JPH0228575A - Magnetometers and magnetometer parts - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a magnetic flux meter and a magnetic flux sensor using a superconducting quantum interferometer, and particularly relates to a ferrite-containing flux sensor used in high-temperature environments such as chemical plants and atomic couplants. The present invention relates to a pickup coil (probe coil) and a core for a pickup coil (probe coil) suitable for detecting high temperature aging embrittlement damage in an actual machine part of a metal material such as stainless steel.

[Conventional technology]

A superconducting sheet that exhibits high critical current characteristics not in a low magnetic field as in the case of deterioration diagnosis of ferrite-containing stainless steel, but in a high magnetic field region used in nuclear fusion toroidal magnets, particle accelerator magnets, superconducting generator magnets, etc. Regarding the manufacturing method of the coil, JP-A-62-2
There is a technique described in Publication No. 77704.

On the other hand, as a method for detecting the degree of high-temperature embrittlement damage of ferrite-containing stainless steel actual machine parts, there is a method described in Japanese Patent Application Laid-Open No. 61-28859. this is.

This method uses a ferrite scope to magnetically measure changes in the amount of ferrite after long-term use at high temperatures in actual machine parts, thereby detecting the degree of embrittlement in the parts concerned.

[Problem to be solved by the invention]

In JP-A No. 61-28859, since the method uses a ferrite scope to measure changes in the amount of ferrite, changes in magnetic properties due to precipitation of α' phase and G phase caused by spinodal decomposition of the initial ferrite phase are measured. The problem was that I couldn't do it.

In Japanese Patent Application Laid-Open No. 62-277704, NbaS
Regarding superconducting conductors such as n-superconducting intermetallic compounds,
A substrate containing at least one of two or more metal elements constituting a superconducting intermetallic compound.

A metal plate containing the remaining metal elements is placed between the metal plates, and in between, Ti, which improves the critical current density in a high magnetic field region, is added.
This is a method of manufacturing a superconducting sheet coil by inserting an additive member containing a third element such as Ta, and performing a circuit forming process using a heating beam such as a laser beam or an electron beam. Since the method can generate a superconducting circuit by adding a third element without alloying the substrate and the metal plate, it is possible to manufacture a superconducting coil that exhibits excellent critical current characteristics in a high magnetic field region. However, the above conventional technology.

There has been no discussion of recent methods for manufacturing coils made of oxide high-temperature superconducting materials, and no consideration has been given to the optimal method for manufacturing superconducting printed coils in low magnetic fields.

In addition, there is a technique described in Japanese Patent Laid-Open No. 140403/1983 as a prior art. According to this, in a superconducting coil used in a bending electromagnet of an accelerator, the critical current characteristics of the superconducting wire are It is possible to generate a uniform magnetic field with few irregular magnetic fields near the central axis of the superconducting coil without degrading the superconducting coil. However, although the above-mentioned conventional technology is effective in high magnetic fields such as in accelerators, it is effective in detecting minute magnetic fields such as in superconducting quantum interference devices (hereinafter also referred to as Suki and Rad).

The influence of the external field and internal noise is greater than the irregular magnetic field caused by the coil outlet.

The purpose of the present invention is to improve the sensitivity and signal resolution of a superconducting quantum interference probe magnetometer equipped with a magnetic flux transfer circuit or a magnetic flux transformer, and to improve the sensitivity and signal resolution of a superconducting quantum interference probe magnetometer equipped with a magnetic flux transfer circuit or a magnetic flux transformer. It is an object of the present invention to provide a method and apparatus that can detect the degree of embrittlement of an actual machine member with high accuracy.

[Means to solve the problem]

The above purpose is to use a printed coil as a pickup coil in a magnetic flux transformer of a superconducting quantum interference probe magnetometer,
This can also be achieved by providing the printed coil with a printed coil core made of a soft magnetic material. The printed coil may be a thin film printed coil or a thin plate printed coil. It is also possible to stack two or more printed coils, and by changing the winding direction of the two printed coils, it can also be used as a magnetic flux gradiometer. Sputtering is a method for manufacturing thin film printed coils.

Laser sputtering, MBE method, 1M0CvD method, spray virolysis method, etc. can be employed, and in the case of a thin film plate printed coil, a doctor blade method can be used.

In addition, in the following explanation, probe coil (flaw detection coil)
is written to correspond to the magnetic flux transfer circuit, and the pickup coil (detection coil) is written to correspond to the magnetic flux transformer, but it is not necessary to make a clear technical distinction between the two, and there is no technical distinction between the magnetic flux transfer circuit and the magnetic flux transformer. Although it is not necessary, the words and phrases are used in this manner for convenience. Further, the printed coil refers to a coil formed in the form of a thin film or a thin plate, and is not limited to those formed by printing.

(Magnetic flux meter) The magnetic flux meter of the present invention includes a magnetic flux transmission circuit or a magnetic flux transformer arranged so that the probe coil or pickup coil faces the object to be measured, and a superconducting circuit provided within the reach of the magnetic flux generated from the circuit or transformer. A quantum interference element is provided, and a printed coil is applied to the coil. More preferably, a core made of soft magnetic material is also used.

If a soft magnetic core is also used, the probe coil does not necessarily need to be a protocoil. It is preferable to insert a member (an inclusion) between these coils and the object to be certified to define the distance between the two members.

The relationship between the coil and the core may be as follows.

■ A core made of soft magnetic material is provided on the opposite side of the printed coil from the sample to be measured.

(2) A core of soft magnetic material is installed between the superconducting ribbons of the printed coil, and the printed coil and the core of soft magnetic material are housed on the same plane.

■ Equipped with a core that is an integral part of the core of (■) above and the core of (■) above.

■ Extend the core between the superconducting ribbons of the printed coil toward the sample to be measured and bring it into contact with the sample to be measured.

■ Layer two or more printed coils.

(Magnetic shielding) There are two methods for magnetic shielding: one is to cover the entire area except the printed coil where the magnetic flux is incident with a magnetic shielding plate, and the other is to cover the lead wire of a magnetic flux transfer circuit or magnetic flux transformer with a magnetic shielding tube and to cover the inside of the circuit or transformer. There is a method in which a coil that transmits magnetic flux to the skid and the skid are covered with a magnetic shielding plate.

The magnetic shielding plate and magnetic shielding tube are preferably made of a high magnetic permeability material or μ metal.

(Magnetic flux gradiometer) The magnetic flux gradiometer of the present invention has a second printed coil wound in the opposite direction to the probe coil or pickup coil on the opposite side of the object to be measured with respect to the probe coil or pickup coil. It is.

(Printed Coil) It is desirable that the probe coil (also referred to as a pickup coil) or the pickup coil (also referred to as a probe coil) be a printed coil.

An example of a method for manufacturing a printed coil is as follows.

(2) A mask prepared in advance according to the shape of the printed coil is placed on the substrate, and a superconducting material target placed in front of the mold is sputtered to form a superconducting thin film coil-like object on the substrate.

■ Electron beam evaporation instead of sputtering in ■ above.

laser sputter deposition, MBE deposition, MOCVD deposition, spray virolysis deposition, or a combination thereof;
Or a combination of these and sputtering is performed.

■ A mixture with plasticity (that is, a superconducting material) that becomes a superconductor is cold-worked into a wire rod, the wire rod is transformed into a coil shape, and then printed into a coil shape using a doctor blade method and fired.

(2) A mixture (of superconducting materials) with plasticity that will become a superconductor is made into a plate material by a doctor blade method, and the plate material is made into a printed coil shape by a direct processing method, and then fired.

■ A negative image of the printed coil is formed on the surface of the substrate, and then a thin film is applied to the entire surface, and then the negative image formed and the superconducting thin film applied thereon are removed in a negative pattern using a solvent. A coil of superconducting thin film is formed as the remainder on top.

■ A positive pattern of printed coils is formed on the superconducting thin film on the surface of the substrate, the negative pattern is removed by etching, and the remaining resist forming the surface of the positive pattern is removed with a solvent or ashed by a dry etching process.■ Substrate The superconducting thin film above is sputtered or ion-implanted with a focused ion beam, and the beam is scanned.

■ Heats the thin film on the substrate by irradiating it with a laser beam.

By scanning, a negative pattern is created at a temperature that forms a non-superconducting phase, and a positive pattern is created at a temperature that forms a superconducting phase.

■ A coil pattern is obtained by making a paste of superconducting material and screen printing it onto a substrate.

[Co., Ltd.] Silk screen printing and photosensitive resin are used to form the negative images and coil patterns.

■Heat treatment in oxygen or air.

(Core) The core of the present invention is made of a soft magnetic material. This manufacturing method is characterized by removing nonuniformity in internal stress due to point defects, lattice defects, and impurity precipitation through heat treatment, and adjusting the direction of easy magnetization by cooling in a magnetic field, rolling, and recrystallization.

(Deterioration Detection Method) The deterioration detection method of the present invention applies a magnetic field to an object to be measured, monitors changes in the magnetic properties specific to the object, and determines the degree of deterioration of the object from the change in magnetic characteristics. The deterioration detection method is characterized in that the change in the magnetic properties is measured using the magnetometer of the present invention.

[Effect]

In a superconducting quantum interference element magnetic transformer (magnetic flux transfer circuit), the self-inductance of the pickup coil is generally reduced by using a printed coil made of a superconducting ribbon as the detection coil. Furthermore, the reduction in self-inductance increases the magnetic flux transmission rate ε (sensitivity) of the magnetic flux transformer (magnetic flux transfer circuit), and as a result, the signal resolution of the magnetometer improves. In addition, by equipping the printed coil with a printed coil core made of soft magnetic material, magnetic lines of force are guided into the core, which suppresses leakage of magnetic flux passing through the superconducting loop of the printed coil, and prevents leakage of magnetic flux from external magnetic fields. Because the noise can be reduced, the sensitivity of the magnetic sensor is further improved. Furthermore, changes in magnetomotive force due to the α' phase and G phase precipitated in the ferrite phase of ferrite-containing stainless steel used in a high-temperature environment can be measured by installing the pickup coil near the measurement sample.
It is measured with high accuracy by the magnetic sensor (magnetic flux meter) of the present invention.

〔Example〕 Examples of the present invention are described below.

(Configuration of magnetic sensor) Fig. 1 and Figs. 20 to 25 show the magnetic flux meter (
FIG. 2 is a schematic configuration diagram of a magnetic sensor. In the embodiment shown in FIG. 1, a superconducting quantum interferometer (skid) 1 was provided at the top, and a pickup coil 3 made of a printed coil was placed near the measurement sample 2. The superconducting quantum interferometer (skid) 1.
The pickup coil 3 will be explained using a shield diagram to shield external noise.

99. As shown in FIG. 1, the approximate dimensions of the device are a diameter W of 20 to 200 m and a height H of 50 to 200 m. In addition, the thickness A of the pickup coil 3 is 50 μm to 3 m.
and the sample 2 are placed in close contact with each other or close to each other. The distance B between the pickup coil 3 and the sample 2 is approximately 100 μm to 5III.

Although the pickup coil 3 can be formed of either a thin film or a thin plate, FIGS. 1 and 20 to 25 illustrate the case of a thin plate as an example. In the embodiment shown in FIG. 20, in order to define the distance between the pickup coil 4 and the measurement sample 2, a member 5 whose relative magnetic permeability is close to 1 and suppresses magnetic flux absorption loss is used.
Insert. Suitable materials for the member 5 include organic insulating materials and inorganic insulating materials such as polyethylene and Teflon.

The printed coil enables tracking of minute magnetic flux changes in the measurement sample 2, improving the sensitivity and signal resolution of the magnetic sensor.

In the embodiment shown in FIG. 21, a printed coil core made of a soft magnetic material (1
)6 was provided. Examples of soft magnetic materials include permalloy (PC) with low hysteresis loss and high hardness permalloy (HP).
Iron-nickel alloys such as C), sendust, or ferrite materials that are resistant to high frequencies are effective. By installing this printed coil core (1) 6, the printed coil 4
This suppresses the leakage of magnetic flux passing through the magnetic sensor and increases the signal strength of the magnetic sensor. In the embodiment shown in FIG. 22, the printed coil core (2) 7 is fitted between the superconducting ribbons of the printed coil 4, and the printed coil 4 and the printed coil core (
2) 7 were housed on the same plane. In addition, in the embodiment shown in FIG. 23, a printed coil core (3) 8 is installed, which is an integral part of the printed coil core (1) 6 shown in FIG. 21 and the printed coil core (2) 7 shown in FIG. 22. did. Furthermore, the second
In the embodiment shown in FIG. 4, the core between the superconducting ribbons of the printed coil 4 shown in FIG. 23 is extended toward the measurement sample side, and a printed coil core (4) 9 in contact with the measurement sample 2 is provided. With this printed coil core (4) 9, the lines of magnetic force emitted from the measurement sample 2 are guided directly into the core, thereby reducing leakage magnetic flux and canceling noise, improving the sensitivity of the magnetic sensor.

FIG. 25 is a schematic diagram of a magnetic flux gradient meter. It has a magnetic flux transfer circuit in which two pickup coils with equal self-inductance are connected in series, one lower pickup coil 10 is set on the side of the constant object to be measured, and the other upper pickup coil is set on the side opposite to the side of the object to be measured. The coils 11 are arranged in opposite directions. In this case, since the uniform magnetic fields cancel each other out, only the difference in the magnetic fluxes picked up by the two pickup coils becomes the signal transmitted to the 5QVID. Although various methods of arranging the cores can be considered, for example, there is a method of arranging the cores 17 as shown in FIG. 25. When using this magnetic flux gradiometer, α generated in the ferrite phase
It is possible to examine the distribution of the ' phase and the G phase in the depth direction, and a uniform external magnetic field is subtracted, so it is more convenient for shielding than the above-mentioned magnetometer, and is also advantageous in terms of S/N.

FIG. 25 shows the sensitivity of the magnetic sensor and a lower printed coil 10 provided near the measurement sample 2, and an upper printed coil 11 wound opposite to the lower printed coil on the opposite side of the lower printed coil 10 from the measurement sample 2. . These two printed coils make it possible to measure magnetic flux gradients, and while the printed coils described above only measure insulation values, it is now possible to measure relative values and detect magnetic flux directions. It is advantageous in

The magnetometer shown in Figure 25 is equipped with two pickup coils, so while the magnetometer described above measures absolute values, it can measure relative values and detect the direction of magnetic flux. It becomes possible to measure the slope.

FIG. 26 shows a magnetometer of the present invention equipped with a cooling system.A magnetic baffle plate 281 of the magnetometer having the shape shown in FIG. 23 is surrounded by an inner vacuum container 290. The inner vacuum container 290 is installed in the outer vacuum container 291, and the vacuum is evacuated through the flexible vacuum tube 300.6 By evacuating to vacuum, the magnetometer and the object to be measured are insulated.
The inner wall of the reactor pressure vessel, which is one of the measurement samples 2, is immersed in reactor water at about 60 degrees during normal inspection.

In order to increase the insulation efficiency between the reactor water and the magnetometer, a multilayer insulation layer 310 is bonded to the inside of the outer vacuum vessel. Inside the inner vacuum container 290, a flexible supply tube 320 is provided.
Liquid helium or liquid nitrogen is then introduced and discharged from the return flexible pipe 330. With these cooling media, the printed coil 4, lead wire 24, coil S25 and r
It is cooled to a temperature that allows it to operate with fSQVID28 and superconductivity. Here, the printed coil 4 is Nb-Ti based and rfS
If the QVID 28 is made of Nb-based superconducting material, liquid helium is introduced, and if both are made of Y-based, Bi-based, or TQ-based superconducting material, liquid nitrogen is introduced. The outer vacuum container 291 and other structures of the magnetometer are made of stainless steel or reinforced plastic.

FIG. 27 is a sectional view illustrating a case where the magnetometer of the present invention is applied to a nuclear power vessel.

When detecting high temperature aging embrittlement damage on the reactor wall 933 of a nuclear pressure vessel, the outer vacuum vessel 2 equipped with the magnetometer of the present invention
91 to drive shaft (1) 934 and drive shaft (2)
) 935, each drive shaft is connected to gearbox 9
36. The outer vacuum container 291 can be moved in the X direction by an X-axis motor 937, and can also be moved in the Y-direction by a Y-axis motor 938. The gear box 936 is supported by a frame 939, and the frame 939 is fixed to the furnace wall 933 at four locations via suction cups 940 as shown in the figure. Here, the suction between the suction cup 940 and the furnace wall 933 is as follows.
This is done by discharging the reactor water in the suction cup 940 using the vacuum pump 941. Furthermore, the frame 939 has a cable 9
42, and can be moved vertically and horizontally using a crane placed above the pressure vessel with the lid open. Note that 930 is a helium tube connected to the vacuum chamber, and a wiring system connecting the magnetometer to the outside is sealed and housed inside the bellows tube.

Examples of the shapes of the printed coils shown in FIGS. 1 and 20 to 25 are shown in FIGS. 2 to 4. Figure 2 printed coil (1) 1
2 has a shape in which superconducting ribbons are arranged in parallel, with grooves (1) 15 grooves (3) 15 grooves (
3) Although the magnetic flux passing through the groove 17 can be measured, the magnetic flux passing through the groove (2) 16 cannot be measured, so that portion becomes a loss. In the printed coil (2) 13 shown in FIG. 3 and the printed coil (3) 14 shown in FIG. The groove (5) has a magnetic flux signal strength corresponding to that.
19 is further added with the self-inductance due to the inner superconducting ribbon and the corresponding magnetic flux signal strength, and as a result, the groove portion (6) 20 becomes the location where the magnetic flux signal strength is the highest. Since the printed coil (3) 14 has rounded corners compared to the printed coil (2) 13, it has the effect of lowering the resistance due to the shape of the current. The above-described printed coil is effective for samples of metal materials in which precipitates that affect magnetic flux are locally distributed.

(Sensitivity and Signal Resolution of Magnetic Flux Sensor) The pickup coil P23 in FIG. 5 is coupled to a coil 825 via a lead wire 24, forming a superconducting closed circuit 26 as a whole. Also.

The coil S25 has one Josephson junction 27.
IILll, which is coupled to fsQUID 28 at Ms, is the self-inductance of the lead wire, and is sufficiently twisted to make La as small as possible. When the pickup coils shown in FIGS. 2-4 are used, the sensitivity and signal resolution of the magnetometer are improved compared to conventional circular multi-turn pickup coils. The above reason will be explained using FIG. 6.

The self-inductance of pickup coil P23 is Lp
The number of turns is np.

If the cross-sectional area is Ape, the equivalent average diameter is d, the self-inductance of the coil 825 is Lsg, the number of turns is ns, and the self-inductance of -turns is Lpo. ,
The transmission rate ε of magnetic flux from Lso 23 to coil 825 is expressed by the equation shown in FIG. The maximum ε is L p ”
At L s, the maximum sensitivity is as shown in the figure. Therefore, by reducing the self-inductance Lpo of one turn of the detection coil, the sensitivity ε and signal resolution ΔΦ of the magnetometer are improved. Also, pickup coil (1) 15. (2)16.
(3) 17 is np compared to the conventional pickup coil.
1 has the effect of reducing Lpo since the cross-sectional area Ap is small and the average diameter d is large.

Furthermore, as a conventional noise countermeasure, as shown in FIG. -'G' The lead wire 24 of the magnetic flux transmission circuit is magnetized with a magnetic jacket tube 282 made of lead or the like, and the 5QUID28 and 5CI
By shielding the coil S25 that transmits magnetic flux to the UID 28 with a magnetic barrier material 283 such as a PC material, noise caused by external magnetism can be sufficiently suppressed.

(Application example of the present invention) In FIG. 8, the measurement sample 2 shown in FIGS. 1 and 20 to 25 is a ferrite-containing stainless steel 29 used in high-temperature environments such as chemical plants and atomic couplants. When the ferrite-containing stainless steel 29 is used in a high-temperature environment for a long time, the internal structure changes and the strength decreases. As shown in Fig. 8, the change in the internal structure is caused by the ferrite phase 3 in the steel.
This is due to the spinodal decomposition of 0, and the ferrite phase is 30
α' phase 31 and G phase 32 are precipitated inside. When the sample is first demagnetized by a demagnetizer and then magnetized by an excitation system provided with an excitation coil, the lines of magnetic force 33 generated from the ferrite phase 30 become as shown in FIG. However, when using the conventional pickup coil 34, the coil is located far from the sample, making it impossible to measure areas with high magnetic flux density.
The measurement sensitivity of magnetic flux density changes due to minute precipitates was low.

On the other hand, if the printed coil 4 of this embodiment is used.

Since the coil can be brought close to the minute precipitates, α
Changes in magnetic flux density due to 'phase 31 and G phase 32 can be measured with high sensitivity. In addition, by inserting a thin plate material with a relative magnetic permeability close to 1 to hold the printed coil 4, fluctuations in the distance between the printed coil 4 and the ferrite-containing stainless steel that is the measurement sample can be reduced. It is possible to further improve sensitivity.

FIG. 9 shows the distribution of magnetic lines of force when the ferrite-containing stainless steel 29 is measured by the magnetic sensor shown in FIG. 21. Compared to the case of only the printed fill 4 shown in FIG. 8, magnetic lines of force are induced by the printed coil core 6, and leakage magnetic flux is reduced. Furthermore, as shown in Fig. 10, when measured with the magnetic sensor shown in Fig. 24, magnetic field lines (2) 35 that could not reach the printed coil in Fig. 9
is induced by the printed coil core 8 made of a soft magnetic material, so that it is possible to further suppress leakage magnetic flux, improve sensitivity, and reduce noise.

FIG. 11 is a magnetic flux density 37 (B) - magnetomotive force 36 (H) characteristic diagram for the ferrite-containing stainless steel 29, which is a housing material, before being used for a long time in a high-temperature environment. Due to the magnetomotive force 36, the magnetization curve becomes a magnetic hysteresis loop 38
The maximum magnetic east density is 39. Residual magnetic flux density 40. Holding power 41. Alternatively, the hysteresis area 42 can be measured. Further, the maximum magnetic flux density 39 depends on the initial amount of ferrite in the material. In contrast, conventional pickup coils 34
When measured using the printed coil 4 of the present invention, the magnetic flux density 37 - magnetomotive force 36 characteristics are shown in FIGS. 12 and 1, respectively.
Figure 3 is shown. As is clear from the figure, the use of the magnetic sensor of the present invention has the effect of significantly improving the measurement sensitivity of the hysteresis area 42 and the residual magnetic flux density 40.

(Manufacturing method of printed coil) A method for manufacturing a printed coil will be explained.

Sputter deposition is used as a printed coil manufacturing method.

Electron beam evaporation, laser sputter evaporation, MBE evaporation, IL
MOCVD deposition and spray virolysis deposition are used.

A case will be described in which a printed coil is created by sputter deposition. In sputter deposition, a substrate made of, for example, MgO is placed in a manufacturing container, a mask made in advance to match the shape of the printed coil is placed on the substrate, and a sintered body of a superconducting material such as B15iCaCuO is placed in the manufacturing container. A superconducting thin film coil is formed on a substrate by sputtering a target in a rare gas plasma such as argon.

A case where it is created by electron beam evaporation will be explained. Electron beam evaporation is a method in which a metal source made of a superconducting material is irradiated with an electron beam in a high vacuum to evaporate the metal in a vacuum, and the resulting flux is evaporated onto a substrate. The higher the degree of vacuum, the better, for example, about 10"-6 Pa, but even at a degree of vacuum of about 10-8 Pa,
An Nb thin film with a transition temperature Tc = 9.8° can be formed on a quartz substrate at a substrate temperature of 500°C or higher and a film formation rate of several 10 nm/min, and this transition temperature Tc is higher than the bulk. There is.

FIG. 14 is a diagram illustrating a method of forming a thin film printed coil according to the present invention using electron beam evaporation as an example. For example 10
- A mask (mold) 44 prepared in advance according to the shape of the printed coil was placed on a quartz substrate 43 in the vacuum of a BTorr table, heated and rotated at a substrate temperature of 600°C, and vacuum evaporated by electron beam irradiation from above. By discarding the flux 45 of the superconducting constituent material, for example Nb, the mask 4
A thin film printed coil 46 is fabricated in the groove portion 4. Here, a thin film can be grown on a quartz substrate at a deposition rate of about several tens of mm/min, Tc is higher than the bulk, and 9.
8K is obtained.

Laser beam evaporation will be explained. As shown in FIG. 15, a mask (mold) 44 is formed on, for example, an MgO substrate and introduced into a vacuum container 47, 10-t.

Evacuate to a vacuum level of ~10-” Torr. Vacuum vessel 47
A target 49 made of a superconducting material made of a B i S i Ca Cu O sintered body or the like is provided at the center of the substrate 43 , and a laser beam 51 of an excimer laser 50 is irradiated onto the target 49 to generate flux 45 . A thin film printed coil 46 is grown.

Incidentally, the state of the flux 45 is monitored by a quadrupole quality analyzer 52. For example, as a laser source, an ArF excimer laser (
By irradiating a laser beam with an output of 30 mJ/pulse for 20 minutes at 20 Hz using a wavelength of 193 nm,
A superconducting film of μm can be formed. Although high vacuum is required, substrate heating is not required.

As an example of the MBE deposition method, a case will be described in which an oxide superelectric printed coil is formed. In ultra-high vacuum (10-1
0 to 10-'1 Torr), for example, metal Ba, metal Cu,
In a metal rare case, using 5bzOa as a solid oxygen source, this evaporation source is heated and evaporated in vacuum, and each constituent element is deposited one atomic layer at a time on the MgO substrate (100) surface heated to 600°C, for example, to form superconductivity. A film (approximately 2 μm film) is formed.

A case will be described in which a printed coil is manufactured by MOCVD deposition.

The MOCVD method is a method in which a material containing constituent elements of a superconducting material is vaporized, and a film is formed on a heated substrate by transporting each gas with a carrier gas. For example, Y
To fabricate a BCO film, organic compound material Y (
D P M) a, Ba (D P M)2゜Cu (D
P M) 2 is vaporized, and the temperature of each gas is 130-160.
'C, kept at 280-300℃, 140-170℃,
200al/min with Ar carrier gas? into the reaction chamber at a flow rate of At the same time, purified oxygen gas is also sent to the reaction chamber at a rate of 200 to 500 d/min. The substrate temperature is 600°C.

Under these conditions, a VBGO thin film can be synthesized at a growth rate of 0.1 to 10 μm per hour.

Next, a method of manufacturing a printed coil using the spray pielysis method will be explained.

The spray pyrolysis method is a method of spraying an aqueous solution containing a superconducting substance onto a heated substrate in the atmosphere, followed by heat treatment in the atmosphere to obtain a superconducting film.

This method has the advantage that it is possible to form a film even on a substrate with a complicated shape, that the composition ratio of the preparation becomes the film composition as is, and that the film formation speed is fast and it is easy to increase the film thickness. For example, Bi
For system superconductors, Bi, Sr.

An aqueous solution is prepared by mixing nitrates of Ca and Cu in a ratio of 1:1:1:2. Next, when an aqueous solution is sprayed in the air onto a substrate heated to 400° C., the water as a solvent evaporates in an instant. Most Cu nitrates turn into oxides in a few seconds, and some Bi nitrates also turn into oxides. Finally, when heat treatment is performed in air at 860° C. for 10 minutes, the remaining metal nitrates become oxides and a superconductor printed coil is formed.

An example of manufacturing by laser sputter deposition is shown.

Laser sputter deposition is a method of obtaining a superconducting film by irradiating a target made of a superconducting material with laser light and depositing flux sputtered from the target onto a substrate. For example, on an MgO substrate, B i S i Ca Cu
Using an O sintered body as a target, laser light with an output of 30 m J/1 pulse from an ArF excimer laser (wavelength 193 nm) was irradiated at 20 Hz for 20 minutes to form a 1 μm superconducting film. The deposition is performed in an ultra-high vacuum on the order of 10-'' Torr, and the substrate is not heated.

FIG. 16 shows an example of the manufacturing procedure for a thin plate-shaped printed coil. An oxide having a BazY CLI07-F film composition prepared in advance is mixed with a binder and ground. As the binder, an epoxy resin or an organic binder is generally used.

Next, it is made into a wire rod by cold working such as extrusion and transformed into a coil shape. Furthermore, the doctor blade 5
3, a thin plate coil 54 is obtained. Finally, the thin coil 54 is fired to evaporate the binder and sinter the powder.

Here, the doctor blade method will be explained.

The doctor blade method is often used to produce raw sheets for dielectric layers for multilayer capacitors, and in principle consists of ceramic powder, a binder, a plasticizer, and a separating agent.

The slurry (slurry) prepared by uniformly mixing the solvent and defoaming is poured onto a flat metal or glass plate, and the thickness is measured by touching it with a blade with a flat part called a doctor blade. This refers to the method of adjusting the For example, when producing a Bi-based superconductor (e.g. tape-shaped material), the oxide raw materials are Bio, 7Pbo, gSrCatCut, a
C) Mix at a composition ratio of x to produce a high 1゛c phase Bi-based superconductor. This is ground and mixed with an organic binder to create a slurry. Next, using a Decter Blade, apply this slurry onto a substrate such as a polyester film with a width of 125 mm.
m, and a thick superconductor film with a thickness of 100 μm is formed. A ribbon with a width of 3 m and a length of 100 m, for example, is cut out from this thick film in the shape of a printed coil.
Heat treatment is performed at ℃ for about 1 hour.

FIG. 17 shows an example of manufacturing a 1a film-like printed coil. A negative image of a printed coil is produced on the substrate 43 using a photosensitive resin 53-1, and a superconducting thin film 54-1 is first deposited on the entire surface. Furthermore, a thin film printed coil 46 is produced by removing the negative image forming material and the thin film thereon using a solvent.

A case in which a pb-based superconductor is used will be described in more detail below as an example. A negative image of the printed coil is created on the substrate 43 using a photosensitive resin 53. The substrate is made of quartz glass or sapphire, and the photosensitive resin is made of bisazide or N-acetyl-4-nitro-1-naphthylamine.

Next, a superconducting thin film 54 is formed on the entire surface. Superconducting material is pb
The formation method uses vacuum evaporation using resistance heating. Here, pure Pb thin film has low resistance to thermal distortion and poor waterproofness, so Au and In are added in addition to Pb, and in reality, Au (about 4W%) and In (about 5 to 14W
%, e.g., 12 W%), and pb (about 82 to 88 W%, e.g., 84 W%). Furthermore, a thin film printed coil 46 is produced by removing the negative image forming material and the thin film thereon using a solvent.

As the solvent, for example, an alkaline aqueous solution or alcohol is used.

In the above description, the material is one example, and the present invention is also applicable to other materials.

As a similar example, an example of manufacturing a thin film printed coil is shown in FIG. 18. A superconducting thin film 54 is formed on a substrate 43, and a positive pattern 55 of the printed coil is formed using a photosensitive resin 54.Next, a negative pattern is formed by chemical etching. 56 is removed, and the photosensitive resin 54 remaining on the positive pattern 55 is further dissolved and removed using a solvent, thereby forming a thin film printed coil 46.

The printed coils of FIGS. 3 and 4 have intersections where the printed coils overlap. The shape and manufacturing method of the intersection will be explained using the printed coil shown in FIG. 4 as an example.

FIG. 28 is a schematic diagram of the manufacturing process of the intersection of the superconducting printed coil shown in FIG. 4, and FIG. 29 is an overview of the intersection. In FIG. 28, for example, Nb, which becomes superconducting at 9.5, is deposited on a glass substrate 43 by electron beam evaporation (6KW) at a growth rate of 2000 (people/I!1 inch) for 50 minutes to a thickness of 10 μm. A printed coil is fabricated by forming a Nb superconducting film (1) 440 having the following properties. A mask (1) 450 is placed on this superconducting film (1) 44, and a film of about 15 μm is formed by sputtering from above.
An insulating film 460 of iOz or LiF is formed.

At this time, care must be taken to ensure that the insulating film does not become locally thin (several tens of layers), otherwise the insulating film will become a Josephson junction. Furthermore, the mask (1) 45 is removed, a mask (2) 451 is installed as shown in the figure, a 20 μm Nb film is deposited from above by electron beam evaporation (6KW), and the mask (2) 451 is removed. An intersection as shown in the figure can be created. However, by extending the insulating film 460 further in the X direction than the superconducting film (1) 440, the superconducting film (1) 440 and the superconducting film (2) 441 do not form a bridge and become a Josephson junction.

Furthermore, the manufacturing method of the superconducting printed coil will be explained.

FIG. 30 shows another embodiment of the method for manufacturing a superconducting printed coil.

A Ti (circuit pattern) 562 is fitted into the groove of the NbH substrate 561 in which a groove corresponding to the negative of the circuit pattern is formed. Cu-S is placed on this Nb substrate in which Ti has been inlaid.
The n-alloy metal plates 563 are overlapped and bonded to form a laminate of the Nb substrate sandwiching Ti and the Cu--Sn alloy plate. This laminate is irradiated with a laser beam along the Ti pattern to cause a diffusion reaction between Nb and Sn on both substrates, and diffuse Ti to form N b s Sn −
NbgS around 0 to obtain the superconducting circuit 564 of T i
The n layer (layer outside the pattern) is removed by chemical means (etching, etc.) or cutting.

Further, as an example of manufacturing a Y-B a-Cu-0 series coil, there is a method as shown in FIG. 31. First, Y-Ba
- A substrate 566 is made by rolling an ingot 565 of a Cua-based alloy. A shielding sheet 567 made of a polymeric material such as polyimide and having a circuit pattern cut out is pasted onto this substrate 566.

When this substrate with a sheet is immersed in an alkaline aqueous solution such as NaOH and electricity is applied to the aqueous solution, an oxide M5 is formed by anodic oxidation in the cutout portion of the sheet (exposed portion of the substrate).
67 is formed. Next, this substrate is heated to 800 to 9
Heat treatment at 50°C for 5 to 100 hours. Through this treatment, oxygen in the oxide layer and each element of the substrate diffuse and react with each other, and the oxide-based superconducting coil 568 (YzBazCuaO
t-8) is obtained. Unnecessary parts may be removed chemically or mechanically.

FIG. 19 shows an example of manufacturing a thin film printed coil. A superconducting thin film 54 is formed on a substrate 43, and a focused ion beam 58 is irradiated onto the thin film from a liquid metal ion source 57 for sputtering. Further, the thin film printed coil 46 is manufactured by controlling the focusing 60 of the focused ion beam 58 using an Einzel lens 59, controlling the ion beam scanning 61, and controlling the positioning 62 of the substrate 43. Although there are various embodiments, for example, a superconducting material YBazCuaO7-δ on a glass, quartz, or YSZ (yttoria stable zirconia) substrate can be processed using Ca or Au as a liquid metal ion source. Of course, it can also be applied to other materials. According to the embodiments of the present invention, there is no need to significantly increase the conventional manufacturing process of superconducting thin films and wires.

This has the advantage that printed coils can be manufactured.

In the above example of manufacturing a thin film printed coil, if the substrate for manufacturing the printed coil is a high magnetic permeability material that does not cause phase separation of the thin film when used as a substrate, the core can be formed without removing the manufactured printed coil from the substrate. It has the advantage that it can be used as Furthermore, by adopting a thin substrate with low magnetic permeability, the substrate can be used as a member for defining the distance between the substrate to be measured and the printed coil.

〔Effect of the invention〕

According to the present invention, in a magnetic sensor consisting of a superconducting quantum interferometer and a magnetic flux transformer, it is possible to improve the magnetic flux transmissibility of the magnetic flux transformer and the sensitivity and signal resolution as a magnetometer, so that it can be used in chemical plants, atomic couplants, etc. This has the effect that the degree of deterioration of ferrite-containing stainless steel used in high-temperature environments can be detected with high accuracy.

[Brief explanation of the drawing]

1, 20, 21, 22, 23, 24, and 25 are longitudinal sectional views, FIG. 2, and 3, respectively, of magnetometers according to embodiments of the present invention. . Fig. 4 is a main perspective view showing examples of printed coils used in the present invention, Fig. 5 is a principle configuration diagram of a magnetometer according to an embodiment of the present invention, and Fig. 6 is a flow diagram showing a detection example of the present invention. , FIG. 7 is a schematic cross-sectional view of a magnetometer that suppresses external magnetic noise, FIG. 8 is a schematic cross-sectional view showing the difference in magnetic flux measurement states between the conventional method and the method of the present invention, and FIG. 9 is a schematic cross-sectional view of the magnetic flux meter that suppresses external magnetic noise. A schematic cross-sectional view showing the state of magnetic flux measurement by the magnetic sensor, Figure 10 is the 24th
Fig. 11 is a characteristic diagram showing the magnetic hysteresis of the ferrite-containing stainless steel receiver and insert material, and Fig. 12 is the ferritic stainless steel deteriorated material. FIG. 13 is a characteristic diagram showing the magnetic hysteresis measured by the conventional method, FIG. 13 is a characteristic diagram showing the magnetic hysteresis measured by the method of the present invention on deteriorated materials, and FIGS. A schematic diagram of an apparatus showing an example of a method for manufacturing a thin film printed coil, FIG. 16 is a flow diagram showing an example of the manufacturing procedure for a thin film printed coil, and FIGS. 17 and 18 are respectively A flowchart showing an example of a method for manufacturing a thin film printed coil, Fig. 26 is a schematic diagram of a magnetometer in which a superconducting material that operates at liquid helium temperature is used for a magnetic flux transformer and 5QVID, and Fig. 27 is a diagram of the present invention. A schematic diagram of detecting the magnetic characteristics of the reactor wall of an atomic couplant using the magnetometer of the invention, FIG. 28 is a diagram showing a method for manufacturing the intersection of the printed coil of the invention, and FIG. 29 is a diagram of the printed coil of the invention. A general view of the intersection of the coils, FIGS. 30 and 31. FIG. 3 is an explanatory diagram showing an example of a method for producing each printed coil. 1...Superconducting quantum interferometer, 2...Measurement sample, 3...
・Pickup coil, 4...Print coil, 5・
··Element. 6... Core for printed coil (1), 7... Core for printed coil (2), 8... Core for printed coil (3), 9... Core for printed coil (4), 10.
...Lower printed coil, 11... Upper printed coil, 12... Printed coil (1), 13... Printed coil (2), 14... Printed coil (3),
15...Groove (1), 16...Groove (2), 17.
...Groove (3), 18...Groove (4), 19...Groove (5), 20...Groove (6), 21...Superconducting ribbon (1). 22...Superconducting ribbon (2), 23...Pickup coil P, 24-...Lead wire, 25...Coil S
, 26...Superconducting loop, 27...Josephson junction, 28-rfsQUID, 28-1-Magnetic barrier plate, 28-2...Magnetic barrier tube, 28-3...Magnetic barrier Material, 29... Ferritic stainless steel, 30... Ferrite phase, 31... α' phase, 32...
...G phase, 33... Lines of magnetic force, 34... Conventional pickup coil, 35... Lines of magnetic force (2), 36... Magnetomotive force, 37... Magnetic flux density, 38... Magnetic hysteresis loop , 39... Maximum magnetic flux density, 40... Residual magnetic flux density, 41... Holding force, 42... Hysteresis area, 43... Substrate, 44... Type, 45... Flux, 46 ... Thin film printed coil, 47... Vacuum container, 48... Vacuum exhaust, 49... Target,
50... Excimer laser, 51... Laser light, 52
... Quadrupole mass spectrometer, 53 ... Doctor blade, 54 ... Thin plate coil, 53-1 ... Photosensitive resin. 54-1...Superconducting thin film, 55...Positive pattern,
56... Negative pattern, 57... Liquid metal ion source, 58... Focused ion beam, 59... Einzel lens, 60... Focusing control, 61... Ion beam scanning control, 62... ...Positioning control, 63...Inner vacuum container, 64...Multilayer insulation material, 65...Flexible tube for vacuum, 66...Flexible tube for supply, 67
... Return flexible tube, 68 ... Outer vacuum container, 69 ... Furnace wall, 70 ... Drive shaft (1), 7
1... Drive shaft (2), 72... Gear box, 73... X-axis motor, 74... Y-axis motor, 75
... Frame, 76... Suction cup, 77... Vacuum pump, 78... Cable, 79... Board, 80...
Superconducting film (1), 81... Superconducting film (2), 82...
・Mask (1), 83...Mask (2), 84...
Insulating film, 85...Nb substrate, 86...Ti (
circuit pattern), 87... Cu-8n alloy metal plate,
88-NbaSn-TiH superconducting circuit, 89...
- Ingot, 90... Substrate, 91... Polymer material shielding sheet, 92... Oxide layer, 93... Oxide-based superconductor coil. At the 22nd opening! ：Electric conductivity"〉(2) 7th figure Otoyahe (1 net, 28.3...
Magnetic shielding power No. 42 - E steresis ω Sei 44 - Mask 4S... Franks 46 - JHU Large Besonto Coil No. 7.5 Country 49゛"Target, 50 ・Eyashimashi - γ No. Figure, 54---Four large coils for bookkeeping. Awant coil's neck. The final sage of the Neka゛° turn, 5.
, S・-Bosino\°y-n,! ;6・-Kikahan 05-N service■,,S9...Finzel LnI Fig.6・-Printed coil m core (υ Quick concave 7 Core for printed coil (2) 23rd Su δ・-・7゛11 Root coil (3) 1st 1111-f print fill core (4) 23rd-10 lower part 1/...J: Anp print coil 1st η?5 block...Tsum -4 2nd δ Surplus rate mouth fist: 31 -0-Ito work with one chair■ Rate coldness

Claims (1)

[Claims] 1. The probe coil comprises a magnetic flux transfer circuit disposed so as to face the object to be measured, and a superconducting quantum interference element disposed within the reach of the magnetic flux generated from the circuit; A magnetometer characterized by applying a printed coil to. 2. A magnetic flux transformer in which a pickup coil is arranged to face the object to be measured, and a superconducting quantum interference element provided within the reach of the magnetic flux generated from the transformer, and a printed coil is applied to the pickup coil. A magnetic flux meter characterized by: 3. A probe coil is provided with a magnetic flux transmission circuit arranged so as to face the object to be measured, and a superconducting quantum interference element provided within the reach of the magnetic flux generated from the circuit, and a printed coil is applied to the probe coil. In addition, a magnetometer characterized in that a core made of a soft magnetic material is used in the probe coil. 4. A magnetic flux transformer in which the pickup coil is arranged to face the object to be measured, and a superconducting quantum interference element provided within the reach of the magnetic flux generated from the transformer, and a printed coil is applied to the pickup coil. In addition, a magnetic flux meter characterized in that a core made of a soft magnetic material is used in the pickup coil. 5. The probe coil is equipped with a magnetic flux transmission circuit placed so as to face the object to be measured, and a superconducting quantum interference element provided within the reach of the magnetic flux generated from the circuit, and the probe coil is provided with a core made of a soft magnetic material. A magnetic flux meter characterized by the combined use of. 6. The pickup coil is equipped with a magnetic flux transformer arranged so as to face the object to be measured, and a superconducting quantum interference element provided within the reach of the magnetic flux generated from the transformer, and the pickup coil is provided with a core made of a soft magnetic material. A magnetic flux meter characterized by the combined use of. 7. A probe coil that forms part of a magnetic flux transmission circuit and is characterized in that it is in the form of a thin film. 8. A pick-up coil that forms part of a magnetic flux transformer and is characterized in that it is in the form of a thin film. 9. A core that forms a magnetic flux transmission circuit in combination with a probe coil and is made of a soft magnetic material. 10. A core that forms a magnetic flux transformer in combination with a pickup coil and is made of a soft magnetic material. 11. A magnetic flux transfer circuit characterized by having a portion in which a thin film probe coil is combined with a core made of a soft magnetic material. 12. A magnetic flux transformer characterized by having a portion in which a thin film pickup coil is combined with a core made of a soft magnetic material. 13. A magnetometer comprising a member that defines a distance between the probe coil according to claim 1, 3, or 5 and the object to be measured. 14. A magnetometer comprising a member for defining a distance between the pickup coil according to claim 2, 4, or 6 and the object to be measured. 15. A deterioration detection method in which a magnetic field is applied to an object to be measured and changes in the magnetic characteristics specific to the object to be measured are monitored, and the degree of deterioration of the object to be measured is determined from the change in the magnetic characteristics,
A deterioration detection method, comprising measuring the change in the magnetic properties using the magnetometer according to any one of claims 1 to 6 or claim 13 or 14. 16. A superconducting thin film coil-shaped object is formed on the substrate by placing a mask prepared in advance according to the shape of the printed coil on the substrate and sputtering a superconducting material target placed in front of the mold. How to make printed coils. 17. Electron beam evaporation instead of sputtering according to claim 16;
laser sputter deposition, MBE deposition, MOCVD deposition, spray virolysis deposition, or a combination thereof;
Or a method for manufacturing a printed coil characterized by combining these with sputtering. 18. After forming a plastic mixture that will become a superconductor into a wire by cold working and deforming the wire into a coil shape,
A method for producing printed coils, which is characterized by forming them into printed coils using the doctor blade method and then firing them. 19. A method for manufacturing a printed coil, which is obtained by forming a plasticized mixture that becomes a superconductor into a plate material by a doctor blade method, forming the plate material into a printed coil shape by a direct processing method, and firing it. 20. A magnetic flux characterized in that a second printed coil wound in the opposite direction to the probe coil according to claim 7 or the pickup coil according to claim 8 is provided on the side opposite to the object to be measured with respect to the probe coil or pickup coil. Gradiometer. 21. A method for manufacturing a core, which comprises performing heat treatment and adjusting the direction of easy magnetization when manufacturing the core according to claim 9 or 10. 22. Form a negative image of the printed coil on the substrate surface, then apply a thin film to the entire surface, and then use a solvent to remove the negative image and the superconducting thin film applied thereon in a negative pattern. A method for producing a printed coil characterized by forming a superconducting thin film coil as the remainder on a substrate. 23. A positive pattern of printed coils is formed on the superconducting thin film on the surface of the substrate, the negative pattern is removed by etching, and the remaining resist forming the surface of the positive pattern is removed with a solvent or ashed by a dry process. Manufacturing method for printed coils. 24. A method for manufacturing a printed coil, characterized in that it is obtained by sputtering or ion implanting a superconducting thin film on a substrate with a focused ion beam and scanning the beam. 25. A method for manufacturing a printed coil characterized by irradiating, heating and scanning a thin film on a substrate with a laser beam to create a negative pattern at a temperature that forms a non-superconducting phase and a positive pattern at a temperature that forms a superconducting phase. . 26. A method for producing a printed coil, characterized in that a coil pattern is obtained by making a superconducting material into a paste form and screen printing it on a substrate. 27. A probe coil is provided with a magnetic flux transmission circuit arranged so as to face the object to be measured, and a superconducting quantum interference element provided within the reach of the magnetic flux generated from the circuit, and a printed coil is applied to the probe coil. . A magnetometer, characterized in that the entire part except the side of the printed coil where magnetic flux is incident is covered with a magnetic shielding plate. 28. A magnetic flux transformer arranged such that a pickup coil faces the object to be measured, and a superconducting quantum interference element provided within the reach of the magnetic flux generated from the transformer, and a printed coil is applied to the pickup coil. . A magnetometer, characterized in that the entire part except the side of the printed coil where magnetic flux is incident is covered with a magnetic shielding plate. 29. A probe coil is provided with a magnetic flux transfer circuit arranged so as to face the object to be measured, and a superconducting quantum interference element provided within the reach of the magnetic flux generated from the circuit, and a printed coil is applied to the probe coil. , characterized in that the lead wire of the magnetic flux transmission circuit is covered with a magnetic shielding tube, and in the circuit, a coil that transmits magnetic flux to the superconducting quantum interference device and the superconducting quantum interference device are covered with a magnetic shielding plate. Magnetic flux meter. 30. A magnetic flux transformer arranged such that a pickup coil faces the object to be measured, and a superconducting quantum interference element provided within the reach of the magnetic flux generated from the transformer, and a printed coil is applied to the pickup coil. , wherein the lead wire of the magnetic flux transformer is covered with a magnetic shielding tube, and a coil that transmits magnetic flux to the superconducting quantum interference device and the superconducting quantum interference device in the transformer are covered with a magnetic shielding plate. Total. 31. A magnetic flux transfer circuit having a superconducting quantum interference element, a pickup coil arranged to face the object to be measured, and a core for the pickup coil for suppressing magnetic flux leakage, and magnetically coupled to the superconducting quantum interference element. A magnetic flux meter characterized by: 32. The magnetometer according to claim 31, wherein the pickup coil is a printed coil having a superconductor. 33. The magnetometer according to claim 32, wherein the pickup coil is formed by sputtering. 34. The magnetometer according to claim 32, wherein the pickup coil is formed by laser sputter deposition. 35. Claim 32, wherein the pickup coil is M
A magnetometer characterized in that it is formed by BE vapor deposition. 36. Claim 32, wherein the pickup coil is M
A magnetometer characterized in that it is formed by OCVD deposition. 37. The magnetometer according to claim 32, wherein the pickup coil is formed by spray virolysis deposition. 38. The magnetometer according to claim 31, further comprising a member that defines a distance to the object to be measured. 39. The magnetometer according to claim 31, wherein the magnetic flux transfer circuit includes two pickup coils connected in series with each other and arranged so as to cancel each other's magnetic fluxes. 40. The magnetometer according to claim 31 includes a magnetic shielding plate, and the magnetic shielding plate magnetically shields the superconducting quantum interference element, the lead wire of the magnetic flux transmission circuit, and the coil that transmits magnetic flux to the superconducting quantum interference element. A magnetic flux meter characterized by: 41. A magnetometer according to claim 31, comprising a magnetic shielding plate to magnetically shield the entire device except for the side of the object to be measured to which the magnetic flux of the pickup coil is incident. 42. Pulverizing and mixing a mixture consisting of a material to become a superconductor and a binder; cold-working the mixture into a wire rod; processing the wire into a coil shape; converting the coil-shaped member into A method for manufacturing a printed coil for a magnetometer, comprising: processing the member into a printed coil shape using a doctor blast method; and firing the member processed into the printed coil shape. 43. Forming a thin film that will become the negative pattern of the printed coil using a photosensitive resin on the substrate; Depositing a superconducting thin film over the entire surface of the substrate on which the thin film that will become the negative pattern is formed; A method for manufacturing a printed coil for a magnetometer, comprising the step of removing the thin film constituting the negative pattern and the superconducting thin film using a melting material. 44. Forming a superconducting thin film on a substrate; forming a positive pattern of a printed coil on the superconducting thin film using a photosensitive resin; removing a negative pattern portion of the superconducting thin film by etching; A method for manufacturing a printed coil for a magnetometer, comprising the steps of removing remaining photosensitive resin with a solvent. 45. The method of manufacturing a printed coil for a magnetometer according to claim 44, wherein the etching is chemical etching. 46. The method of manufacturing a printed coil for a magnetometer according to claim 44, wherein the etching is plasma etching. 47. The method of manufacturing a printed coil for a magnetometer according to claim 44, wherein the etching is performed using a focused ion beam. 48. Applying a magnetic field to the object to be measured, comprising a pickup coil arranged to face the superconducting quantum interference element and the object to be measured, and a core for the pickup coil that suppresses magnetic flux leakage, the superconducting quantum interference element and the magnetism A deterioration detection method in which a change in magnetic characteristics specific to the object to be measured is measured by a magnetometer comprising a magnetic flux transfer circuit that is coupled to the object, and the degree of deterioration of the object to be measured is determined from the change in the magnetic characteristic.