JPH09288074A - Method and apparatus for controlling temperature of sample - Google Patents
Method and apparatus for controlling temperature of sampleInfo
- Publication number
- JPH09288074A JPH09288074A JP12395796A JP12395796A JPH09288074A JP H09288074 A JPH09288074 A JP H09288074A JP 12395796 A JP12395796 A JP 12395796A JP 12395796 A JP12395796 A JP 12395796A JP H09288074 A JPH09288074 A JP H09288074A
- Authority
- JP
- Japan
- Prior art keywords
- temperature
- sample
- heating
- difference
- signal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 88
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000001514 detection method Methods 0.000 claims description 10
- 230000000630 rising effect Effects 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000009529 body temperature measurement Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 3
- 238000002955 isolation Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000809 Alumel Inorganic materials 0.000 description 1
- 229910000629 Rh alloy Inorganic materials 0.000 description 1
- LIXXICXIKUPJBX-UHFFFAOYSA-N [Pt].[Rh].[Pt] Chemical compound [Pt].[Rh].[Pt] LIXXICXIKUPJBX-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
Landscapes
- Control Of Temperature (AREA)
- Investigating Or Analyzing Materials Using Thermal Means (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、熱電材料の熱起
電力を測定する場合の試料温度制御方法及び装置に関
し、特に、試料の二つの位置を別個の加熱装置で加熱す
ることによって、第１位置と第２位置の温度差を一定に
保ちながら試料の温度を変化させる試料温度制御方法及
び装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and apparatus for controlling a sample temperature when measuring a thermoelectromotive force of a thermoelectric material, and in particular, by heating two positions of the sample by separate heating devices, The present invention relates to a sample temperature control method and apparatus for changing the temperature of a sample while keeping a temperature difference between a position and a second position constant.
【０００２】[0002]
【従来の技術】熱電材料の主要な特性として、単位温度
差当たりの熱起電力があり、この熱起電力は温度に依存
して変化する。したがって、熱電材料を室温から高温ま
で変化させながら、単位温度差当たりの熱起電力を各温
度で測定することが行なわれている。熱起電力の測定装
置としては、特開平４−１２５４５８号公報、特開平５
−１８９１３号公報、特開昭６０−３９５４１号公報な
どに記載されているものが知られている。2. Description of the Related Art A major characteristic of thermoelectric materials is a thermoelectromotive force per unit temperature difference, which thermoelectromotive force changes depending on temperature. Therefore, the thermoelectromotive force per unit temperature difference is measured at each temperature while changing the thermoelectric material from room temperature to high temperature. As a thermoelectromotive force measuring device, Japanese Patent Laid-Open Nos. 4-125458 and 5-
Those described in JP-A-18913, JP-A-60-39541 and the like are known.
【０００３】単位温度差当りの熱起電力を測定するに当
たっては、熱電材料の二つの地点の温度差とその間の熱
起電力を測定する必要がある。その場合、温度差を一定
に保った状態で熱起電力を測定すれば、実測された熱起
電力の温度依存性は、そのまま、単位温度差当たりの熱
起電力の温度依存性に等しくなり、データ分析に便利で
ある。また、温度差を一定に保った状態で熱起電力を測
定すれば、測定結果の再現性や信頼性が向上すると考え
られる。そこで、試料の二つの地点の温度差を一定に保
った条件で熱起電力の温度依存性を測定できるような装
置が開発されてきている。In measuring the thermoelectromotive force per unit temperature difference, it is necessary to measure the temperature difference between two points of the thermoelectric material and the thermoelectromotive force between them. In that case, if the thermoelectromotive force is measured while the temperature difference is kept constant, the temperature dependency of the actually measured thermoelectromotive force becomes equal to the temperature dependency of the thermoelectromotive force per unit temperature difference, It is convenient for data analysis. In addition, if the thermoelectromotive force is measured with the temperature difference kept constant, it is considered that the reproducibility and reliability of the measurement result are improved. Therefore, an apparatus has been developed that can measure the temperature dependence of the thermoelectromotive force under the condition that the temperature difference between two points of the sample is kept constant.
【０００４】図４は温度差を一定に保った条件で熱起電
力の温度依存性を測定するための従来の測定装置の構成
図である。熱電材料からなる試料１０の両端は、石英製
の赤外線導入ロッド１２、１４を介して、それぞれ専用
の赤外線ランプ１６、１８で加熱される。試料１０の両
端には電極板２０、２２が接触しており、この電極板２
０、２２にそれぞれ熱電対２４、２６が接着されてい
る。試料１０の上端の温度Ｔａ（以下、第１温度とい
う。）は、熱電対２４で起電力として検出され、これが
第１温度計測装置２８で温度に変換される。この検出温
度は第１温度制御装置３０に送られ、この第１温度制御
装置３０では、第１温度Ｔａが所定の第１昇温曲線に追
従するように、第１加熱電源３２に加熱信号が出力され
る。そして、第１加熱電源３２からの供給電力によって
赤外線ランプ１６が加熱される。FIG. 4 is a block diagram of a conventional measuring apparatus for measuring the temperature dependence of thermoelectromotive force under the condition that the temperature difference is kept constant. Both ends of the sample 10 made of a thermoelectric material are heated by infrared lamps 16 and 18 for exclusive use via infrared introducing rods 12 and 14 made of quartz, respectively. The electrode plates 20 and 22 are in contact with both ends of the sample 10.
Thermocouples 24 and 26 are bonded to 0 and 22, respectively. The temperature Ta (hereinafter referred to as the first temperature) at the upper end of the sample 10 is detected as an electromotive force by the thermocouple 24, and this is converted into a temperature by the first temperature measuring device 28. This detected temperature is sent to the first temperature control device 30, and in the first temperature control device 30, a heating signal is sent to the first heating power supply 32 so that the first temperature Ta follows a predetermined first temperature rising curve. Is output. Then, the infrared lamp 16 is heated by the electric power supplied from the first heating power source 32.
【０００５】一方、試料１０の下端の温度Ｔｂ（以下、
第２温度という。）は、熱電対２６で起電力として検出
され、これが第２温度計測装置３４で温度に変換され
る。この検出温度は、第２温度制御装置３６に送られ、
第２温度Ｔｂが所定の第２昇温曲線に追従するように、
第２加熱電源３８に加熱信号が出力される。そして、試
料の両端の温度差を一定に保ちながら試料温度を上昇さ
せるには、目標となる第１昇温曲線と第２昇温曲線の間
に温度差を付けておけばよい。試料１０の両端で発生す
る熱起電力は電圧計４０で検出される。On the other hand, the temperature Tb at the lower end of the sample 10 (hereinafter,
The second temperature. ) Is detected as an electromotive force by the thermocouple 26, and this is converted into a temperature by the second temperature measuring device 34. This detected temperature is sent to the second temperature control device 36,
So that the second temperature Tb follows a predetermined second temperature rise curve,
A heating signal is output to the second heating power source 38. Then, in order to raise the sample temperature while keeping the temperature difference between both ends of the sample constant, a temperature difference may be provided between the target first temperature rising curve and the second temperature rising curve. The thermoelectromotive force generated at both ends of the sample 10 is detected by the voltmeter 40.
【０００６】図５は従来装置における昇温曲線のグラフ
である。試料の上端の温度Ｔａは、第１昇温曲線４２を
目標値として一定の昇温速度で上昇する。また、試料の
下端の温度Ｔｂは、第２昇温曲線４４を目標値として一
定の昇温速度で上昇する。第１昇温曲線４２と第２昇温
曲線４４は、昇温速度が同じに設定され、かつ、二つの
昇温曲線４２、４４の温度差ΔＴが一定になるように設
定される。試料の熱起電力の測定を開始するには、ま
ず、第１温度Ｔａが第１昇温曲線４２に追従するように
赤外線ランプ１６に電力を供給する。試料の上端が室温
から昇温を開始して、時間ｔだけ経過すると、第１昇温
曲線４２は室温よりもちょうどΔＴだけ高くなる。この
ときに、試料の下端側の赤外線ランプ１８にも電力供給
を開始して、第２温度Ｔｂが第２昇温曲線４４に追従す
るように制御する。このようにして、試料の両端の温度
は、それぞれの目標とする昇温曲線に追従するように制
御され、その結果として、温度差ΔＴが一定に保たれな
がら試料温度が上昇する。このような条件のもとで熱起
電力の温度依存性が測定される。FIG. 5 is a graph of a temperature rise curve in the conventional device. The temperature Ta at the upper end of the sample rises at a constant heating rate with the first heating curve 42 as a target value. Further, the temperature Tb at the lower end of the sample rises at a constant heating rate with the second heating curve 44 as a target value. The first temperature increase curve 42 and the second temperature increase curve 44 are set so that the temperature increase rates are the same and the temperature difference ΔT between the two temperature increase curves 42 and 44 is constant. To start measuring the thermoelectromotive force of the sample, first, power is supplied to the infrared lamp 16 so that the first temperature Ta follows the first temperature rising curve 42. When the upper end of the sample starts to rise in temperature from room temperature and time t elapses, the first temperature rise curve 42 becomes higher than room temperature by exactly ΔT. At this time, power supply is also started to the infrared lamp 18 on the lower end side of the sample, and the second temperature Tb is controlled so as to follow the second temperature rising curve 44. In this way, the temperatures at both ends of the sample are controlled so as to follow the respective target temperature rising curves, and as a result, the sample temperature rises while the temperature difference ΔT is kept constant. Under such conditions, the temperature dependence of the thermoelectromotive force is measured.
【０００７】[0007]
【発明が解決しようとする課題】上述した従来の熱起電
力測定装置では、試料の両端の温度は、それぞれ、目標
となる温度曲線に追従するようにフィードバック制御さ
れ、その結果として、両端の温度差が一定に保たれなが
ら昇温する。しかしながら、試料の両端の温度が別個の
フィードバック制御系で昇温制御されるので、実際に
は、試料の両端の温度差は必ずしも一定に保たれない。
なぜならば、二つのフィードバック制御系の特性の違い
や、制御開始時点が時間ｔだけずれることに伴う乱れ、
などが影響して、温度差はかなり変動する。In the conventional thermoelectromotive force measuring apparatus described above, the temperature at both ends of the sample is feedback-controlled so as to follow the target temperature curve, and as a result, the temperature at both ends is increased. The temperature rises while the difference is kept constant. However, since the temperature of both ends of the sample is controlled by the separate feedback control system, the temperature difference between both ends of the sample is not always kept constant in practice.
This is because the difference between the characteristics of the two feedback control systems and the turbulence caused by the control start point being displaced by the time t,
As a result, the temperature difference fluctuates considerably.
【０００８】この発明は上述の問題点を解決するために
なされたものであり、その目的は、試料の二つの位置を
別個の加熱装置で加熱することによって、第１位置と第
２位置の温度差を一定に保ちながら試料の温度を変化さ
せる場合に、その温度差を高精度に一定に保つことにあ
る。The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to heat two positions of a sample by separate heating devices so that the temperatures of the first position and the second position are increased. When the temperature of the sample is changed while keeping the difference constant, the temperature difference is kept constant with high accuracy.
【０００９】[0009]
【課題を解決するための手段】この発明の試料温度制御
方法は、熱電材料からなる試料の二つの位置（以下、第
１位置と第２位置という。）を別個の加熱装置で加熱す
ることによって、第１位置と第２位置の温度差を一定に
保ちながら試料の温度を変化させて、前記温度差に起因
する試料の熱起電力を試料温度の関数として測定する場
合の試料温度制御方法において、次の（イ）〜（ニ）の
段階を備える。（イ）前記第１位置の温度と前記第２位
置の温度をそれぞれ検出する段階。（ロ）前記第１位置
の温度が所定の温度変化曲線に追従するように、第１位
置加熱用の第１加熱装置を制御することによって、前記
第１位置の温度をフィードバック制御する段階。（ハ）
検出された第１位置の温度と第２位置の温度からその温
度差を求める段階。（ニ）前記温度差が所定の一定値に
なるように、第２位置加熱用の第２加熱装置を制御する
ことによって、前記温度差をフィードバック制御する段
階。The sample temperature control method of the present invention comprises heating two positions (hereinafter, referred to as a first position and a second position) of a sample made of a thermoelectric material by separate heating devices. A sample temperature control method in which the temperature of the sample is changed while keeping the temperature difference between the first position and the second position constant and the thermoelectromotive force of the sample caused by the temperature difference is measured as a function of the sample temperature. The following steps (a) to (d) are provided. (A) Detecting the temperature of the first position and the temperature of the second position, respectively. (B) Feedback controlling the temperature of the first position by controlling the first heating device for heating the first position so that the temperature of the first position follows a predetermined temperature change curve. (C)
A step of obtaining a temperature difference between the detected temperature at the first position and the detected temperature at the second position. (D) Feedback controlling the temperature difference by controlling the second heating device for the second position heating so that the temperature difference becomes a predetermined constant value.
【００１０】また、この発明の試料温度制御装置は、熱
電材料からなる試料の二つの位置（以下、第１位置と第
２位置という。）を別個の加熱装置で加熱することによ
って、第１位置と第２位置の温度差を一定に保ちながら
試料の温度を変化させて、前記温度差に起因する試料の
熱起電力を試料温度の関数として測定する場合の試料温
度制御装置において、次の（イ）〜（ト）の構成を備え
る。（イ）前記第１位置の温度を検出する第１温度検出
装置。（ロ）前記第２位置の温度を検出する第２温度検
出装置。（ハ）前記第１位置を加熱するための第１加熱
装置。（ニ）前記第２位置を加熱するための第２加熱装
置。（ホ）前記第１温度検出装置からの温度信号を受け
て、前記第１位置の温度が所定の温度変化曲線に追従す
るように前記第１加熱装置に加熱信号を出力する第１温
度制御装置。（ヘ）前記第１温度検出装置からの温度信
号と前記第２温度検出装置からの温度信号とを受けて、
前記第１位置と第２位置の温度差を求める温度差演算装
置。（ト）前記温度差演算装置からの温度差信号を受け
て、前記温度差が所定の一定値になるように前記第２加
熱装置に加熱信号を出力する第２温度制御装置。Further, the sample temperature control device of the present invention heats the two positions (hereinafter, referred to as the first position and the second position) of the sample made of the thermoelectric material by separate heating devices so that the first position. In the sample temperature control device in the case where the temperature of the sample is changed while keeping the temperature difference between the second position and the second position constant and the thermoelectromotive force of the sample caused by the temperature difference is measured as a function of the sample temperature, the following ( A) to (g) is provided. (A) A first temperature detection device that detects the temperature at the first position. (B) A second temperature detecting device that detects the temperature at the second position. (C) A first heating device for heating the first position. (D) A second heating device for heating the second position. (E) A first temperature control device that receives a temperature signal from the first temperature detection device and outputs a heating signal to the first heating device so that the temperature at the first position follows a predetermined temperature change curve. . (F) receiving a temperature signal from the first temperature detection device and a temperature signal from the second temperature detection device,
A temperature difference calculation device for obtaining a temperature difference between the first position and the second position. (G) A second temperature control device that receives a temperature difference signal from the temperature difference calculation device and outputs a heating signal to the second heating device so that the temperature difference becomes a predetermined constant value.
【００１１】この発明によれば、試料の二つの位置の温
度差自体を制御対象としてフィードバック制御している
ので、温度差が高精度に一定に保たれる。According to the present invention, the temperature difference between the two positions of the sample is feedback-controlled as a control target, so that the temperature difference can be maintained constant with high accuracy.
【００１２】試料の二つの位置としては、試料の両端と
するのが便利であるが、これに限定することなく、試料
の途中の任意の２か所であってもよい。加熱装置として
は、温度制御の応答性が高いとの理由で赤外線ランプが
好ましいが、これ以外のヒータを用いてもよい。It is convenient for the two positions of the sample to be both ends of the sample, but the present invention is not limited to this and may be any two positions in the middle of the sample. As the heating device, an infrared lamp is preferable because it has high responsiveness in temperature control, but a heater other than this may be used.
【００１３】この発明の試料温度制御方法及び装置は、
熱電材料の熱起電力の測定以外にも、試料の２地点間の
温度差を一定に保持しながら試料温度を変化させるよう
なその他の熱分析方法及び装置にも適用できる。The sample temperature control method and apparatus of the present invention are
In addition to the measurement of the thermoelectromotive force of the thermoelectric material, the present invention can be applied to other thermal analysis methods and devices that change the sample temperature while keeping the temperature difference between two points of the sample constant.
【００１４】[0014]
【発明の実施の形態】図１は、この発明の試料温度制御
装置の一実施形態を示す構成図である。熱電材料からな
る試料５０は、真空排気された赤外線加熱炉の内部に配
置される。試料５０の両端は、石英製の赤外線導入ロッ
ド５２、５４を介して、それぞれ専用の赤外線ランプ５
６、５８で加熱される。試料５０の両端にはニッケル製
の電極板６０、６２が接触しており、この電極板６０、
６２にそれぞれ熱電対６４、６６が接着されている。試
料５０の上端の温度Ｔａ（以下、第１温度という。）
は、熱電対６４で起電力として検出され、これが第１温
度計測装置６８で温度に変換される。熱電対の起電力・
温度変換表はその材質に応じた公知のものを使用でき
る。この第１温度計測装置６８で計測された第１温度Ｔ
ａは、第１温度制御装置７０に送られ、この第１温度Ｔ
ａが所定の昇温曲線に追従するように、第１加熱電源７
２に加熱信号が出力される。そして、この第１加熱電源
７２から赤外線ランプ５６に電力が供給される。1 is a block diagram showing an embodiment of a sample temperature control device of the present invention. A sample 50 made of a thermoelectric material is placed inside an infrared heating furnace that has been evacuated. Both ends of the sample 50 are respectively provided with dedicated infrared lamps 5 via infrared introducing rods 52 and 54 made of quartz.
Heated at 6,58. The electrode plates 60 and 62 made of nickel are in contact with both ends of the sample 50.
Thermocouples 64 and 66 are adhered to 62, respectively. The temperature Ta at the upper end of the sample 50 (hereinafter referred to as the first temperature).
Is detected as an electromotive force by the thermocouple 64, and this is converted into temperature by the first temperature measuring device 68. Electromotive force of thermocouple
As the temperature conversion table, known ones can be used depending on the material. The first temperature T measured by the first temperature measuring device 68
a is sent to the first temperature control device 70, and the first temperature T
The first heating power supply 7 is set so that a follows a predetermined temperature rising curve.
A heating signal is output to 2. Then, electric power is supplied from the first heating power source 72 to the infrared lamp 56.
【００１５】一方、試料５０の下端の温度Ｔｂ（以下、
第２温度という。）は、熱電対６６で起電力として検出
され、これが第２温度計測装置７４で温度に変換され
る。そして、第１温度計測装置６８で計測された第１温
度Ｔａと、第２温度計測装置７４で計測された第２温度
Ｔｂは、温度差演算装置７６に入力され、両者の温度差
ΔＴ＝Ｔａ−Ｔｂが求められる。この温度差ΔＴが第２
温度制御装置７８に送られて、温度差ΔＴが所定の一定
値に保たれるように、第２加熱電源８０に加熱信号が出
力される。そして、この第２加熱電源８０から赤外線ラ
ンプ５８に電力が供給される。その結果、試料５０の下
端の第２温度Ｔｂは、上端の第１温度Ｔａに対して常に
一定の温度差ΔＴを保つように追従していく。試料５０
の両端で発生する熱起電力は電圧計８２で検出される。
また、第１温度計測装置６８の出力と、第２温度計測装
置７４の出力と、電圧計８２の出力は、記録装置に入力
されて、この記録装置で、単位温度差当たりの熱起電力
と試料温度とが記録される。On the other hand, the temperature Tb at the lower end of the sample 50 (hereinafter,
The second temperature. ) Is detected as an electromotive force by the thermocouple 66, and this is converted into a temperature by the second temperature measuring device 74. Then, the first temperature Ta measured by the first temperature measurement device 68 and the second temperature Tb measured by the second temperature measurement device 74 are input to the temperature difference calculation device 76, and the temperature difference ΔT = Ta between the two. -Tb is required. This temperature difference ΔT is the second
The heating signal is sent to the temperature control device 78, and a heating signal is output to the second heating power supply 80 so that the temperature difference ΔT is maintained at a predetermined constant value. Then, electric power is supplied from the second heating power source 80 to the infrared lamp 58. As a result, the second temperature Tb at the lower end of the sample 50 follows the first temperature Ta at the upper end so as to always maintain a constant temperature difference ΔT. Sample 50
The thermoelectromotive force generated at both ends of the voltage is detected by the voltmeter 82.
Further, the output of the first temperature measuring device 68, the output of the second temperature measuring device 74, and the output of the voltmeter 82 are input to the recording device, and in this recording device, the thermoelectromotive force per unit temperature difference is calculated. The sample temperature and is recorded.
【００１６】図１の装置とこの発明の構成要件との対応
関係を説明すると、第１加熱電源７２と赤外線ランプ５
６がこの発明の第１加熱装置を構成し、第２加熱電源８
０と赤外線ランプ５８がこの発明の第２加熱装置を構成
する。また、熱電対６４と第１温度計測装置６８がこの
発明の第１温度検出装置を構成し、熱電対６６と第２温
度計測装置７４がこの発明の第２温度検出装置を構成す
る。The correspondence between the apparatus of FIG. 1 and the constituent features of the present invention will be described. The first heating power source 72 and the infrared lamp 5 are described.
6 constitutes the first heating device of the present invention, and the second heating power source 8
0 and the infrared lamp 58 constitute the second heating device of the present invention. Further, the thermocouple 64 and the first temperature measuring device 68 form the first temperature detecting device of the present invention, and the thermocouple 66 and the second temperature measuring device 74 form the second temperature detecting device of the present invention.
【００１７】図１の装置において、熱起電力の測定に加
えて、各温度における試料の電気抵抗も同時に測定する
ようにしてもよい。In the apparatus of FIG. 1, in addition to the measurement of thermoelectromotive force, the electrical resistance of the sample at each temperature may be simultaneously measured.
【００１８】図２は、図１の装置で使われる昇温曲線の
グラフの一例である。試料の上端の第１温度Ｔａは昇温
曲線８４に追従して上昇する。この実施形態では、室温
から１０００℃まで昇温できる。図１の第１温度制御装
置７０にはこの昇温曲線８４が目標値として記憶されて
いる。この第１温度制御装置７０は、第１温度計測装置
６８の出力信号すなわち第１温度Ｔａを受け取って、こ
の第１温度Ｔａが昇温曲線８４に追従するように、第１
加熱電源７２に加熱信号を出力する。この加熱信号に基
づいて第１加熱電源７２は赤外線ランプ５６に電力を供
給する。このようにして、第１温度Ｔａはフィードバッ
ク制御される。この第１温度制御装置７０によるフィー
ドバック制御では公知のＰＩＤ制御が用いられている。FIG. 2 is an example of a graph of a temperature rising curve used in the apparatus of FIG. The first temperature Ta at the upper end of the sample rises following the temperature rising curve 84. In this embodiment, the temperature can be raised from room temperature to 1000 ° C. The temperature rising curve 84 is stored as a target value in the first temperature control device 70 of FIG. The first temperature control device 70 receives the output signal of the first temperature measuring device 68, that is, the first temperature Ta, so that the first temperature Ta follows the temperature rising curve 84.
A heating signal is output to the heating power source 72. Based on this heating signal, the first heating power source 72 supplies power to the infrared lamp 56. In this way, the first temperature Ta is feedback-controlled. In the feedback control by the first temperature control device 70, known PID control is used.
【００１９】一方、第２温度制御装置７８には目標とな
る一定の温度差が記憶されている。この目標値は時間と
共に変化せずに常に一定である。この第２温度制御装置
７８は、温度差演算装置７６の出力信号すなわち実測し
た温度差ΔＴを受け取って、この温度差ΔＴが目標の温
度差となるように、第２加熱電源８０に加熱信号を出力
する。この加熱信号に基づいて第２加熱電源８０は赤外
線ランプ５８に電力を供給する。このようにして、試料
の上端と下端の温度差が一定となるようにフィードバッ
ク制御される。この第２温度制御装置７８によるフィー
ドバック制御においても公知のＰＩＤ制御が用いられて
いる。この実施形態では、目標の温度差は２℃〜５０℃
の間で設定できる。On the other hand, the second temperature control device 78 stores a target constant temperature difference. This target value does not change with time and is always constant. The second temperature control device 78 receives the output signal of the temperature difference calculation device 76, that is, the actually measured temperature difference ΔT, and outputs a heating signal to the second heating power supply 80 so that the temperature difference ΔT becomes a target temperature difference. Output. The second heating power supply 80 supplies power to the infrared lamp 58 based on the heating signal. In this way, feedback control is performed so that the temperature difference between the upper end and the lower end of the sample becomes constant. The known PID control is also used in the feedback control by the second temperature control device 78. In this embodiment, the target temperature difference is 2 ° C to 50 ° C.
Can be set between.
【００２０】以上説明したように、この試料温度制御装
置では、試料温度を所定の昇温曲線に追従させるフィー
ドバック制御は第１温度制御装置７０が担当し、試料の
両端の温度差を一定に保つフィードバック制御は第２温
度制御装置７８が担当している。このようにして、温度
差を一定に保つためのフィードバック制御系が昇温フィ
ードバック制御系とは別個になっているので、温度差は
高精度に一定に保たれる。As described above, in this sample temperature control device, the first temperature control device 70 takes charge of feedback control for making the sample temperature follow a predetermined temperature rising curve, and keeps the temperature difference between both ends of the sample constant. The second temperature control device 78 is in charge of the feedback control. In this way, since the feedback control system for keeping the temperature difference constant is separate from the temperature raising feedback control system, the temperature difference can be kept constant with high accuracy.
【００２１】図３は図１の装置で測定した熱起電力のグ
ラフの一例である。横軸の温度は、試料の第１温度Ｔａ
と第２温度Ｔｂの平均値であり、この平均値をもって試
料温度としている。縦軸は単位温度差当たりの熱起電力
である。FIG. 3 is an example of a graph of thermoelectromotive force measured by the apparatus of FIG. The temperature on the horizontal axis is the first temperature Ta of the sample.
And an average value of the second temperature Tb, and this average value is used as the sample temperature. The vertical axis represents the thermoelectromotive force per unit temperature difference.
【００２２】図１において、この装置の具体的な仕様例
を以下に説明する。温度範囲は室温〜１０００℃であ
り、試料５０の両端の目標温度差は２℃〜５０℃の間で
数段階に設定できる。温度制御の性能としては、第１温
度Ｔａの目標温度追従性が±０．５℃以下であり、温度
差ΔＴの変動も±０．５℃以下である。試料５０の寸法
は、その断面が一辺５〜１０ｍｍの正方形で、長さが５
〜１５ｍｍである。ニッケル製の電極板６０、６２は厚
さ０．２ｍｍの円板である。使用する熱電対６４、６６
は白金−白金ロジウム合金か、クロメル−アルメルであ
る。In FIG. 1, a specific example of the specifications of this device will be described below. The temperature range is room temperature to 1000 ° C., and the target temperature difference between both ends of the sample 50 can be set in several steps between 2 ° C. and 50 ° C. Regarding the performance of temperature control, the target temperature followability of the first temperature Ta is ± 0.5 ° C. or less, and the variation of the temperature difference ΔT is also ± 0.5 ° C. or less. The sample 50 has a square cross section with a side of 5 to 10 mm and a length of 5
~ 15 mm. The electrode plates 60 and 62 made of nickel are circular plates having a thickness of 0.2 mm. Thermocouples 64 and 66 used
Is platinum-platinum-rhodium alloy or chromel-alumel.
【００２３】図６は、この発明の試料温度制御装置の別
の実施形態を示す構成図である。図１の構成と異なる点
は、図１の温度差演算装置７６を削除して、その代わり
に、差分出力装置８６を設けたことである。図１の構成
と同じ部分には同じ符号を付けてあり、その説明は省略
する。FIG. 6 is a block diagram showing another embodiment of the sample temperature control device of the present invention. The difference from the configuration of FIG. 1 is that the temperature difference calculation device 76 of FIG. 1 is deleted and a difference output device 86 is provided instead. The same parts as those in FIG. 1 are designated by the same reference numerals, and the description thereof will be omitted.
【００２４】図６において、熱電対６４の起電力は、第
１温度計測装置６８に入力されると共に、差分出力装置
８６の第１増幅器８８にも入力される。そして、熱電対
６４の出力は、第１増幅器８８と第１アイソレーション
・アンプ９２で増幅されてから、差動増幅器９４の一方
の入力端子に入力される。また、熱電対６６の起電力
は、第２温度計測装置７４に入力されると共に、差分出
力装置８６の第２増幅器９０にも入力される。そして、
熱電対６６の出力は、第２増幅器９０と第２アイソレー
ション・アンプ９６で増幅されてから、差動増幅器９４
の他方の入力端子に入力される。そして、この差動増幅
器９４からは、熱電対６４の起電力と熱電対６６の起電
力との差分に比例した電圧信号ΔＶが出力される。In FIG. 6, the electromotive force of the thermocouple 64 is input to the first temperature measuring device 68 and also to the first amplifier 88 of the differential output device 86. The output of the thermocouple 64 is amplified by the first amplifier 88 and the first isolation amplifier 92, and then input to one input terminal of the differential amplifier 94. Further, the electromotive force of the thermocouple 66 is input to the second temperature measuring device 74 and also to the second amplifier 90 of the differential output device 86. And
The output of the thermocouple 66 is amplified by the second amplifier 90 and the second isolation amplifier 96, and then the differential amplifier 94.
Is input to the other input terminal of. The differential amplifier 94 outputs a voltage signal ΔV proportional to the difference between the electromotive force of the thermocouple 64 and the electromotive force of the thermocouple 66.
【００２５】この電圧信号ΔＶは第２温度制御装置９８
に入力される。この第２温度制御装置９８は、入力され
た電圧信号ΔＶが、所定の目標温度差に相当する目標電
圧になるように、第２加熱電源８０に加熱信号を出力す
る。これにより、試料の下端の温度は、上端に対して所
定の目標温度差になるように制御される。This voltage signal ΔV is the second temperature control device 98.
Is input to The second temperature control device 98 outputs a heating signal to the second heating power supply 80 so that the input voltage signal ΔV becomes the target voltage corresponding to the predetermined target temperature difference. Thereby, the temperature of the lower end of the sample is controlled so as to have a predetermined target temperature difference with respect to the upper end.
【００２６】この図６の実施形態では、各熱電対の起電
力をそれぞれの温度計測装置で温度に変換してからその
差分を求める代わりに、各熱電対の起電力の差分を直接
求めて、これを第２温度制御装置にフィードバックして
おり、次の利点がある。図１において、試料の両端の目
標温度差を小さい値に設定する場合を考えると、第１温
度計測装置６８と第２温度計測装置７４における起電力
・温度変換の精度を高くする必要がある。この変換精度
が低いと、各温度計測装置６８、７４での変換誤差が温
度差演算装置７６の出力精度に大きく影響する。したが
って、変換精度の高い高価な温度計測装置を使う必要が
ある。これに対して、図６に示すように、二つの熱電対
の起電力について温度変換をすることなく、差分出力装
置８６で起電力の差分を求めれば、温度計測装置での温
度変換精度の影響を受けることがなく、目標温度差が小
さい場合でも、試料の両端の温度差を高精度に一定に制
御できる。In the embodiment of FIG. 6, instead of converting the electromotive force of each thermocouple into a temperature with each temperature measuring device and then obtaining the difference, the difference of the electromotive force of each thermocouple is directly obtained. This is fed back to the second temperature control device, which has the following advantages. Considering the case where the target temperature difference between both ends of the sample is set to a small value in FIG. 1, it is necessary to increase the accuracy of electromotive force / temperature conversion in the first temperature measuring device 68 and the second temperature measuring device 74. When the conversion accuracy is low, the conversion error in each of the temperature measuring devices 68 and 74 greatly affects the output accuracy of the temperature difference calculation device 76. Therefore, it is necessary to use an expensive temperature measuring device with high conversion accuracy. On the other hand, as shown in FIG. 6, if the difference between the electromotive forces of the two thermocouples is not converted and the difference between the electromotive forces is obtained by the difference output device 86, the influence of the temperature conversion accuracy in the temperature measuring device is affected. Even if the target temperature difference is small, the temperature difference between both ends of the sample can be controlled with high accuracy and constant.
【００２７】なお、図１と図６の実施形態では、試料に
加熱エネルギーを導入するのに、石英製の赤外線導入ロ
ッド５２、５４を用いているが、この石英製ロッドを使
わずに、反射板による集光加熱で試料を加熱してもよ
い。In the embodiments shown in FIGS. 1 and 6, the infrared introducing rods 52 and 54 made of quartz are used to introduce the heating energy into the sample. The sample may be heated by converging heating with a plate.
【００２８】[0028]
【発明の効果】この発明は、試料の二つの位置の温度差
自体を制御対象としてフィードバック制御しているの
で、その温度差を高精度に一定に保った状態で、試料温
度を変化させることができる。According to the present invention, the temperature difference between the two positions of the sample is feedback-controlled as a control target, so that the sample temperature can be changed while keeping the temperature difference highly accurately constant. it can.
【図１】この発明の試料温度制御装置の一実施形態を示
す構成図である。FIG. 1 is a configuration diagram showing an embodiment of a sample temperature control device of the present invention.
【図２】図１の装置で使われる昇温曲線のグラフの一例
である。FIG. 2 is an example of a graph of a temperature rising curve used in the apparatus of FIG.
【図３】図１の装置で測定した熱起電力のグラフの一例
である。3 is an example of a graph of thermoelectromotive force measured by the apparatus of FIG.
【図４】従来の熱起電力測定装置の構成図である。FIG. 4 is a configuration diagram of a conventional thermoelectromotive force measuring device.
【図５】従来装置における昇温曲線のグラフである。FIG. 5 is a graph of a temperature rise curve in a conventional device.
【図６】この発明の試料温度制御装置の別の実施形態を
示す構成図である。FIG. 6 is a configuration diagram showing another embodiment of the sample temperature control device of the invention.
５０ 試料 ５２、５４ 石英ロッド ５６、５８ 赤外線ランプ ６０、６２ 電極板 ６４、６６ 熱電対 ６８ 第１温度計測装置 ７０ 第１温度制御装置 ７２ 第１加熱電源 ７４ 第２温度計測装置 ７６ 温度差演算装置 ７８ 第２温度制御装置 ８０ 第２加熱電源 ８２ 電圧計 50 sample 52, 54 quartz rod 56, 58 infrared lamp 60, 62 electrode plate 64, 66 thermocouple 68 first temperature measurement device 70 first temperature control device 72 first heating power supply 74 second temperature measurement device 76 temperature difference calculation device 78 Second temperature control device 80 Second heating power source 82 Voltmeter
Claims (5)
下、第１位置と第２位置という。）を別個の加熱装置で
加熱することによって、第１位置と第２位置の温度差を
一定に保ちながら試料の温度を変化させて、前記温度差
に起因する試料の熱起電力を試料温度の関数として測定
する場合の試料温度制御方法において、次の段階を備え
る試料温度制御方法。 （イ）前記第１位置の温度と前記第２位置の温度をそれ
ぞれ検出する段階。 （ロ）前記第１位置の温度が所定の温度変化曲線に追従
するように、第１位置加熱用の第１加熱装置を制御する
ことによって、前記第１位置の温度をフィードバック制
御する段階。 （ハ）検出された第１位置の温度と第２位置の温度から
その温度差を求める段階。 （ニ）前記温度差が所定の一定値になるように、第２位
置加熱用の第２加熱装置を制御することによって、前記
温度差をフィードバック制御する段階。1. A temperature difference between a first position and a second position is made constant by heating two positions (hereinafter, referred to as a first position and a second position) of a sample made of a thermoelectric material by separate heating devices. A sample temperature control method comprising the following steps in a sample temperature control method in which the temperature of the sample is changed while maintaining the temperature of the sample and the thermoelectromotive force of the sample caused by the temperature difference is measured as a function of the sample temperature. (A) Detecting the temperature of the first position and the temperature of the second position, respectively. (B) Feedback controlling the temperature of the first position by controlling the first heating device for heating the first position so that the temperature of the first position follows a predetermined temperature change curve. (C) Obtaining the temperature difference from the detected temperature at the first position and the detected temperature at the second position. (D) Feedback controlling the temperature difference by controlling the second heating device for the second position heating so that the temperature difference becomes a predetermined constant value.
下、第１位置と第２位置という。）を別個の加熱装置で
加熱することによって、第１位置と第２位置の温度差を
一定に保ちながら試料の温度を変化させて、前記温度差
に起因する試料の熱起電力を試料温度の関数として測定
する場合の試料温度制御装置において、次の構成を備え
る試料温度制御装置。 （イ）前記第１位置の温度を検出する第１温度検出装
置。 （ロ）前記第２位置の温度を検出する第２温度検出装
置。 （ハ）前記第１位置を加熱するための第１加熱装置。 （ニ）前記第２位置を加熱するための第２加熱装置。 （ホ）前記第１温度検出装置からの温度信号を受けて、
前記第１位置の温度が所定の温度変化曲線に追従するよ
うに前記第１加熱装置に加熱信号を出力する第１温度制
御装置。 （ヘ）前記第１温度検出装置からの温度信号と前記第２
温度検出装置からの温度信号とを受けて、前記第１位置
と第２位置の温度差を求める温度差演算装置。 （ト）前記温度差演算装置からの温度差信号を受けて、
前記温度差が所定の一定値になるように前記第２加熱装
置に加熱信号を出力する第２温度制御装置。2. The temperature difference between the first position and the second position is made constant by heating two positions (hereinafter, referred to as a first position and a second position) of the sample made of a thermoelectric material by separate heating devices. A sample temperature control device having the following configuration in a sample temperature control device in the case of measuring the thermoelectromotive force of the sample due to the temperature difference as a function of the sample temperature by changing the temperature of the sample while maintaining (A) A first temperature detection device that detects the temperature at the first position. (B) A second temperature detecting device that detects the temperature at the second position. (C) A first heating device for heating the first position. (D) A second heating device for heating the second position. (E) Receiving the temperature signal from the first temperature detecting device,
A first temperature control device that outputs a heating signal to the first heating device so that the temperature at the first position follows a predetermined temperature change curve. (F) The temperature signal from the first temperature detection device and the second signal
A temperature difference calculation device that receives a temperature signal from a temperature detection device and obtains a temperature difference between the first position and the second position. (G) Upon receiving the temperature difference signal from the temperature difference calculation device,
A second temperature control device that outputs a heating signal to the second heating device so that the temperature difference becomes a predetermined constant value.
れぞれ、赤外線ランプを備えることを特徴とする請求項
２記載の試料温度制御装置。3. The sample temperature control device according to claim 2, wherein each of the first heating device and the second heating device includes an infrared lamp.
２位置という。）を別個の加熱装置で加熱することによ
って、第１位置と第２位置の温度差を一定に保ちながら
試料の温度を変化させる試料温度制御方法において、次
の段階を備える試料温度制御方法。 （イ）前記第１位置の温度と前記第２位置の温度をそれ
ぞれ検出する段階。 （ロ）前記第１位置の温度が所定の温度変化曲線に追従
するように、第１位置加熱用の第１加熱装置を制御する
ことによって、前記第１位置の温度をフィードバック制
御する段階。 （ハ）検出された第１位置の温度と第２位置の温度から
その温度差を求める段階。 （ニ）前記温度差が所定の一定値になるように、第２位
置加熱用の第２加熱装置を制御することによって、前記
温度差をフィードバック制御する段階。4. The sample is heated while two positions (hereinafter, referred to as a first position and a second position) of the sample are heated by separate heating devices, and the temperature difference between the first position and the second position is kept constant. A sample temperature control method for changing the temperature of a sample, comprising the following steps. (A) Detecting the temperature of the first position and the temperature of the second position, respectively. (B) Feedback controlling the temperature of the first position by controlling the first heating device for heating the first position so that the temperature of the first position follows a predetermined temperature change curve. (C) Obtaining the temperature difference from the detected temperature at the first position and the detected temperature at the second position. (D) Feedback controlling the temperature difference by controlling the second heating device for the second position heating so that the temperature difference becomes a predetermined constant value.
２位置という。）を別個の加熱装置で加熱することによ
って、第１位置と第２位置の温度差を一定に保ちながら
試料の温度を変化させる試料温度制御装置において、次
の構成を備える試料温度制御装置。 （イ）前記第１位置の温度を検出する第１温度検出装
置。 （ロ）前記第２位置の温度を検出する第２温度検出装
置。 （ハ）前記第１位置を加熱するための第１加熱装置。 （ニ）前記第２位置を加熱するための第２加熱装置。 （ホ）前記第１温度検出装置からの温度信号を受けて、
前記第１位置の温度が所定の温度変化曲線に追従するよ
うに前記第１加熱装置に加熱信号を出力する第１温度制
御装置。 （ヘ）前記第１温度検出装置からの温度信号と前記第２
温度検出装置からの温度信号とを受けて、前記第１位置
と第２位置の温度差を求める温度差演算装置。 （ト）前記温度差演算装置からの温度差信号を受けて、
前記温度差が所定の一定値になるように前記第２加熱装
置に加熱信号を出力する第２温度制御装置。5. A sample is heated while two positions of the sample (hereinafter, referred to as a first position and a second position) are heated by separate heating devices, while maintaining a constant temperature difference between the first position and the second position. A sample temperature control device for changing the temperature of a sample temperature control device, comprising: (A) A first temperature detection device that detects the temperature at the first position. (B) A second temperature detecting device that detects the temperature at the second position. (C) A first heating device for heating the first position. (D) A second heating device for heating the second position. (E) Receiving the temperature signal from the first temperature detecting device,
A first temperature control device that outputs a heating signal to the first heating device so that the temperature at the first position follows a predetermined temperature change curve. (F) The temperature signal from the first temperature detection device and the second signal
A temperature difference calculation device that receives a temperature signal from a temperature detection device and obtains a temperature difference between the first position and the second position. (G) Upon receiving the temperature difference signal from the temperature difference calculation device,
A second temperature control device that outputs a heating signal to the second heating device so that the temperature difference becomes a predetermined constant value.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12395796A JP3670757B2 (en) | 1996-04-23 | 1996-04-23 | Sample temperature control method and apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12395796A JP3670757B2 (en) | 1996-04-23 | 1996-04-23 | Sample temperature control method and apparatus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09288074A true JPH09288074A (en) | 1997-11-04 |
| JP3670757B2 JP3670757B2 (en) | 2005-07-13 |
Family
ID=14873536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12395796A Expired - Fee Related JP3670757B2 (en) | 1996-04-23 | 1996-04-23 | Sample temperature control method and apparatus |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3670757B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005134276A (en) * | 2003-10-31 | 2005-05-26 | Matsushita Electric Ind Co Ltd | Thermal analysis information providing method and thermal analysis information providing system |
| CN111811957A (en) * | 2019-11-11 | 2020-10-23 | 上海交通大学 | The heating method based on the control of the heating device for the thermal tensile test |
| JP2024036025A (en) * | 2022-09-05 | 2024-03-15 | 東京エレクトロン株式会社 | Substrate processing equipment |
-
1996
- 1996-04-23 JP JP12395796A patent/JP3670757B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005134276A (en) * | 2003-10-31 | 2005-05-26 | Matsushita Electric Ind Co Ltd | Thermal analysis information providing method and thermal analysis information providing system |
| CN111811957A (en) * | 2019-11-11 | 2020-10-23 | 上海交通大学 | The heating method based on the control of the heating device for the thermal tensile test |
| JP2024036025A (en) * | 2022-09-05 | 2024-03-15 | 東京エレクトロン株式会社 | Substrate processing equipment |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3670757B2 (en) | 2005-07-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4195935B2 (en) | Thermophysical property measuring method and apparatus | |
| KR100308439B1 (en) | Method and device for effecting temperature compensation in load detector | |
| CN108548844B (en) | Thermal physical property sensor for measuring temperature of circular ring heating excitation central point and measuring method | |
| EP0962763A1 (en) | Differential scanning calorimeter | |
| JP2013228346A (en) | Thermal conductivity sensor using time integration of output, hydrogen gas sensor using the same, absolute humidity sensor, and thermal conductivity sensor chip | |
| US7626144B2 (en) | Method and apparatus for rapid temperature changes | |
| JPH07294541A (en) | Measurement device | |
| JPH09503049A (en) | Calibration of high temperature thermoelectric elements | |
| JPS6140062B2 (en) | ||
| JP3670757B2 (en) | Sample temperature control method and apparatus | |
| JP3687030B2 (en) | Micro surface temperature distribution measurement method and apparatus therefor | |
| JP2949314B2 (en) | Calorimeter and method | |
| JPH07113777A (en) | Atmosphere detecting device | |
| JPH1123505A (en) | Thermal analyzer | |
| JP2020139834A (en) | Thermoelectric characterization unit, thermoelectric characterization device and thermoelectric characterization method | |
| JP2007218591A (en) | Hybrid surface thermometer, temperature distribution measuring device and measuring method | |
| JPH03237345A (en) | Method for measuring thermal conductivity | |
| JP2000206022A (en) | Sample heating method for thermal desorption | |
| JPH1096703A (en) | Heat conduction parameter sensing method with resistor, and sensor circuit | |
| JP2000275261A (en) | Scanning microscope with temperature compensation mechanism | |
| JPS63159740A (en) | Heat constant measuring instrument by laser flash method | |
| JP3338456B2 (en) | Radiation thermometer and method of measuring temperature of radiation thermometer | |
| JPH11241962A (en) | pressure sensor | |
| JPS59184829A (en) | Thermometer | |
| JP3834633B2 (en) | Ultra-high temperature measuring device and gas sensor for ultra-high temperature |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20040816 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20041012 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20050412 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20050415 |
|
| R150 | Certificate of patent (=grant) or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090422 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090422 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 5 Free format text: PAYMENT UNTIL: 20100422 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100422 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 6 Free format text: PAYMENT UNTIL: 20110422 |
|
| LAPS | Cancellation because of no payment of annual fees |