polymer material.   The detecting means for detecting the distance the piston (7) is lifted attaches a neodymium magnet (12) to the tip of the piston (7), and the tip of the piston (7) to which the neodymium magnet (12) is attached. A float (20) attracted by the permanent magnet (12) is provided on the outer peripheral surface of the measurement container (1) so that it can roll on the outer peripheral surface side of the measurement container (1) corresponding to the position. The method for measuring the volume expansion coefficient of a solid organic polymer material according to claim 6, which is a means for detecting the distance by which the piston (7) is lifted by the movement distance of 20).   The detection means for detecting the distance the piston (7) has moved up causes a part of the piston (7) to be bare outside the measurement container (1), and a scale is provided on the tip side of the piston (7), The method for measuring the volume expansion coefficient of a solid organic polymer material according to claim 6, which is means for detecting the distance by which the piston (7) has risen by the scale of the piston (7) rising outside the measurement container (1).   The method for measuring the volume expansion coefficient of a solid organic polymer material according to any one of claims 6 to 9, wherein the expansion and flow medium comprises an aggregate of a large number of spherical bodies (28) having a surface excellent in slidability.

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