JP2669308B2 - Amorphous coating and method for forming the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION The present invention uses an amorphous metal as a mother material.
Of the amorphous coating that is formed as a coating on the surface of the material
The present invention relates to a molding method. [0002] 2. Description of the Related Art Amosphas metal has high mechanical strength.
Low thermal expansion coefficient,ChemistryCorrosion resistance and abrasion resistance
Because it has excellent characteristics, it can be applied to various parts.
Is being done. Also, the moss of Amosfus metalMindCharacteristic
It is being used in many products as a magnetic material.
You. For example, as a magnetic material for torque sensors,
Are being used. As a method of forming such an amorphous
For that reason, many methods have been considered from the past. example
For example, in Japanese Patent Laid-Open No. 57-211030, a thin strip is formed.
Adhesive (epoxy) on the surface of the drive shaft
Bonded by xy resin or soldering
A method is disclosed. Further, in Japanese Patent Laid-Open No. 58-90345.
Is an amorphous metal ribbon fixed as a magnetostrictive material
A torque sensor is disclosed. [0005] SUMMARY OF THE INVENTION However, Japanese Patent Application Laid-Open
In the method of Japanese Patent Publication No. 57-211030, the drive shaft and the
To obtain a sufficient adhesive strength of the bonded part with the thin metal ribbon.
As it cannot be used, peeling due to fatigue after long-term use,
Or magnetism associated with stressMindChanges in characteristics do not occur sufficiently
There will be a problem of "no". Furthermore, JP-A-58-90345
The report discloses a specific method for fixing amorphous metal.
Not. Therefore, the object of the present invention is to solve the above problems.
In view of this, amorphous metal is used as the coating layer on the surface of the base metal.
Solidly fixed amorphous coating layer and method for forming the same
It is to provide. [0007] Therefore, according to the present invention,
1 inventionMetal base material placed in the center of the cylindrical container
And in the space between the base material and the container,Particle size is 0.
Amorphous metal powder of 01 μm to 200 μmFilling
And after sealing the container,Molding pressure of 0.7-80 GPa
High speed machiningIn the containerBy applying,
Amorpha for forming a coating layer of amorphous metal on the surface
The present invention provides a method for forming a sheathed body. Further, as a second invention, a base material and a base material
High energy with a molding pressure of 0.7-80 GPa on the surface
Amorpha molded by Gee-speed processing
To provide an amorphous coating comprising a metal coating layer.
Things. Here on forming amorphous coating
In particular, points to be noted are described. Generally, the inside of the base metal is
Stress, grain boundaries, non-uniform composition, lattice defects, impurity deposition
It is uneven due to various reasons such as the appearance. For this reason
Permeability differs depending on the location and direction.
Become. Therefore, simply place the amorphous metal on the surface of the base metal.
And try to fix them by high energy speed machining
Then, between the amorphous metal powder and the atoms,
Problems such as child defects, grain boundaries, non-uniform composition, and precipitation of impurities
Live. The problem is that they are not firmly fixed
It is a cause. Therefore, in the present invention, the following points
The amorphous coating is formed by paying attention to the above. First of both
Before high-speed machining,
No. 1 is an inert gas when producing amorphous metal powder.
The atmosphere is argon (Ar). this is
No oxide layer is formed on the surface of amorphous metal powder
That's why. Second, amorphous metal powder
The final particle size is 0.01 to 200 μm. This is high
Amorphous metal ribbon and base material are good during energy speed processing
This is because they are firmly fixed. Third, the coating layer is formed
Surface of base metal and amorphous metal powder
, 10^-2Plasma treatment in a hydrogen atmosphere of -10 Torr
Manage. This is the same as removing the oxide layer on the surface.
To improve the stickiness during high energy speed machining
This is for activating the surface. Fourth, during high energy speed machining
The energy per unit time depends on the base metal and amorpha.
A method of uniformly adding to the metal is used. This is amorpha
Metal powder and powder, amorphous metal powder and base material table
Because the surfaces are bonded and fixed evenly in any part
is there. Fifth, high energy after high energy speed processing
Base metal and amorpha generated by the addition of ghee
Strain at the boundary with metal or amorphous metal grain
The heat treatment to remove the strain inside the child is an inert atmosphere.
Do inside. And the heat treatment temperature is notCrystalAmorph that is quality
It shall be performed at a temperature at which the gas metal does not crystallize. By paying attention to the points described above,
Ming is an object in which amorphous metal is firmly adhered to the surface of the base metal.
Morphos dressings can be formed. [0012] By adopting the above molding method,
High energy by high energy speed machining
Can be reliably transmitted to the base metal, and
Amorphous coating layerStrongly adhered amorphous coating
You can get the body. [0013] 【Example】 (First Example) When the amorphous metal is powder,
Will be described. Here, the amorphous metal is a metal element
Iron (Fe), cobalt (Co), nickel (Ni),
At least one of chromium (Cr) and silicon (Si)
Amorphous metal powder as the main component. This amorph
Asus metal powder is composed of metal elements and metalloids (phosphorus (P), carbon
(C), boron (B), silicon (Si), etc.)
Gold or iron-based elements and rare earth metals (Gd, Tb, Dy
Etc.) can be used. Representative Amol
Fe as the fass metal powder₇₀Co_FifteenB_Fifteen, Fe ₈₀B
_FifteenBi_Five, Fe₄₀Ni₄₀P₁₄B₆, Fe₇₀Co_FifteenB_Fifteen,
Co₈₀B_FifteenC_Fifteen, Ni₇₈B_TwoSi_Tenand so on. (here
Numerical values such as 70, 15, 5 and the like indicate atomic%. ) Amol
The particle shape of fass metal powder is spherical and fine with excellent symmetry.
Long gourds are good, but in some cases flakes and
It may be a bon shape or a linear shape. In the present invention, the particle size of the amorphous metal powder is
One having a thickness of about 0.01 to 200 μm is used. Where 0.
The reason why the numerical value is limited to 01 to 200 μm is as follows.
is there. That is, if it is less than 0.01 μm, it is
The volume of the powder particles is reduced as a whole. Therefore, do not use explosive molding
Amorphous when subjected to high energy speed machining
The heat generated on the surface of metal powder particles is absorbed inside the particles.
It will be insufficient to take it. As a result, it exists on the surface of the particle
The amorphous nature of ultrafine amorphous metal powder is lost.
This is because it becomes easier. If it exceeds 200 μm, powder
Since the packing density is low and the bondability of powder particles is low
It is. Amorphous with a particle size of 0.01 to 200 μm
The metal powder can be produced by a commonly used method. For example, times
Rolling roll method, atomizing method, spray method, spark method,
A cavitation method or the like can be used. Particles
Spherical amorphous metal powder is spark method, atomized
It can be manufactured by the method. Amorphous metal powder by the rotating roll method
A typical example of manufacturing the will be described more specifically.
That is, 65 parts of Fe, 15 parts of Co, 15 parts of B, and 5 parts of Si
Powder with a composition and a particle size of 1 to 1000 μm into a ball mill
After mixing, 13.56MH_Z14 by high frequency heating
Dissolve above 00 ° C. After that, this molten metal is
It is formed in a rod shape of 0 mm. Next, this rod shaped body is made of quartz.
Or 1350 ° C to 1400 ° C in a ceramic container
Dissolve by heating at the temperature of. High frequency melting is preferable for heat melting.
Next, rotate the molten metal formed as above from the nozzle of the container.
While jetting it toward the roll and crushing it on the water surface,
0^Four-10⁶Quench at ℃ / sec. This makes the particle size
Manufactures amorphous metal powder of 0.01-200 μm
You. In this way, when manufacturing amorphous metal powder,
Argon (Ar) gas so that no oxide layer is formed on the surface
Is preferred. Particles of powder produced in this way
The shapes are spherical, rugby ball, elliptical, peanut
It can be shaped like a box. Next, the above amorphous metal powder is
The case of coating as a magnetic material for
This will be described in detail. In this example, the above-mentioned powder
On the surface of the drive shaft that is the base material on which the coating layer is formed.
Then, by processing both with high energy speed,
To form an amorphous coating. FIG. 1 drives the amorphous coating of the present invention.
FIG. 2 is a schematic diagram of a torque sensor used as a shaft, and FIG.
Partial external view showing the arrangement state of magnetic coils, FIG. 3 is II of FIG.
Sectional drawing which follows the I-III line, FIG. 4 is a partially enlarged view of FIG.
is there. As is clear from Fig. 4, high energy speed machining
In this condition, the amorphous metal powder is
Covered by being fixed to the surfacelayerIs formed. High energy here
Energy-speed machining is an extremely short time (generally 10^-3~
10^-8Energy in a very short time of about 2 seconds)
It means a processing method of discharging and molding. High energy
-If speed machining is used, the energy
The energy speed is so high that it generates too much heat
Can be solidified without letting Therefore,Amorphous
Can be solidified without damage. Due to high energy speed machining
The forming pressure is preferably 0.7 to 80 GPa. Molding pressure here
If the force is 0.7 GPa or more, integral molding is possible,
More preferably, the pressure exceeds 1.5 GPa,
A quality coating material can be obtained. Typical high energy
-As speed processing, there is explosion molding processing. Explosion molding processing
Is the impact of TNT explosives caused by the dynamite explosion
This is a method of instantaneously applying pressure by a striking wave or gas expansion. LOL
In general, the molding is performed by exploding an explosive in water. explosion
The molding pressure is the depth from the water surface to the explosive,
Distance to shape, amount of gunpowderThereforeCan be adjusted. Explosion molding
Is preferably 0.7 to 80 GPa.
If a higher pressure is applied, the amount of heat during joining increases.
Too much and some of the amorphous metal crystallizes
If the fuzziness is easily lost and the pressure is lower than that
This is because the particles do not bond sufficiently. Specifically, first, the above-mentioned amorphous metal
Powder containing 10^-2-10 Torr reducing atmosphere
In air, perform reduction treatment under plasma for 10 to 30 minutes
You. The temperature at this time is such that the amorphous metal crystallizes.
Temperature (450 ° C)
You. As a result, the powder surface of the amorphous metal becomes oxide
The layer is removed at the same time it is activated. Again
The drive shaft of diameter 20 mm and length 250 mm is also plasma
Activated by treating below. At this time, as the drive shaft material
A Vickers hardness of 100 to 300 Hv is suitable.
It is. It is an iron-based or Ni-based metal such as S4
5C, S55C, SUS416, SUS304, SUS
316 is good. 3 reasons to limit Vickers hardness
At over 00Hv, the surface of the base metal does not deform, so powder
Sticking because the powder cannot easily get inside the base metal
The strength is poor. If it is less than 100Hv, the base material will change during explosion compression.
This is because the shape cannot be maintained because of the shape. Next, the center of the cylindrical container of copper or iron-based material
The drive shaft on which the above-mentioned processing has been performed is arranged in the. And drive
Vibration (5-100Hz) in the space between the driving shaft and the cylindrical container
Amorphous metal powder that has been subjected to the above treatment while giving
To about 50% of the theoretical density, vacuum degassing, and then sealing the container.
To seal. Then explode the sheet explosive,
A pre-compression treatment is performed on the fass metal powder and the drive shaft. Next
Place the container in the center of the explosive in the molding chamber
Make a shape. At this time, the point explosion due to the detonator is the explosive lens
Resulting in a plane explosion wave that propagates simultaneously to the top surface of the main explosive
And detonate the main explosive. The powder in the container is
As a result, they are compressed simultaneously in the radial and axial directions. And
The morphus metal powder is affected by the shock wave received through the container.
Firmly adhered to each other and ensure that the powders are in contact with each other
Is fixedly bonded to. This explosion shock wave causes the powder to collide.
The time to be hit is 10^-6On the order of seconds. Also at this time
Is 0.7 to 80 GPa. FIG. 5 shows the pressure received by this impact action.
Based on the ratio of particle size of amorphous metal powder as shown
Then, control is performed as described below. As shown in FIG.
When the particle size ratio of such powder is 50-200 μm
Pressure is about 10-80 GPa)
You. When the particle size ratio is as shown in FIG.
5 to 20% of 50 μm, 50 to 130 μm
Is 80 to 95%), apply a pressure of about 8 to 50 GPa
You. When the particle size ratio is as shown in FIG.
0.1-0.5% of ultrafine powder of ~ 0.08 μm,
5 to 30% of 10 to 40 μm, 50 to 130 μm
Is 55 to 95%) is 0.7 to 10 GPa.
Apply pressure. Then, the amorphous metal powder is theoretically dense.
90% to 99.9% of the density, and it becomes solid on the drive shaft surface.
Be worn. Also, consider the deformation of the base material during explosive molding.
And the pressure should be small. Therefore, FIG. 5 (c)
The one using the amorphous metal powder with the particle size ratio shown in
Preferably, the pressure is 0.7 to 10 GPa.
You. In this explosion pressure range, the boundary between particles is
The lower pressure determines the lower limit, and the upper limit occurs during an explosion
Determined by maintaining the amorphous phase by heat
You. That is, at 90 GPa or more, powder particles and powder at the time of explosion
The heat generated between the particles heats the amorphous particles,
As a result, the amorphous phase changes to a crystalline phase, which rapidly cools.
Even if it does, it will not return to the original amorphous phase. Copper or iron installed on the outer periphery of the drive shaft
After the explosion is formed, the container of the system material is removed by grinding or cutting.
The drive shaft from which this container was removed,
At a temperature that does not crystallize (100 ° C to 350 ° C),
(1000-2000 Oersted) while applying
Heat treatment for 1 to 2 hours significantly improves magnetic properties.
The amorphous coating thus formed is shown in FIG.
As shown, the surface of the drive shaft 4 is coated with an amorphous metal coating layer.
(100-500 μm) is firmly fixed.
You. At this time, the coating phase of the amorphous metal is powder particles
It was a uniform layer with good connection. Amorpha
Inside the metal coating layer, the boundary between the powder particles
There are almost no fields or defects. Also amorphous metal
At the interface between the powder and the surface of the drive shaft that is the base material,
Atoms enter, and bonds between atoms are strong.
Furthermore, as a result of analyzing it by electron diffraction,
You must submit the
It was a fuss state. The following amorphous coating formed in this way
About the operation of the torque sensor using the covering material as a magnetic material
Will be explained. This coating layer was formed as shown in FIG.
A coil 2 for exciting the coating layer near the surface of the drive shaft 4;
A detection coil 3 for detecting the magnetostriction characteristics of the coating layer is provided.
And the electromotive force caused by distortion due to torque transmitted to the drive shaft
Can be measured. The electromotive force is amplified and collected as an electrical signal.
Be sent out. As the detection circuit, the oscillator 11
The signal is converted into a square wave by the drive circuit 12, and the excitation coil 3 is electrically charged.
Add flow. Distortion caused by driving in the detection coil 2
The electromotive force generated at
Sampling by the pulling circuit 14
The torque is detected by comparing with. In the above-described embodiment, the torque
The driving shaft of the sensor, that is, a cylindrical member was used. I
However, the shape of the base material is limited to such a cylindrical shape.
Not an amorphous metal coating layer is formed.
Any other shape may be used as long as it has a surface having a predetermined surface. And
For example, it may be a prism, an ellipse, a flat plate, or the like. Furthermore, mother
The material has a complicated shape like an electromagnetic clutch, magnetic head, etc.
There may be. High energy velocities in base materials of these shapes
When working, especially the impact pressure is applied evenly to the surface.
Needless to say, it is necessary to do so. Further, the amorphous metal of the above embodiment is powder.
Impact pressure for high energy speed machining, etc.
Even if it does, it can be firmly fixed. And this pressure
Since the strength may be small, the base material on which the coating layer is formed
There is no deformation of. As a result, the amorphous coating formed
The dimensional accuracy of the body is improved. Amo formed in the above embodiment
Although the thickness of the coating layer of the rufus coating is different, its characteristics
Does not change, the amorpha formed in the example below is
The measured value of the coating is described. FIG. 6 shows the composition of amorphous metal powder and its composition.
It is a figure which shows the relationship of the magnetostriction characteristic of the coating body obtained as a result.
According to this, according to the present invention, the reference example (conventional nickel alloy
With a 10 μm-thick coating layer formed by a knuckle)
The magnetostrictive properties are all significantly improved. This is the coating layer
Is a value when 5 Kθe (oersted) at 10 μm.
You. FIG. 7 shows No. 1 in FIG. 2 composition (Fe₇₆
B₈Si₁₆) Formed from an amorphous metal powder consisting of
Torque applied to the amorphous coating and its output
FIG. According to this is the drive shaft
The torque applied to the amorphous coating and the resulting torque
The output obtained from the morphus coating layer is the conventional (N
A good proportional relationship is established compared with i plating 20 μm).
I have. In addition, the hysteresis caused by the rise and fall of the applied torque
The difference in cis is also compared with the conventional one (Ni plating 20 μm)
And the sensitivity (the ratio between torque and output) is good. This
As described above, the magnetic properties of the present invention are improved. Next, the amorphous coating of the present invention
Body (No. 2 in FIG. 6) and conventional one (thickness 25 to 30 μ)
m amorphous ribbon is used for driving.
(Bonded with a oxy resin)
Compare. Conventionally, a torque of 14 kg · m is applied to the drive shaft.
The one feels when used with about 100 times of torque applied.
The output has dropped due to a drop in power. However, the above-mentioned invention
Has no change even after using 100,000 times and outputs
Did not decline. Therefore, the present invention is
It has sufficient durability compared to conventional ones. Further, No. 5 to No. 8 in FIG. 7 are corrosion resistant.
It can be used in a corrosion resistant environment. Next
On the surface of the drive shaft (diameter 20 mm, material: S45C)
Amorpha fixed with different amorphous metal powders
CoatingbodyHardness of Vickers and magnetic
Characteristics (Fig. 8), Relationship between coating layer thickness and Vickers hardness
(FIG. 9), Relationship between thickness of coating layer and peeling load (FIG. 10)
Will be described. FIG. 8 shows the magnetic characteristics (saturation magnetic flux) of the present invention.
Density, permeability, coercivity) and Vickers hardness diagram,
Each amorphous coatingbodyHas a thickness of 100 to 500 μm
You. This reduces the thickness of the coating layer formed on the surface of the drive shaft.
Because it is difficult to control strictly on the experiment, 100
There is a range of up to 500 μm. However, it is also clear from FIG.
As you can see, when the coating layer thickness exceeds 100 μm,
Since the Vickers hardness of is saturated,
As data to be compared, if the thickness is 100 μm or more
There is no problem if they are different. FIG. 9 shows the relationship between the thickness of the coating layer and Vickers hardness.
FIG. 3 is a diagram showing the relationship between the coating pair of the present invention (composition: Ni
₈₂B₁₈) Indicates the measured value, and the x mark indicates the conventional value (plating,
Composition: Ni₈₂B₁₈) Indicates the measured values, and the triangles indicate
Overcoat (Composition: Fe₇₀Co_FifteenB _Fifteen) Indicates the measured value. ○ mark
Compare (invention) and x (conventional)
And, Vickers hardness is large at any thickness. One
It can be said that the present invention is harder than the conventional one. FIG. 10 shows the thickness of the coating layer and the load when peeled.
FIG. This is a drive with a coating layer formed
The shaft is rotatably installed in an air atmosphere at 120 ° C.
Through a plate material with a friction coefficient of 0.3 to 0.4 on the surface of the coating layer
And load each. Rotate for 30 minutes in this state
After that, the smallest load among the coating layers peeled off
It is a lot. ○ indicates the present invention (composition: N
i₈₂B₁₈) X mark is conventional (plating, composition: Fe₇₀C
o_FifteenB_Fifteen) Indicates the measured value. For example, the thickness of the coating layer is 1
When the thickness is 00 μm, the weight of the present invention is 21 kg / mm^TwoLoad of
After rotating for 30 minutes with the weight added, the coating layer peeled off
3.7 kg / mm^Two
When applying the above load and rotating, all coating layers
(Plating layer) has peeled off. That is, the present invention
Is a firmer coating layer than the conventional one (plating).
It is worn. Further, according to the present invention (composition: Ni₈₂B₁₈)
Is conventional (platingsetComposition: Ni₈₂B₁₈) Compared toConversion
StudyCorrosion resistance is 5~Improved by 10%. This is 1 rule (1
After immersing them in a hydrochloric acid solution of N) for 48 hours,
Measure and compare the weight of chloride generated in each solution
did. Then, according to the present invention, the chloride content in the dipping solution is
5-10% lessThe above-mentioned chemical corrosion resistance
I can understand the above.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram of a torque sensor using an amorphous coating of the present invention as a drive shaft. FIG. 2 is a partial external view showing an arrangement state of exciting coils. FIG. 3 is a sectional view taken along the line III-III in FIG. 1; FIG. 4 is a partially enlarged view of FIG. 5 (a), 5 (b) and 5 (c) are diagrams showing the distribution ratio of the particle size of the amorphous metal powder. FIG. 6 is a diagram showing the composition of an amorphous metal powder and the magnetostriction characteristics after forming a coating layer . FIG. 7 is a characteristic diagram showing characteristics of the amorphous coating of the present invention. FIG. 8 is a characteristic diagram showing the composition of the amorphous coating of the present invention. FIG. 9 is a characteristic diagram showing characteristics of the amorphous coating of the present invention. FIG. 10 is a characteristic diagram showing characteristics of the amorphous coating of the present invention. [Description of Signs] 1 Amorphous metal coating layer 4 Base material (drive shaft of torque sensor)

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C23C 24/06 C23C 24/06

Claims (1)

(57) [Claims] A metal base material is disposed at the center of the cylindrical container, and a particle size of 0.01 μm to 2 μm is provided in a space between the base material and the container.
After filling the container with 00 μm amorphous metal powder and sealing the container, the container is subjected to high-speed processing with a molding pressure of 0.7 to 80 GPa to form a coating layer of amorphous metal on the surface of the base material. A method for forming an amorphous coating body, comprising: 2. The method for forming an amorphous coating according to claim 1, wherein the amorphous metal is a metal mainly composed of at least one of silicon, iron, cobalt, nickel, chromium, and boron. 3. Method of molding the amorphous coating of claim 1, wherein the plasma treatment of the powder of the amorphous metal in a reducing atmosphere.