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JPS6052543

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DESCRIPTION JPS6052543
[0001]
The present invention relates to, for example, a sound generator such as a speaker, and more
particularly to the material of its diaphragm. スピーカにはコーンスピーカ、ホーンスピーカ。
There are various structures such as a dome speaker, a capacitor speaker, a ceramic speaker, and
a ribbon speaker. A variety of materials and shapes have been studied, such as a cone speaker, a
cone of a ceramic speaker, a horn speaker and a dome speaker, a diaphragm of a capacitor
speaker, and a conductor serving as a diaphragm of a ribbon speaker. The present inventors
succeeded in producing a second-phase particle dispersed ultra-quenched magnetic alloy using a
liquid quenching method conventionally known as a method of producing an ultra-quenched
alloy, and this new composite material It has been found that the excellent properties of both of
the constituent materials (super-quenched magnetic alloy and second phase particles) of 9 are
selectively combined with the 9 functions to be very suitable as a vibrator of one sounding body.
That is, according to the present invention, a vibrating body is formed of a composite material in
which second phase particles are uniformly dispersed in at least one kind in a three-dimensional
manner in an ultraquenched alloy matrix consisting of amorphous, crystalline or mixed phase
thereof. It is characterized by the fact that In the present invention, as an alloy base material
constituting the super-quenched alloy matrix, for example, cobalt-based alloys such as cobalt-iron
alloys mainly containing cobalt, iron-silicon-boron alloys mainly containing iron, ironmolybdenum alloys Iron-based alloys such as Ni, nickel-based alloys such as nickel-silicon-boron
alloys mainly composed of nickel, or copper-zirconium alloys. Alloys of various systems such as
zirconium-niobium alloy are used. In the present invention, as the second phase particles, for
example, carbon or carbides such as C2WC, Tic, NbC and the like. Nitrides such as NbN and TaN,
Cr20: I, Ce0z. MgO,Zr()z、YzOs、WO−s、Th0z。 Oxides such as A11zO3,
Fez gg, ZnZn, 5iOz, borides such as BN, silicates such as SiC, metals such as Ti, Fe, Mo, W, etc. are
used. Next, a production example of a ribbon according to the present invention will be
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described. 1 and 2 are diagrams for explaining the principle of the first production example, and
FIG. 1 is a diagram for explaining the process of producing an ingot, and FIG. 2 is for producing a
ribbon using the ingot. It is a figure for demonstrating a process. In FIG. 1, an alloy base material
1 constituting an ultra-quenched alloy matrix is heated and melted by a vacuum high-frequency
melting furnace 2, and “f: 1” is injected into a mold 3 for an inbottle 1.
-1lf, 2nd phase particles 4 are powder for plasma spraying r? ! The second phase is used to
forcibly inject and add the molten alloy base material 1 injected into the mold 3 to the second
phase, and the second phase is cooled and solidified as it is to obtain an ingot in which the
second phase particles 4 are uniformly dispersed and held. For the injection and dispersion of the
particles 4, an injection medium made of an inert gas such as argon gas filled in the cylinder 6 is
used. In order to avoid deterioration of the alloy base material 1 at the time of injection and
dispersion, it is preferable to use an inert gas such as argon gas as the injection medium. As a
powder feeder for supplying the second phase particles 4, the second phase powder 4 can be
always supplied uniformly, the injection conditions such as the injection pressure can be
relatively easily performed, and the heat resistance of the nozzle is excellent. The powder supply
device for plasma spraying is preferable from the viewpoints of the above. As a method of
producing a ribbon-like thing by the super-quenching method, there are a two-sink roll method, a
twin roll method, a centrifugal method and the like. In these ultra-quenching methods,
metastable substances not in the equilibrium phase diagram such as amorphous phase and nonequilibrium crystalline layer, or equilibrium crystalline phase, etc., by controlling the quenching
conditions such as selection of alloy composition or quenching rate. Is obtained. FIG. 2 shows a
manufacturing process for producing a ribbon by a twin roll method. An ingot 8 in which the
aforementioned second phase particles are uniformly dispersed is placed in a heat resistant tube
7 made of quartz glass having a nozzle at its lower end, and the tube is sufficiently substituted
with an inert gas 9 such as argon gas in the tube. A high frequency melting furnace 10 is
installed on the outer periphery of the heat resistant tube 7, and the ingot 8 is remelted by the
melting furnace 10 to such an extent that the second phase particles are not melted. Thereafter,
the piston 11 is operated to make the nozzle tip of the heat resistant tube 7 as close as possible
to the junction of the two rolls 12.12 rotating at high speed, and the gas pressure in the heat
resistant tube 7 is rapidly increased. Due to the pressure increase, the remelted ingot 8 is
gradually supplied from the nozzle as a uniform continuous jet to the joint of the roll 12.12.
Since the roll 1.2.12 is rotating at a high speed and always in pressure contact, when the melt =
7-metal is ejected, it is instantaneously cooled and solidified to obtain a continuous ribbon 13.
FIG. 3 is an enlarged cross-sectional view of this ribbon 13, in which a very fine second phase
particle 4 is three-dimensionally uniformly dispersed in an ultraquenched alloy matrix 14
consisting of amorphous, crystalline or their mixed phase. It is done. The thickness, width and the
like of the ribbon 13 can be adjusted by changing the circumferential speed of the roll 12 and
the pressure contact force, the temperature of the m melt, the ejection speed, and the like.
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The twin-roll method described with reference to FIG. 2 has advantages such as uniform
thickness of the obtained ribbon, small surface roughness on both sides, and easy manufacture of
relatively thick ones. . Although the twin roll method was used in this production example, a
single roll method can be applied instead. FIG. 4 is a principle explanatory view for explaining a
second manufacturing example of the ribbon according to the present invention. The ingot of A8material 1 is put into a heat-resistant tube 7 made of quartz glass having a nozzle at the lower
end, into an alloy mother-ro of the superquenched alloy matrix, and an inert gas 9 such as argon
gas is sufficient in the tube. Replace. A high frequency melting furnace 4 is installed on the outer
periphery of the heat resistant tube 7, and the ingot of the alloy base material 1 is melted by the
melting furnace 4 to such an extent that the second phase particles 4 described later do not melt.
Thereafter, the piston 11 is operated to make the nozzle tip of the heat resistant tube 7 as close
as possible to the upper circumferential surface of the roller 6 rotating at high speed, and the
inert gas pressure in the heat resistant tube 7 is rapidly increased. The molten alloy base material
I is supplied to the circumferential surface of the roll 6 as a thin uniform continuous jet from the
nozzle due to pressure increase. The second phase particles 4 are forcibly injected and added to
the jet stream of the alloy base material 1 from the heat-resistant tube 7 by means of the plasma
spraying powder feeder 5 together with a jet medium such as argon gas. The alloy base material
1 in the molten state to which the second phase particles 4 are added is rapidly solidified while
being stretched on the roll 12, and a continuous ribbon 13 is obtained. In the ribbon 13 thus
obtained, the very fine second phase particles 4 are uniformly dispersed in the third dimension in
the ultra-quenched alloy 71-lix 10-! 4 in the same manner as shown in FIG. ing. The skewer roll
method described with reference to FIG. 4 has the advantage that relatively wide, thin films are
easy to obtain. In this production example, the skewer roll method is used, but it is also possible
to apply the twin roll method instead. FIG. 5 is a principle explanatory view for explaining a third
manufacturing example of the ribbon according to the present invention. An ingot of the alloy
base material 1 constituting the ultraquenched alloy matrix is placed in a heat resistant tube 7
made of quartz glass having a nozzle at its lower end, and the tube is sufficiently substituted with
an inert gas 9 such as argon gas. The high frequency melting furnace 10 is installed on the outer
periphery of the heat-resistant tube 7 and the ingot of the alloy base material I is melted by the
melting furnace 10 to such an extent that the second phase particles 4 described later do not
melt. Thereafter, the piston 11 is operated to rapidly increase the inert gas pressure in the heatresistant tube 7, and the molten alloy base material 1 is gendered in the molten metal reservoir
15 disposed therebelow.
The second phase particles 4 are forcibly injected and added from the plasma spraying powder
feeder 5 to the jet stream of the alloy base material 1 from the heat resistant tube 7. The high
frequency melting furnace 16 is also attached to the outer periphery of the molten metal
reservoir 15, and the molten state of the alloy base material 1 is maintained. Thus, the alloy base
material 1 containing the second phase particles 4 is thin from the lower nozzle of the molten
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metal reservoir 15 to the bonding portion of the roll 12.12 by the high pressure charging of the
inert gas (argon gas) not shown. The ribbon 13 is supplied as a uniform continuous jet and is
super-quenched as in the production example to obtain a continuous ribbon 13. This ribbon 13 is
also the same as that shown in FIG. Very fine second phase particles 4 are three-dimensionally
uniformly dispersed in the ultraquenched alloy matrix 14. Although the twin roll method is used
in this production example, it is also possible to apply the single roll method instead. The second
phase particles are melted without using the jet dispersion method as described above in forming
the in-bottle 1 of the alloy base material constituting the super-quenched alloy matrix or
remelting the ingot for super-quenching The second phase particles can also be threedimensionally dispersed in the alloy matrix by simply adding to the alloy base material in the
state, stirring by high frequency, and then super-quenching 11-and then quenching. However,
this method has limitations in the types of second phase particles that can be applied and in the
range in which they can be dispersed. In particular, when the second phase particles are metal
oxides such as Cr: O = + and CeO2, the wettability to metal melts such as iron, cobalt and nickel is
poor, and only a very small amount is dispersed. It tends to be unevenly distributed in the surface
layer of 71-lithium. The interface phenomenon that occurs when the second phase particles are
added and dispersed in the alloy base material in the molten state can be considered in the
following two stages. すなわち。 In the first stage, the second phase particles come into contact
with the molten alloy base material, in which case the liquid phase of the molten alloy base
material, the solid phase of the second phase particles, argon gas (inert gas), etc. It is a gas phase
three phase system. The second stage is a stage in which the second phase particles are
suspended in the molten alloy base material, which is a two-phase system in which the liquid
phase of the molten alloy base material and the second phase particles are in phase.
Furthermore, the interface phenomenon of the above-mentioned three-phase system can be
roughly classified into adhesion wetting, 12-extended wetting, and one use of immersion.
Assuming that the work when adhesion wetting occurs is W a, and the amount of work when
extended wetting occurs is k W s HIfk The work amount when immersion occurs is Wi, and is
defined as follows. Wa = γsv-γSL + γLV ° = (1) Ws = γS Scy γSL−γL XI (2) Wj, =
γsv−γSL − (3) where γSL: solid phase-liquid phase 1 plane tension γSL: solid Of the surface,
stomach surface tension γLv: interfacial surface tension at liquid phase-solid phase and liquid
phase-solid phase interface of liquid phase is considered to be hardly deformed, so the contact
angle with liquid phase is assumed to be θ Then the following equation (4) is established.
.gamma.sv-.gamma.SL = .gamma.Ly 'cos .theta.-44) Substituting these equations into the above
equations (1), (2) and (3), the following equation is obtained. Wa = r L (C, OS B +)-(5) Ws = γ L
(cos θ-1) (6) W i = γ L V 'CO 9 θ-(' 7) In these formulas, W is positive σ) At the same time, f + I
will cause 1 system wettability. As apparent from the above formulas (5) to (7), the contact angle
of the second phase particles with respect to the alloy H) in the first stage where the second
phase particles are in contact with the molten alloy base material. θ greatly affects the
wettability. For metal melts such as iron, cobalt and nibbles, metal oxides generally have large
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contact angles O and thus poor wettability. Therefore, if the second phase particles are added to
the molten alloy base material in 4 and stirred with high frequency applied, so-called alloy base
material and second phase particles are not well matched, and the second layer on the surface
layer side of the alloy base material 2 Sum particles are likely to be unevenly distributed. Because
of this, when metal oxide is used as the second phase particles, the amount of dispersion is as
small as at most about 0.1% by volume as a beast which can be dispersed in the alloy base
material, The addition effect of phase particles can not be sufficiently exhibited. In this respect, as
described above, when making the in-box 1 of H for alloy, or melting it for super-quenching the
in-box 1-, the second phase particles are melted in an alloy matrix using a jet dispersion method.
If a method of adding to the material is adopted, the strong injection energy causes the second
phase particles to be mechanically pushed into the alloy base material. Therefore, even the
second phase particles having poor wettability to the alloy base material can be forcibly
uniformly dispersed, and the type of second phase particles that can be applied and the base that
can be dispersed also have a margin, and the core material Property 9 Contributes significantly
to the improvement of functions. An example of the in-phase contact angle to the metal melt is
shown in Table 1 below. = 15-1 \ 7-16 As apparent from this table, metal oxides generally have a
large contact angle and poor wettability to metal melts as compared to other common phases.
Next, an embodiment of the present invention will be described. Example 1 (Co-, o, +; Fe 4.5 Si 1
ski O) 9 g 5 (ll IC) 0.5 (CO 7 o, 5 Fea 5 si 15 B: Lo) q s (VC) i (Co-, o, 5 Fe 4.5six 5 B 10) 9 s (IIC) =
(CO7 o, +; Fea 55 i 15 B 10) 9 S (uc) s (CO 7 o S Fe 45 s ii 5 B 10) 9 o (uc) 1 ° A ribbon
consisting of the second phase particle dispersed type super quenched alloy of the above
composition formula is prepared.
In the above composition formula, the left () shows the composition of the ultra-quenched alloy,
the numbers at the lower right of each element thereof indicate atomic%, and in the composition
formula, the second phase particle composition is shown in the cloth (). The numbers at the lower
right of both () represent the respective volume%. The other embodiment adopted the same
display method as this. Next, a specific creation procedure will be described. First of all, make up
the composition gold RCo to obtain the desired composition of the rapidly quenched alloy.
Measure Fe, Si, B by 420.9 g of Co, 22.5 g of Fe, 18-42.7 g of Si, B ITO g, respectively, and melt
them together in the vacuum high-frequency melting furnace 2 (see Fig. 2). , To form a molten
alloy base material 1. The alloy base material I is injected into the mold 3 as it is. On the other
hand, WC fine powder (second phase particles 4) is filled in advance in the powder supply device
5 for plasma spraying, and is jetted toward the mold injection flow of the alloy base material 1 by
high pressure argon gas from the cylinder 6 Ru. The injection amount of the WC fine powder is
adjusted by the powder feeder 5 so that the body f #% represented by the above-described
composition formula with respect to the alloy base material 1 is obtained. The temperature of the
alloy base material 1 when injected into the mold 3 is adjusted so that the molten state of the WC
fine powder which is the second phase particles is maintained, that is, about 1200 ° C. There is.
The w c * powder forcibly injected toward the mold injection flow of the molten alloy base
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material 1 is dispersed in an individually refined state in the alloy base material 1 in a nonconsuming manner, and the inter-particle spacing is constant. short. As described above, the WC
fine powder dispersed in a finely divided state without coarsening has a low floating speed in the
alloy base material 1 and thus segregates when the alloy base material 1 solidifies in the mold 3
There is no problem and the dispersed state is stable. From such a thing, the ingot 8 which
consists of a Co-Fe-8i-B type | system | group alloy which WC fine powder disperse | distributed
uniformly is obtained. Next, this ingot 8 is placed in a heat resistant tube 7 made of quartz glass
as shown in FIG. 2, the tube is sufficiently replaced with argon gas 9, and then the ingot 8 is
melted in a high frequency melting furnace 10. Also at this time, the WC fine powder is
maintained at such an extent that it does not dissolve, that is, about 1200.degree. Next, the piston
11 is operated to make the lower end nozzle of the heat resistant tube 7 as close as possible to
the junction of the two rollers 12 and 12 rotating at high speed, and the argon gas pressure in
the heat resistant tube 7 is rapidly increased. Is supplied from the nozzle as a uniform continuous
jet to the joint of roll 12.12. Since the roll 12 ° 12 is rotating at high speed while being cooled
and always pressed against each other, the jetted alloy base material is instantaneously cooled
and solidified to obtain a ribbon 13 having a thickness of 30 μm and a length of 5 m.
When the surface of the ribbon 13 and the cut 19-plane in the thickness direction are observed
with a scanning electron microscope, the WC fine powders are aggregated into one another with
a short particle spacing in the ultra-quenched alloy matrix. The powder is dispersed uniformly in
the form of fine particles individually, without any pores. From this, it was confirmed that WC
fine powder was uniformly dispersed three-dimensionally in the alloy matrix. Also, it was
confirmed by X-ray diffraction that this ultraquenched alloy matrix alloy was amorphous. FIG. 6
is a cross-sectional view of a ceramic speaker configured using the ribbon obtained in this
manner. Reference numeral 17 in the figure is a vibrator made of a piezoelectric ceramic plate of
the p b (ZrTj) Os-BaTiO: l system, and electrodes 18. 18 are attached to both surfaces thereof. A
cone 19 is a thin plate of the second phase particle dispersion type rapidly quenched alloy. When
a voltage is applied between the charge WAis 18, the vibrator 17 expands and contracts in the
radial direction as shown by the arrow. As shown in the figure, since one end of the cone 19 is
connected to the outer periphery of the vibrator 17, as the vibrator 17 expands and contracts,
the cone 20-n 19 vibrates in the direction of the arrow to generate sound. . Example 2 (Ni ae Si1.
O B x 2)-y (WC) 3 (Nj 7 ta 5-i o B: L z)! z (WC) e (Nj7CI Six o Blz) e 2 (WC) 1s Ribbons of the
second phase particle dispersed type rapidly quenched alloy of the above composition formula
are respectively prepared. Next, a specific creation procedure will be described. The constituent
metal Ni to obtain the composition of the desired ultraquenched alloy first. Si and B are
respectively weighed so as to be Ni 459 g, 5128 g and B 13 g, these are melted in a vacuum high
frequency melting furnace to make an alloy base material, and this is poured into a mold. The
WC @ powder (second phase particles) is sprayed from the plasma spraying powder feeder to the
injection flow of the alloy base material 1 together with high pressure argon gas, and then cooled
to uniformly disperse WC fine powder. Make an in-bo- made of B-based alloy. If the temperature
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of the alloy base material when the WC fine powder is jetted and dispersed is adjusted to about
1200 ° C., the added WCWi powder does not dissolve in the alloy base material, and the fine
particles are uniformly dispersed as it is. Ru. The ingot is placed in a heat-resistant tube placed in
the true position of one roll, and the tube is sufficiently substituted with argon gas. Then, it is
heated and held at about 1200 ° C. by a high frequency melting furnace provided on the outer
periphery of the heat resistant tube, and only the alloy base material is remelted.
Thereafter, the argon gas pressure in the heat-resistant tube is rapidly increased, and a molten
alloy base material containing WC @ powder is spouted from the lower nozzle of the heatresistant tube to the roll rotating at 2000 r, p, m. When ejected, it is instantaneously cooled and
solidified to obtain a ribbon of 30 μm in thickness and 5 m in length. When the surface of the
ribbon and the cut surface in the thickness direction were observed with a scanning electron
microscope, WC fine powder was uniformly dispersed as fine particles in the ultra-quenched
alloy matrix, as in the example described above. Moreover, it was confirmed by X-ray diffraction
that the ultra-quenched alloy 71-lithium is amorphous. The procedure for producing a speaker as
shown in FIG. 6 using this ribbon is the same as in the previous embodiment. Their description is
omitted. Example 3 (Co-, oSFea, 5sii sBi T)) 93.9 (Cr: 0+) o, 1 (CO7o5 Fea5 si1s B10) 99. −,
(Cr203) o, + (Coy o, qFe4.r, S, 11SBIO) 9! ! , * (Cr20 = +) o, 5 (Co-, o, 5Fea, 5silEB: Lo) sq (CrzOs) 1
(Coyo 5Fe4.5si15Bxo) 9-, (CrzOi): I, second phase of the above composition formula A speaker is
assembled in the same manner as in the above embodiment using a ribbon made of a particle
dispersion type rapidly quenched alloy. Example 4 (Co7o, 5Fe4, 5six5B1o) 9j9 (Ce0z) o, i (CoAo,-,
Fea, 5siisBio) g = s,-, (Ce0z) 0.3 (Co7o, 5Fe45si1se10) 9 g 5 (Ce 0 z) o, s (Co-, o 5 Fe 45 si 15 B 1
o) ti Q (Ce 0 z)] (Coyo, 5 Fe 45 Si x * B 1 o) 97 (Ce O z) 3 Using a ribbon comprising a second
phase particle dispersed type super quenched alloy of the above composition formula The
speaker is assembled in the same manner as in the previous embodiment. 23 Example 5 (Co7 o 5
Fe 4, 5 six ski O) 99.9 (WO 3) o,: i (CO 7 o, s Fe 45 Six Sn] O) +1! 1.7 (WO: l) o, i (Coy o, 5Fe 45
Siz 5 RI O), 3 *, q (WOq) 05 (Coy o, 5 Fea, 5si1 gBu O) 9 9 (WO: I) 1 (Coy o) 5Fe4.1sii 5B] O) g7
(WO3): 1 A speaker is assembled in the same manner as in the above example, using a ribbon
composed of the second phase particle dispersed type rapidly quenched alloy of the above
composition formula.
Example 6 (Co7 o, 5 Fe (ssico 51 'h o) s 9.! I(ZrOz)o、x(CO7o、
sFe4.s5i15BxO)991.7(ZrOz)o、a(Co705F64.!
5Sii5n1o)Q9,5(ZrOz)o、s(Coyo5Fe(5Si150xo)! 39
(ZrOz) t ((oyo5Fe, + 5siigr1.i, o) sy (ZrOz) q A speaker is assembled in the same manner as in the
above example, using a ribbon consisting of the second phase particle dispersed type rapidly
quenched alloy of the above composition formula. Example 7 ((o 7 o, 5 Fe 4, 5 si) r, B 1 o) i 9.9
('Y 20 s) ol (CO 7 o SF ea, ss j) 5 ex (1) 99.7 (Y 20 s) o, +-′ ′) − − − A1-24 = (Co + o 5 Fe 4, 5
si l s Bi o) s 9.5 (Y = 03) l: l 5 (Coy o, 5 Fe (ssils B: + O) 9! l(Y:! ○ヨ)](Co? o, i F 645
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Sj, iv Eho ',) 97 (v 203) 3 A speaker is assembled in the same manner as in the above example,
using a ribbon made of the second phase particle dispersed rapidly quenched alloy of the above
composition formula. Example 8 (Ni7 GSj, xoB: i =) 9 o (ThCJz) l. (Ni7e 5j1o B12) oo (ThOz) 2 Q A
speaker is assembled in the same manner as in the above example, using a ribbon made of the
second phase particle dispersed type rapidly quenched alloy of the above composition formula.
Example 9 (Ni = 5 Sj1 o B × 5) -IG (TiC) s (N-y-c; Six o B-co 5) 0 (T-y C) 10 Second-phase particle
dispersion of the above composition formula A speaker is assembled in the same manner as in
the previous embodiment, using a ribbon made of a mold-quenched alloy. In addition, scanning
electron microscope ll! Intuitively, T i C is three-dimensionally uniformly dispersed in the Ni-5i-B
super-quenched alloy 71-lix, no holes, and 26--an alloy of l-jl-sogs by X-ray diffraction. It is
confirmed that it is amorphous Example 3 (FCl 29.4 Mo-q CJ, r,) q s (NbC) 2 (Fe: 194 Mo <+ C1, t) 95 (NbC) 5+ (Fei 9 JMo, v CI-, e,) 90 (1 ′ ′ J b C) i. A speaker is assembled in the same
manner as in the above-mentioned example, using a ribbon made of the 24th day particle
dispersion type rapid quench alloy of the above composition formula. Nb C is three-dimensionally
uniformly dispersed in the Fe-Mo-C ultra-quenched alloy matrix by scanning electron microscope
observation, and there are no holes, and the alloy mad 11 is dispersed by X-ray diffraction. It was
confirmed that is a non-equilibrium γ-austenite V phase having a structure of ultrafine grains.
Since this non-equilibrium γ-austenite phase is a crystalline alloy, it has higher thermal stability
than an amorphous alloy. Example 11 (Cu6oZt- + o) G'O (Sj, C) +.
(Cu6oZra(1)70(SjC’):+。 A speaker is assembled in the same manner as
in the above embodiment, using a ribbon made of the second phase particle dispersion type
rapidly quenched alloy of the above composition formula. In addition, it is confirmed by scanning
electron microscope observation that SiC is uniformly dispersed three-dimensionally uniformly in
the Cu-Zr system super-quenched alloy matrix and there are no holes, and [the alloy matrix is
amorphous by line diffraction] did. Example 12 (Ni7e 5i1o Bi,! )90(BN)10(Niア
aSiloB1z)8o(BN)z。 A speaker is assembled in the same manner as in the
above embodiment, using a ribbon made of the second phase particle dispersion type rapidly
quenched alloy of the above composition formula. In addition, BN is three-dimensionally
uniformly dispersed in the Ni-8i-B superquenched alloy matrix by scanning electron microscope
observation, there are many holes, and the alloy 71-lithium is amorphous by X-ray diffraction. It
was confirmed. Example 13 (ZraaNb4o5i1s) so (NbN) 2 [deg.] A speaker 27- is assembled in the
same manner as in the previous example, using a ribbon made of the second phase particle
dispersed type super quenched alloy of the above composition formula. Incidentally, according to
the standing electron microscope 11i11, it is three-dimensionally uniformly dispersed in the
NbNh <Zr-Nb-8j system of rapidly quenched alloy 71-lithium, without any wrinkles, and the base
metal matrix is amorphous by X-ray diffraction. It confirmed that it was quality. Example 14
(CO7o,-, Fe, + sSii = -rP, 11-1) 9G (C)) (CO70, 51 ") 4.
−.5j1sl’+IQ)95(C)q(Coyo! l+Fea、=、Sj、
t5B]O)9Q(C)1。 A speaker is assembled in the same manner as in the above
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embodiment, using a ribbon made of the second phase particle dispersion type rapidly quenched
alloy of the above composition formula. In addition, C is three-dimensionally uniformly dispersed
in the Co-Fe-Si-B system ultra-quenched alloy matrix by scanning electron microscope
observation, and there are no holes, and the alloy 71-lithium is amorphous by X-ray diffraction. I
confirmed that it was an eve. Example l5 (Fee:! B1[])9g(F’e)1(Fea2r!
1a)! N (FQ) 2 A speaker is assembled in the same manner as in the above embodiment,
using a ribbon consisting of a 28 <-> second rapidly solidified Iif-type rapidly quenched alloy of
the above composition formula.
In addition, it was confirmed by scanning electron microscope observation that FFI was threedimensionally uniformly dispersed in the Fe-B-based rapidly quenched alloy matrix, and the alloy
matrix was an amorphous invar alloy by X-ray diffraction. Fig. 7 shows the particle size
distribution of second phase particles in the superquenched alloy matrix, Fig. CF3) shows T j, C
shows Fig. (B) shows WC, Fig. (C) shows CrzOi, Fig. ) Were dispersed in a superquenched alloy
matrix of Co = og Fe4 ssix 5 Blo system by the injection parting method using Zr0z as second
phase particles, and the particle size was measured with an electron microscope. The average
particle size of each of these second phase particles was about 0.06 μ river. As apparent from
each of these times, the particle diameter of about 70% or more of the second phase particles
being divided is less than about 0.1 μm, and thus the second phase particles are In order to
make the time t1 in the state, it is necessary to appropriately adjust the particle size of the
second phase particles before the addition and the injection conditions thereof. Table 2 below
shows the average particle sizes of other second phase particles in the rapidly quenched alloy
matrix (Co7Q, 5Fe- +, 5Si1sB1o). As described above, when most of the second phase particles
are ultrafine particles, the dispersed state of the second phase particles is stable even in the
molten alloy base material. That is, in the stage where the second phase particles are suspended
in the molten alloy base material, there is a dispersion system in which the alloy base material is
a dispersion medium and the second phase particles are a dispersoid. Since this dispersion
system is thermodynamically unstable, the free energy change ΔF greatly contributes to the
dispersion or aggregation of the second phase particles. In general, the free energy change ΔF is
1. There are changes in interface free energy and changes due to chemical reaction. By the way,
when the molten alloy base material and the second phase particles are in equilibrium, it is
considered that the free energy change due to the chemical reaction is zero, so the dispersed
state of the second phase particles is a change of the interface free energy. It will be ruled.
Dispersion of the second phase particles in the molten alloy matrix eliminates the in-phase
(second phase particles) -solid phase (second phase particles) interface, and the in-phase (second
phase particles) one liquid phase (molten alloy matrix) B) the change in which the interface is
formed. Therefore, the change ΔFs of the interface free energy at this time is defined as the
following equation (8). In the formula, γ ss is the interfacial tension at the solid phase-solid
phase interface. ΔFs = 2γs L −y ss − (8) According to this equation, if the value of 8 Fs is
negative, the second phase particles will be dispersed or spontaneously suspended in the molten
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alloy matrix, and if positive, they will aggregate.
In order to make Fs negative to change in interface free energy when changing from this solid
phase-solid phase boundary 31-plane to the solid phase-liquid phase interface, the particle size of
the second phase particles should be as small as possible And if the particle size of at least about
70%, preferably at least 90%, of the dispersed second phase particles as described above is less
than about 0.1 μm, the second phase particles are The dispersion state is stable without being
aggregated to one another and dispersed uniformly. Since the composite material according to
the present invention is non-porous and has no so-called nest, there is no unevenness in the
transmission of vibration. Moreover, since it has strong toughness, is strong against bending, and
has a high Young's modulus, it is possible to obtain a reliable sounding body that is suitable as a
diaphragm of a sounding body. In the embodiment, the composite material according to the
present invention is used for the cone of the ceramic speaker, but the present invention is not
limited to this, for example, vibration of cone speaker cone, horn speaker, dome speaker,
capacitor speaker, etc. The present invention can also be applied to a conductor used as a
diaphragm of a plate or ribbon type speaker. 32−
[0002]
Brief description of the drawings
[0003]
1 and 2 are principle explanatory views showing a second manufacturing example of the core
material according to the present invention, FIG. 3 is an enlarged sectional view of the
manufactured core material, and FIG. 4 is the core material according to the present invention
FIG. 5 is a principle explanatory view showing a second production example of the present
invention, FIG. 5 is a principle explanatory view showing a third production example of the core
member according to the present invention, and FIG. 6 is a cross section of the ceramic speaker
according to Example 1 of the present invention Figures 7 (a), (b), (c) and (d) are particle size
distributions of second phase particles in the alloy matrix.
DESCRIPTION OF SYMBOLS 1 ... Alloy base material, 4 ... 2nd phase particle | grain, 13 ... Ribbon,
14 ... Super quenching alloy matrix, 17 ... Vibrator, 18 ... Electrode, 19 ·····corn. Figure 14 Figure 4
Procedure correction (form) 1984 1st January 3rd Patent Office Secretary Kazuo Wakasugi Hall
1, Representation of the Case 1958 Patent Between Interventions 157900 No. 2, Name of
Invention Sounding body 3, Relationship with the case to make correction Applicant's place Ota-
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ku, Tokyo V, Tani Otsukacho, Ota-ku, Tokyo 7, Agent 7, Field 7 of the brief description of the
depression of the target statement of correction, contents of correction (1) Description 34 line 8
line IP r Correct the figure 7 (a), (b), (C)-(d) to "figure 7".
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