JP3822604B2 - Heat treatment equipment - Google Patents

Description

  The present invention relates to a heat treatment apparatus that realizes a large temperature rise or fall temperature change in a short time.

  Observation of behavior near the melting point is extremely important in crystal structure analysis of polymer compounds and organic compounds, or in the initial crystallization process and amorphous structure research. For example, the melting process with increasing temperature greatly varies depending on the polymorphism of the crystal structure or the melting from the glass state. Conversely, the temperature lowering process from the molten state is directly reflected in the degree of supercooling for crystallization, and the glass state is realized and fixed by rapid cooling from the molten state.

  In this way, by changing the temperature in the vicinity of the melting point in various ways along with the time development of the process, various crystal structures or physical properties can be expressed and a deeper structure can be understood. In other words, it is important to change the temperature condition “from time to time” and “within how long”, and it is necessary to perform the experiment in an environment corresponding to that.

  Conventionally, a flow cell type apparatus or a chamber type apparatus is known as a heat treatment apparatus provided in a structural analysis apparatus using X-rays or the like. In the former, a sample is fixed on a cell that can transmit incident light, and the temperature of the cell is increased by heating with a heater, and at the same time, the temperature is controlled by antagonizing both of them (for example, , See Patent Document 1). In the latter, a chamber with a constant temperature is prepared in advance, and the temperature change of the cell is achieved by moving a sample prepared in another position as quickly as possible into the chamber.

  Moreover, thin film samples or bulk samples are often handled in ordinary polymer sample temperature jump methods, but from the viewpoint of crystal growth, for example, temperature jump processing (rapid heating or rapid cooling) of solution samples is also an interesting theme. . However, there are not many examples of in-situ observation in such an environment. One of the reasons is that it is difficult to control the temperature of the cell containing the sample, or that the cell must be airtight against bumping of the solvent while the surroundings must be vacuum degassed. It is. However, if the strength and tightness of the sample cell are sufficiently increased, it is possible to rapidly heat or cool dilute solutions and perform in situ observation by diffraction or optical methods. Not yet started. As such a theme, for example, a study of high-speed time-sharing observation of single crystal growth from a polymer dilute solution can be considered.

  Research on these themes can improve the accuracy of optical measurements and scattering experiments, and heat treatment equipment using cells with improved airtightness, temperature measurement performance of the sample itself, heat capacity design, that is, temperature tracking capability. It has been demanded.

On the other hand, in recent years, it has become relatively easy to use a high-intensity radiation source by using synchrotron radiation such as Spring-8, and within a short time such as several tens of msec as long as the temperature change condition can be achieved. There is a need for a heat treatment apparatus capable of tracking changes over time and capable of temperature control by rapid heating or rapid cooling.
JP 07-286945 A

  However, since the flow cell type heat treatment apparatus controls the temperature by the balance between the heat removal by the refrigerant and the heating by the heater, depending on the cell, overshoot (over temperature change) occurs in both the temperature rising and cooling processes, If a temperature change for a short time is intended, the control tends to become unstable. A flow cell type apparatus includes a control device and a program that suppress overshoot to some extent, but a dedicated cell for that purpose must be used, and as a result, the sample size is limited. In addition, in the flow cell type apparatus, the temperature of the stage for fixing the sample is actually controlled, which is suitable for the thin film sample from the viewpoint of heat conduction, but the temperature control of the thick bulk sample itself is insufficient. It is. In addition, it is difficult to introduce the sample exchanger into the flow cell type apparatus from the mechanism.

  On the other hand, a chamber-type heat treatment apparatus can realize a temperature change within a short time or with a large change width, but after a sample is moved into a heated chamber, a temporal change in structure is measured. Therefore, in many cases, only one of temperature rise and temperature fall is supported. In addition, there is no sample at the radiation irradiation position at the start of measurement, and since the sample interrupts the irradiation position from a certain time zone, it cannot be measured during the movement time of the sample, and changes within a short time are tracked. Can be difficult. In addition, due to the mechanism of moving the sample, it is difficult to measure the temperature of the sample and to precisely control the temperature.

  An object of this invention is to provide the heat processing apparatus which implement | achieves the temperature change of a large width | variety temperature rise or temperature fall in a short time about the to-be-processed object fixed to the specific position.

  (1) In order to achieve the above object, a heat treatment apparatus according to the present invention is supported by a holding unit that holds an object to be heated or cooled at an installation position and on both sides of the installation position. First and second swing members provided so as to be swingable, first and second heat baths provided at both ends of the first swing member, and the second swing A third heat bath and a fourth heat bath provided at both ends of the member; and first temperature control means for controlling the temperatures of the first to fourth heat baths, respectively, When the second swing member is swung in the first direction, the first heat bath and the third heat bath abut each other with the object to be heat-treated at the temperature control position, When the first and second swing members are swung in the second direction, the second heat bath and the fourth heat bath are located at the installation position. Across the object to be heat-treated is characterized by abutting one another.

  As described above, in the heat treatment apparatus of the present invention, the swinging member swings so that the heat baths are brought into contact with each other from the upper and lower sides and are brought into close contact with the holding portion. Thus, for example, the first and third heat baths are kept at the same low temperature, the second and fourth heat baths are kept at the same high temperature, and the heat baths are alternately brought into contact with each other. In the case where the heat baths are in contact with each other, it is spatially uniform over the entire heat-treated object, but the heat-treated object having a uniform structure that has undergone a temperature history accompanied by a rapid temperature change. Obtainable. As a result, it is possible to change the temperature of the heat treatment object with a large change width with respect to time in a state where the heat treatment object is fixed. In addition, the heat treatment apparatus of the present invention can equally handle both the temperature rising and temperature lowering processes, and can rapidly and rapidly repeat the rapid cooling and rapid heating.

  In addition, since the object to be heat-treated is fixed at the installation position during temperature control, it is easy to directly measure the temperature of the object to be actually heat-controlled by heat radiation, thermocouple, etc. Become. As a result, physical property experiments can be performed while rapidly changing the sample temperature. For example, in the case of performing structural analysis by radiation irradiation, the structure can be analyzed while applying radiation to the same position of the object to be heat-treated and changing the temperature of the object to be heat-treated abruptly. Therefore, various behaviors in the vicinity of the melting point can be observed in the crystal structure analysis of polymer compounds and organic compounds, or in the study of the initial crystallization process and the amorphous structure. As a result, various crystal structures and physical properties can be expressed and the structure of the object to be heat treated can be understood more deeply by changing the temperature in the vicinity of the melting point in combination with the time development of the process.

  Further, since the structure as described above is adopted, it is possible to control the temperature of the bulk-shaped heat-treated object having a thickness, and the restriction on the size of the heat-treated object can be relaxed as compared with the conventional apparatus. . As a result, the irradiation volume of a large amount of radiation can be secured in the object to be heat-treated, so that the accuracy of optical measurement and scattering experiments can be increased.

  In addition, the temperature of the object to be heat-treated is held at a fixed position, and the temperature is controlled by bringing the heat baths into contact with each other. Performance can be easily pursued. Further, for example, a vacuum can be created around the cell, and the radiation slit, the cell of the heat treatment apparatus of the present invention, and the detector of the scattering intensity can be housed in an integrated vacuum chamber. As a result, it is possible to suppress air scattering that causes background in a radiation diffraction experiment.

  Further, it is suitable for in-situ observation by a diffraction method or an optical method under conditions of rapid heating or rapid cooling of a dilute solution, and it is possible to study such unseen scientific fields.

  (2) Further, the heat treatment apparatus according to the present invention is characterized in that the first temperature control means controls the temperatures of the first to fourth heat baths independently.

  Thereby, the temperature of the first to fourth heat baths can be set independently. As a result, a spatial temperature gradient can be applied to the object to be heat-treated in the cell while performing rapid heating or rapid cooling. With respect to the object to be heat-treated, it is possible to perform temperature control that simultaneously realizes a rapid temperature change and a spatial temperature gradient.

  For example, the temperature of the first, second and third heat baths is maintained at the melting point temperature, and the temperature of the fourth heat bath is maintained at a temperature sufficiently lower than the melting point temperature. After the two heat baths are brought into contact with each other, the second and fourth heat baths are brought into contact with each other, so that the object to be heat-treated in the cell is melted from the state where the whole is melted. The lower half can be rapidly changed to the crystallization temperature. Alternatively, the temperature of the first and third heat baths is the melting point temperature, the temperature of the second heat bath is slightly lower than the melting point temperature, and the temperature of the fourth heat bath is sufficiently lower than the melting point temperature. If the same process is carried out, half of the material to be heat-treated in the cell is rapidly cooled and crystallized, but half can be subjected to the condition of slow cooling and crystallization, and it is possible to create a temperature gradient in the cell. Become. As a result, such a temperature gradient in the cell allows organic materials or polymer materials to grow in a certain direction, or to give a concentration gradient to the cross-linking density of the gel. Can be adjusted.

  (3) Further, the heat treatment apparatus according to the present invention is characterized in that each of the swinging members is arranged so that the axis of each of the swinging members is point-symmetric with respect to the installation position.

  Thereby, the structure of the heat treatment apparatus can be simplified most. As a result, the apparatus can be made compact, and the space required for the heat treatment apparatus can be minimized. Further, the apparatus can be configured by manufacturing a plurality of swing members and heat baths having the same shape, and the labor and cost of manufacturing the apparatus can be reduced.

  (4) Moreover, the heat processing apparatus which concerns on this invention has several said holding | maintenance parts, It is further provided with the supply part which supplies any one holding | maintenance part to the said installation position.

  Thereby, the trouble of exchanging a plurality of heat treatment objects can be saved, and the plurality of heat treatment objects can be processed at a time. It can also be used for industrial line processes.

  (5) Moreover, the heat processing apparatus which concerns on this invention is further provided with the 2nd temperature control means which controls the temperature of the said holding | maintenance part or the said to-be-processed object independently.

  As a result, the second temperature control means can be used supplementarily, and the temperature of the object to be heat-treated can be changed with a large change width with respect to time.

  According to the heat treatment apparatus according to the present invention, for example, the first and third heat baths are kept at the same low temperature, and the second and fourth heat baths are kept at the same high temperature. When the heat baths are alternately abutted, the heat baths are in contact with each other, and even though they are spatially uniform over the entire object to be heat treated, they are uniformly subjected to a temperature history with sudden temperature changes. An object to be heat-treated having a simple structure can be obtained. As a result, it is possible to change the temperature of the heat treatment object with a large change width with respect to time in a state where the heat treatment object is fixed. In addition, the heat treatment apparatus of the present invention can equally handle both the temperature rising and temperature lowering processes, and can rapidly and rapidly repeat the rapid cooling and rapid heating.

  In addition, since the object to be heat-treated is fixed at the installation position during temperature control, it is easy to directly measure the temperature of the object to be actually heat-controlled by heat radiation, thermocouple, etc. Become. As a result, physical property experiments can be performed while rapidly changing the sample temperature. For example, in the case of performing structural analysis by radiation irradiation, the structure can be analyzed while applying radiation to the same position of the object to be heat-treated and changing the temperature of the object to be heat-treated abruptly. Therefore, various behaviors in the vicinity of the melting point can be observed in the crystal structure analysis of polymer compounds and organic compounds, or in the study of the initial crystallization process and the amorphous structure. As a result, various crystal structures and physical properties can be expressed and the structure of the object to be heat treated can be understood more deeply by changing the temperature in the vicinity of the melting point in combination with the time development of the process.

  Further, since the structure as described above is adopted, it is possible to control the temperature of the bulk-shaped heat-treated object having a thickness, and the restriction on the size of the heat-treated object can be relaxed as compared with the conventional apparatus. . As a result, the irradiation volume of a large amount of radiation can be secured in the object to be heat-treated, so that the accuracy of optical measurement and scattering experiments can be increased.

  In addition, the temperature of the object to be heat-treated is held at a fixed position, and the temperature is controlled by bringing the heat baths into contact with each other. Performance can be easily pursued. Further, for example, a vacuum can be created around the cell, and the radiation slit, the cell of the heat treatment apparatus of the present invention, and the detector of the scattering intensity can be housed in an integrated vacuum chamber. As a result, it is possible to suppress air scattering that causes background in a radiation diffraction experiment.

  Further, it is suitable for in-situ observation by a diffraction method or an optical method under conditions of rapid heating or rapid cooling of a dilute solution, and it is possible to study such unseen scientific fields.

  Further, according to the heat treatment apparatus of the present invention, the temperatures of the first to fourth heat baths can be set independently. As a result, a spatial temperature gradient can be applied to the object to be heat-treated in the cell while performing rapid heating or rapid cooling. With respect to the object to be heat-treated, it is possible to perform temperature control that simultaneously realizes a rapid temperature change and a spatial temperature gradient.

  For example, the temperature of the first, second and third heat baths is maintained at the melting point temperature, and the temperature of the fourth heat bath is maintained at a temperature sufficiently lower than the melting point temperature. After the two heat baths are brought into contact with each other, the second and fourth heat baths are brought into contact with each other, so that the object to be heat-treated in the cell is melted from the state where the whole is melted. The lower half can be rapidly changed to the crystallization temperature. Alternatively, the temperature of the first and third heat baths is the melting point temperature, the temperature of the second heat bath is slightly lower than the melting point temperature, and the temperature of the fourth heat bath is sufficiently lower than the melting point temperature. If the same process is carried out, half of the material to be heat-treated in the cell is rapidly cooled and crystallized, but half can be subjected to the condition of slow cooling and crystallization, and it is possible to create a temperature gradient in the cell. Become. As a result, such a temperature gradient in the cell allows organic materials or polymer materials to grow in a certain direction, or to give a concentration gradient to the cross-linking density of the gel. Can be adjusted.

  Further, according to the heat treatment apparatus of the present invention, the structure of the heat treatment apparatus can be simplified most. As a result, the apparatus can be made compact, and the space required for the heat treatment apparatus can be minimized. Further, the apparatus can be configured by manufacturing a plurality of swing members and heat baths having the same shape, and the labor and cost of manufacturing the apparatus can be reduced.

  In addition, according to the heat treatment apparatus of the present invention, it is possible to save the trouble of exchanging a plurality of heat-treated objects, and it is possible to process a plurality of heat-treated objects at a time. It can also be used for industrial line processes.

  Further, according to the heat treatment apparatus of the present invention, the temperature of the object to be heat treated can be changed with a large change width with respect to time by using the second temperature control means as an auxiliary.

  When the heat treatment apparatus according to the present invention is replaced with a conventional chamber heat treatment apparatus, the heat treatment apparatus is based on the idea that the chamber is moved instead of the sample portion and both the temperature rise and the temperature fall are dealt with. The essence of the heat treatment apparatus according to the present invention is that two temperature conditions are achieved as rapid cooling or rapid heating by contacting a hot or cold heat bath without moving the object to be heat treated. The best mode for carrying out the present invention will be described below with reference to the drawings.

[Embodiment 1]
(Constitution)
FIG. 1 is a perspective view of a heat treatment apparatus 1a according to the first embodiment. The heat treatment apparatus 1a includes a holding portion 2a, shafts 3a and 3c, swing members 4a and 4c, and heat baths 5a to 5d. The holding part 2a includes a cell 11a and a holding column 12a. The cell 11a is made of metal and has a cylindrical shape. The shape is not limited to a cylindrical shape, and may be a rectangular parallelepiped, an elliptic cylinder, an ellipsoid, or the like, and is preferably a shape that can easily come into contact with a heat bath. The material may be other than copper as long as the material has a small heat capacity and a high thermal conductivity. The cell 11a has a space for accommodating a sample as an object to be heat treated, and the space can be opened and closed by a lid. The cell 11a is provided with a radiation transmitting hole 13a so as not to block the radiation incident on the sample and the scattered radiation scattered by the sample when radiation is applied for the structural analysis of the sample. In FIG. 1, the radiation is irradiated from the back side of the paper toward the front side in parallel with the central axis of the shafts 3a and 3c. FIG. 2 is a plan view of the holding portion 2a according to the first embodiment when viewed from a direction perpendicular to the central axes of the shafts 3a and 3c. As shown in FIG. 2, the cell 11a is fixed at a fixed position by a holding column 12a fixed to the wall. Therefore, the sample accommodated in the cell 11a is also held at a certain position. The center position of this sample is the installation position. The holding strut 12a is preferably made of a material having low thermal conductivity such as ceramics or resin. A thermocouple (not shown) is inserted into the cell 11a so that the temperature of the sample itself can be measured. Instead of a thermocouple, a sensor may be inserted to measure the temperature of the sample by thermal radiation.

  The two shafts 3a and 3c are connected to the motor via a pulley (not shown) provided on the wall side, and are provided so as to extend in a direction perpendicular to the wall with the installation position interposed therebetween. Further, the positions of the central axes of the two shafts 3a and 3c are set so as to be point-symmetric with respect to the installation position, that is, the center position of the sample in the projection onto the rocking surface of the rocking member. . Thereby, the structure of the heat processing apparatus 1a can be simplified most. As a result, the apparatus can be made compact and the space required for the heat treatment apparatus 1a can be minimized. Further, the apparatus can be configured by manufacturing a plurality of swing members and heat baths having the same shape, and the labor and cost of manufacturing the apparatus can be reduced.

  The shaft 3a is provided with a first swinging member 4a that can swing around its central axis, and the shaft 3c is provided with a second swinging member 4c that can swing around its central axis. It has been. The swinging members 4a and 4c have a plate shape and are the same shape as each other. The shafts 3a and 3c are made of copper, but are preferably made of a material having thermal conductivity. The motor mechanically connected to the shafts 3a and 3c is provided so that it can be remotely operated by a switch or the like. It is good also as controlling a motor by a program on the control board electrically connected to the motor. By this. When used in a hatch of a synchrotron radiation facility, the temperature of the sample can be safely controlled by remote control. The shafts 3a and 3c are mechanically connected via a pulley or the like so that the swinging members 4a and 4c swing in synchronization. Note that the first and second swinging members 4a and 4c may be configured to swing in synchronism by electrical control.

  FIG. 3 is a side view of the first swing member 4a and the first heat bath 5a when viewed from one end of the first swing member 4a in the length direction of the swing member 4a. At one end of the first swing member 4a, a first heat bath 5a is fixed to the first swing member 4a by a fixing plate 21a and a bolt 22a. The 1st heat bath 5a is provided with the hole by which the thread groove fitted to the volt | bolt 22a was cut. Similarly, a third heat bath 5c is fixed to the second swing member 4c at one end of the second swing member 4c by a fixing plate 21c and a bolt 22c. The third heat bath 5c is provided with a hole having a thread groove that fits into the bolt 22c.

  Further, the heat baths 5a and 5c are designed to collide with each other with the sample interposed when the swinging members 4a and 4c are swung in the direction A shown in FIG. Collision means that the portions of the heat bath that conduct the heat to the sample meet each other with the sample interposed therebetween. In this case, the A direction shown in FIG. 1 is the first direction. The position of the center of the sample when the heat baths collide is called the installation position. The swing members 4a and 4c are made of metal, but the material is not particularly limited as long as it has good thermal conductivity.

  On the other hand, the second heat bath 5b is similarly fixed to the first swing member 4a at the other end of the first swing member 4a by a fixing plate 21b and a bolt 22b. The second heat bath 5b is provided with a hole in which a thread groove is fitted to the bolt 22b. The fourth heat bath 5d is fixed to the second swing member 4c at the other end of the second swing member 4c by a fixing plate 21d and a bolt 22d. The fourth heat bath 5d is provided with a hole in which a thread groove is fitted to the bolt 22d.

  The heat treatment apparatus 1a is provided with a hot wire heater and a control board, a copper cooling pipe, and a thermocouple (not shown) as first temperature control means. Each of the four hot wire heaters and the thermocouple is provided so as to be in contact with the heat baths 5a to 5d, respectively, and the output of each heat wire heater is adjusted so that each heat bath can be maintained independently at a set temperature. And electrically connected to a control board having a CPU. On the other hand, the cooling pipe is provided so as to penetrate through the shafts 3a and 3c, and a coolant such as water is allowed to flow therethrough.

  Thereby, the temperature of the heat baths 5a to 5d can be independently set and controlled. As a result, it is possible to give a spatial temperature gradient to the object to be heat-treated in the cell while performing rapid heating or rapid cooling. With respect to the object to be heat-treated, it is possible to perform temperature control that simultaneously realizes a rapid temperature change and a spatial temperature gradient.

  The first temperature control means has a function of keeping the temperature of each heat bath constant, and is not particularly limited to the above specific example. For example, instead of a thermocouple, a sensor may be inserted to measure the temperature of the sample by thermal radiation. Moreover, it is good also as a structure which provides a heater so that it may become symmetrical only about one set of the heat baths 5a and 5c, and always performs the same output about the heater. In this case, the temperature is not controlled independently for each heat bath, and the temperature change is given only between two temperatures of high temperature and low temperature by reciprocating the swing member. That is, only a spatially uniform temperature change can be given to the object to be heat treated. In this case, there is an advantage that the structure is simple and the device can be manufactured easily.

  Further, the heat baths 5b and 5d are designed so that the respective rocking members 4a and 4c are brought into contact with each other with the sample sandwiched at the above installation position when the rocking members 4a and 4c are swung in the B direction shown in FIG. Yes. In this case, the B direction shown in FIG. 1 is the second direction. The heat baths 5a to 5d are each provided with an electromagnetic holder mechanism (not shown) in order to fix the heat baths 5a and 5c or the heat baths 5b and 5d in contact with each other. The electromagnetic holder has an electrical configuration that releases the fixation in conjunction with the motor when separating the heat baths fixed in contact with each other. In this way, the heat baths 5a and 5c are kept at a high temperature, the heat baths 5b and 5d are kept at a low temperature, and a semicircular orbit of approximately 180 ° is drawn and reciprocated. To achieve.

  In this way, the heat treatment apparatus 1a causes the heat baths to abut from above and below to closely contact the holding part 2a as the swinging members 4a and 4c swing. Thus, for example, the heat baths 5a and 5c are kept at the same low temperature, the heat baths 5b and 5d are kept at the same high temperature, and the heat baths 5a and 5c or the heat baths 5b and 5b When 5d is brought into contact with each other, in the state where the heat baths are in contact with each other, the object to be heat-treated has undergone a temperature history accompanied by a rapid temperature change, although spatially uniform over the whole object to be heat-treated. Can be obtained. As a result, it is possible to change the temperature of the heat treatment object with a large change width with respect to time in a state where the heat treatment object is fixed. Moreover, the heat processing apparatus 1a can respond | correspond equally to both temperature rising and temperature falling processes, and can repeat rapid cooling and rapid heating continuously.

  In addition, since the object to be heat-treated is fixed at the installation position during temperature control, it is easy to directly measure the temperature of the object to be actually heat-controlled by heat radiation, thermocouple, etc. Become. As a result, physical property experiments can be performed while rapidly changing the sample temperature. For example, in the case of performing structural analysis by radiation irradiation, the structure can be analyzed while applying radiation to the same position of the object to be heat-treated and changing the temperature of the object to be heat-treated abruptly. Therefore, various behaviors in the vicinity of the melting point can be observed in the crystal structure analysis of polymer compounds and organic compounds, or in the study of the initial crystallization process and the amorphous structure. As a result, various crystal structures and physical properties can be expressed and the structure of the object to be heat treated can be understood more deeply by changing the temperature in the vicinity of the melting point in combination with the time development of the process.

  Further, since the structure as described above is adopted, it is possible to control the temperature of the bulk-shaped heat-treated object having a thickness, and the restriction on the size of the heat-treated object can be relaxed as compared with the conventional apparatus. . As a result, the irradiation volume of a large amount of radiation can be secured in the object to be heat-treated, so that the accuracy of optical measurement and scattering experiments can be increased.

  In addition, the temperature of the object to be heat-treated is held at a fixed position, and the temperature is controlled by bringing the heat baths into contact with each other. Performance can be easily pursued. Further, for example, a vacuum can be created around the cell, and the radiation slit, the cell of the heat treatment apparatus, and the detector of the scattering intensity can be housed in an integrated vacuum chamber. As a result, it is possible to suppress air scattering that causes background in a radiation diffraction experiment.

  Further, it is suitable for in-situ observation by a diffraction method or an optical method under conditions of rapid heating or rapid cooling of a dilute solution, and it is possible to study such unseen scientific fields.

  As described above, the heat baths 5a to 5d have a semi-cylindrical shape and are fixed by the fixing plates 21a to 21d and the bolts 22a to 22d, so that the contact area with the swinging members 4a and 4c is small. Thereby, the influence of the expansion / contraction by thermal expansion can be suppressed.

  FIG. 4 is a perspective view of the heat bath 5a. As shown in FIG. 4, the abutting surface of the heat bath 5a has a cell groove 31a having substantially the same shape as the cylindrical shape of the cell 11a. The cell groove 31a is processed into a shape that is in close contact with the outer surface of the cell 11a when the heat baths abut each other across the cell 11a. When the heat baths collide with each other, the side surfaces of the cells 11a are in close contact with the cell grooves of the respective heat baths. Thereby, heat conduction occurs between the cell and the heat bath, and the cell can be rapidly heated or cooled. A small amount of heat conductive grease is applied to the cell groove 31a. Further, at the end in the direction parallel to the shaft 3a, a semi-cylindrical concave portion 32a for incident line is provided along the incident direction of the radiation represented by the arrow C, and the scattered radiation from the sample is also provided. A semi-conical scattered ray recess 33a is provided so as not to block the light. The heat baths 5b to 5d have the same shape. The shape of the recess is not particularly limited as long as it does not block radiation. As a result, the object to be heat-treated is irradiated with the radiation from the recessed portions of the heated baths 5a and 5c or 5b and 5d, and the temperature of the object to be heat-treated is changed with a large change width or a large gradient with respect to time. The heat-treated product can be observed in situ.

  In the first embodiment, the cell 11a and the cell groove 31a are cylindrical, but the shape is not particularly limited. However, if the cell 11a and the cell groove 31a are cylindrical, the cell 11a and the cell groove 31a can be easily processed. In addition, although the heat baths 5a to 5d are made of copper, the material is not particularly limited as long as the heat conductivity is good.

(Operation)
Next, the operation of the heat treatment apparatus 1a according to the embodiment configured as described above will be described. For example, a case will be described in which an operation for in-situ observation of a rapidly heating and rapidly cooling sample with radiation is performed. First, the heat baths 5a and 5c are previously held at the same and constant high temperature by the first temperature control means. For example, the temperature is set to 200 ° C or the like. Further, the heat baths 5b and 5c are kept at the same and constant low temperature. For example, the room temperature is set to 20 ° C. Next, the sample is accommodated in the holding part 2a.

  Thereby, in a state where the heat baths are in contact with each other, the temperature is made uniform over the entire sample, so that a heat-treated object having a uniform structure having a spatially uniform temperature history can be obtained. In addition, the structure of the sample at a uniform temperature can be observed.

  Next, the heat baths 5b and 5d are brought into contact with each other with the cell 11a interposed therebetween, and the sample is kept at 20 ° C. Irradiate the sample with radiation and start detecting scattered radiation. Next, the swinging members 4a and 4c are swung, and the heat baths 5a and 5c are brought into contact with each other with the cell 11a interposed therebetween. FIG. 5 is a side view of the heat treatment apparatus 1a according to Embodiment 1 as viewed in the axial direction of the shaft. FIG. 5A shows a state where the heat bath of the heat treatment apparatus 1a does not collide, and FIG. 5B shows a state where the heat bath of the heat treatment apparatus 1a collides. As shown in FIG. 5, the heat bath is abutted by swinging the swing member. At this time, the sample is rapidly heated to 200 ° C. At the same time, the scattered radiation is detected and the structure of the sample is analyzed. When the temperature of the sample reaches 200 ° C and becomes constant and sufficiently detects scattered radiation, the rocking members 4a and 4c are rocked in the opposite direction to the above, and the heat baths 5b and 5d are brought into contact with each other with the cell 11a interposed therebetween. . While rapidly cooling the sample to 20 ° C., the scattered radiation is detected and the structure of the sample is analyzed.

  In the above process, the temperature of the heat bath 5a is maintained at substantially the same temperature as the temperature of the heat bath 5c, and the temperature of the heat bath 5b is maintained at substantially the same temperature as the temperature of the heat bath 5d. Heat baths that collide with each other are held at the same temperature, but one of the two heat baths that collide with each other is held at a temperature different from that of the other heat bath. It may be.

  For example, after the temperature of the heat baths 5a, 5b and 5c is maintained at the melting point temperature and the temperature of the heat bath 5d is maintained at a temperature sufficiently lower than the melting point temperature, the heat baths 5a and 5c are first brought into contact with each other. By performing the process of abutting the heat baths 5b and 5d, the sample in the cell is rapidly changed from a state where the whole is melted to a state where the upper half is close to melting but the lower half is at the crystallization temperature. Can be changed. Alternatively, the temperature of the heat baths 5a and 5c is maintained at the melting point temperature, the temperature of the heat bath 5b is maintained at a temperature slightly lower than the melting point temperature, and the temperature of the heat bath 5d is maintained at a temperature sufficiently lower than the melting point temperature. Then, half of the sample in the cell is rapidly cooled and crystallized, but half can be brought into the condition of slow cooling crystallization, and a temperature gradient can be provided in the cell. As a result, such a temperature gradient in the cell can cause organic substances or polymer materials to grow in a certain direction or give a concentration gradient to the cross-linking density of the gel, thus having a gradient structure. The material can be adjusted.

  In addition, when using the heat processing apparatus 1a for such a process, it is preferable to use a cell material having a relatively large heat capacity and a low thermal conductivity.

  The inventor produced the heat treatment apparatus 1a according to the first embodiment and tested it. Hereinafter, examples of the heat treatment apparatus 1a according to Embodiment 1 will be described.

  First, the temperature of the heat baths 5a and 5c was set to 204 ° C, and the temperature of the heat baths 5b and 5d was maintained at 19 ° C, which is room temperature. Under this condition, the sample was rapidly heated. Specifically, the swinging members 4a and 4c were swung from the state in which the heat baths 5b and 5d were in contact, and the heat baths 5a and 5c were brought into contact. FIG. 6 is a graph showing temporal changes in the temperature of the sample and the heat bath at that time. The heat baths 5a and 5c are brought into contact with the cell 11a, and the time when the heating of the sample is started is set to 0 second. The temperature of the sample is indicated by a solid line, and the temperature of the heat bath is indicated by a dotted line. As shown in FIG. 6, a temperature change condition of 60 to 130 ° C./second, that is, about 360 to 7000 ° C./min was achieved. This is a temperature gradient three to several tens of times that of a conventional flow cell type apparatus. In this experimental example, rapid heating was performed, but even when rapid cooling is performed, it is considered that the same effect can be obtained because the material or shape of the heat bath is the same. Further, it is considered that the maximum achieved temperature gradient is further improved if the thermal contact is improved and the heat capacity of the sample cell is designed and manufactured.

[Embodiment 2]
FIG. 7 is a side view of the heat treatment apparatus 1e according to Embodiment 2 when viewed in a direction parallel to the shafts 3e and 3g. In the first embodiment, the two shafts 3a and 3c are installed such that their center axes are point-symmetric with respect to the installation position when the heat treatment apparatus 1a is viewed in a direction parallel to the axis of the shaft. However, as shown in FIG. 7, the positions of the central axes of the shafts 3e and 3g are not point-symmetric with respect to the installation position, and the swinging members 4e and 4g are the same. May be different in length. Thus, even when there is a situation where the position of the central axis of the shaft is limited to a position that is not point-symmetric with respect to the position of the sample, a heat treatment apparatus that can cope with such a situation can be configured.

[Embodiment 3]
FIG. 8 is a side view when the heat treatment apparatus 1p according to the third embodiment is viewed in a direction parallel to the shafts 3p and 3r. In the first embodiment, the two shafts 3a and 3c are installed such that the installation position and the position of the central axis of the shaft are aligned in a straight line when the heat treatment apparatus 1a is viewed in a direction parallel to the axis of the shaft. The shapes of the swinging members 4a and 4c are the same, but as shown in FIG. 8, the installation position and the shaft position are not arranged in a straight line, and the shapes of the swinging members 4p and 4r and 4q and 4s. May be different. Thereby, even when there is a situation where the installation position and the position of the shaft are restricted to a position on a straight line, a heat treatment apparatus corresponding to such a situation can be configured. For example, the heat treatment apparatus 1p can be configured even when the position where radiation can be irradiated with respect to the position where the shaft can be installed must be above or below.

[Embodiment 4]
In the first embodiment, the object to be heat-treated is exchanged by opening and closing the lid of the cell 11a in the fixed holding portion 2a. However, the holding portion for storing the plurality of holding portions 2t and any one holding from the holding portion You may provide the supply part which supplies the part 2t to an installation position. That is, you may provide the so-called exchanger of to-be-heated material. FIG. 9 is a perspective view illustrating an example of a holding unit and a supply unit for an object to be heat treated. As shown in FIG. 9, the holding part 2t is composed of a cell 11t and a holding column 12t. For example, the storage portion (not shown) has a rectangular parallelepiped box shape so that the plurality of holding portions 2t can be stored. The accommodating portion has a space that allows the holding portions 2t to be stacked, and a stopper is provided below to limit the holding portions 2t to be sent out one by one to the guide 41t. As shown in FIG. 9, the guide 41t serving as the supply unit is a two narrow strips having a curved surface, and the tip portion is bent upward. The guide 41t is made of metal, for example, and has a strength that does not deform with the weight of the holding portion.

  Below, operation | movement of the holding | maintenance part 2t which concerns on Embodiment 4, the guide 41t, and an accommodating part is demonstrated easily. First, when the temperature of the heat bath is kept constant and preparation for temperature control is completed, the holding portion 2t is sent from the housing portion to the guide 41t. The holding part 2t supplied from the storage part is moved to the tip thereof along the curved surface of the guide 41t. Next, the heat baths are brought into contact with each other with the holding part 2t interposed therebetween, and a temperature control process necessary for the heat-treated object is performed. When the temperature control process is finished, the holding portion 2t is released and dropped downward by swinging and moving in the direction of arrow D around the upper end of the guide 41t. The guide 41t is returned to the original position. If the holding part 2t requiring the temperature control process remains, the holding part 2t is further sent from the storage part to the guide 41t, and the above operation is repeated until the holding part 2t remains in the storage part.

  Thereby, the trouble of exchanging a plurality of heat treatment objects can be saved, and the plurality of heat treatment objects can be processed at a time.

[Embodiment 5]
In the first embodiment, the object to be heat-treated is exchanged by opening and closing the lid of the cell 11a in the fixed holding unit 2a, but has a plurality of holding units 2v and supplies any one holding unit 2v to the installation position. You may provide the supply part to do. For example, you may provide the exchanger of the to-be-heated material by a belt conveyor. FIG. 10 is a perspective view of a heat treatment apparatus 1v according to the fifth embodiment. The heat treatment apparatus 1v shown in FIG. 10 is a perspective view showing an example including a belt conveyor 51v as a supply unit. As shown in FIG. 10, the holding part 2v is installed on the belt conveyor 51v. For example, when the object to be heat-treated is a film-like resin product and rapid heating or rapid cooling is included in the resin product production process, the heat treatment apparatus 1v can be used on the production line. The belt conveyor 51v is preferably driven when both swinging members swing 90 °. That is, it is preferable to drive when the first to fourth heat baths are just in the middle of oscillation. Accordingly, it is possible to make it difficult for the swing member or the heat bath to come into contact with the holding unit and the belt conveyor by driving the belt conveyor 51v.

  Further, in the heat treatment apparatus 1v shown in FIG. 10, the holding unit 2v is installed on the belt conveyor 51v. However, the object to be heat treated itself may be installed on the belt conveyor to control the temperature. In this case, a part of the belt conveyor that supports the object to be heat-treated becomes the holding unit. Thereby, the trouble of exchanging a plurality of heat treatment objects can be saved, and the plurality of heat treatment objects can be processed at a time. Also, it can be used for industrial line processes.

[Embodiment 6]
In the heat treatment apparatus 1a according to the first embodiment, the heat baths 5a to 5d are brought into close contact with the holding unit 2a, thereby rapidly heating or rapidly cooling the object to be heat-treated. Two temperature control means may be provided. For example, a hot wire heater or a cooling pipe may be provided as the second temperature control means so as to be incorporated in the holding unit 2a. Thereby, the second temperature control means can be used supplementarily, and the temperature of the object to be heat-treated can be changed with a large change width with respect to time.

  In addition, when using the heat processing apparatus of this invention for the structural analysis accompanying a temperature change, it can apply not only to the structural analysis by a radiation but optical analysis, such as IR and Raman measurement, and the magnetic analysis by NMR.

1 is a perspective view of a heat treatment apparatus according to Embodiment 1. FIG. 3 is a plan view of a holding unit according to Embodiment 1. FIG. It is a side view of the 1st rocking | swiveling member which concerns on Embodiment 1, and a 1st heat bath. 2 is a perspective view of a heat bath according to Embodiment 1. FIG. (A) It is a side view of the heat processing apparatus of the state which the heat bath does not collide. (B) It is a side view of the heat processing apparatus of the state which the heat bath has collided. It is a graph showing the time change of the temperature of the sample and heat bath in an experiment example. 5 is a side view of a heat treatment apparatus according to Embodiment 2. FIG. 6 is a side view of a heat treatment apparatus according to Embodiment 3. FIG. 10 is a perspective view showing an example of a holding unit and a supply unit according to Embodiment 4. FIG. FIG. 10 is a perspective view of a heat treatment apparatus according to Embodiment 5.

Explanation of symbols

1a Heat treatment apparatus 1e Heat treatment apparatus 1p Heat treatment apparatus 1v Heat treatment apparatus 2a Holding part 2t Holding part 2v Holding part 3a Shaft 3c Shaft 3e Shaft 3p Shaft 4a-c Swing member 4e Swing member 4p Swing member 5a-5d Heat bath 11a Cell 11t Cell 12a Holding column 12t Holding column 13a Radiation transmitting holes 21a to 21d Fixing plates 22a to 22d Bolt 31a Cell groove 32a Incident ray recess 33a Scattered ray recess 41t Guide 51v Belt conveyor

Claims (5)

A holding unit that holds an object to be heated or cooled at an installation position;
First and second swing members pivotally supported on both sides of the installation position and swingably provided;
A first heat bath and a second heat bath provided at both ends of the first rocking member;
A third heat bath and a fourth heat bath provided at both ends of the second rocking member;
First temperature control means for controlling the temperatures of the first to fourth heat baths, respectively,
When the first and second oscillating members are oscillated in the first direction, the first heat bath and the third heat bath collide with each other with the object to be heat-treated at the installation position. Together
When the first and second oscillating members are oscillated in the second direction, the second heat bath and the fourth heat bath collide with each other with the object to be heat-treated at the installation position. A heat treatment apparatus characterized by combining them.   The heat treatment apparatus according to claim 1, wherein the first temperature control means controls the temperatures of the first to fourth heat baths independently.   3. The heat treatment apparatus according to claim 1, wherein each of the swinging members is disposed so that an axis of each of the swinging members is point-symmetric with respect to the installation position.   The heat treatment apparatus according to any one of claims 1 to 3, further comprising a supply unit that includes a plurality of the holding units and supplies any one holding unit to the installation position. 5. The heat treatment apparatus according to claim 1, further comprising second temperature control means for independently controlling a temperature of the holding unit or the object to be heat treated.

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