U.S. patent application number 13/244027 was filed with the patent office on 2012-01-26 for anti-seizing agent, sensor and assembly including sensor.
This patent application is currently assigned to NGK SPARK PLUG CO., LTD.. Invention is credited to Noboru FUJITA, Akiyoshi KATO, Takuya TAKASE, Naoki YAMADA.
Application Number | 20120021955 13/244027 |
Document ID | / |
Family ID | 38047822 |
Filed Date | 2012-01-26 |
United States Patent
Application |
20120021955 |
Kind Code |
A1 |
KATO; Akiyoshi ; et
al. |
January 26, 2012 |
ANTI-SEIZING AGENT, SENSOR AND ASSEMBLY INCLUDING SENSOR
Abstract
An anti-seizing agent including: a first solid lubricant
containing at least one of bismuth and a bismuth compound; and a
second solid lubricant containing at least one of graphite,
molybdenum disulfide and boron nitride. The anti-seizing agent
satisfies the relationships 20 weight %.ltoreq.a.ltoreq.90 weight %
and 10 weight %.ltoreq.d.ltoreq.80 weight %, in which a sum of the
contents of the first solid lubricant and the second solid
lubricant in the anti-seizing agent is taken as 100 weight %, and a
represents a content of the first solid lubricant and d represents
a content of the second solid lubricant.
Inventors: |
KATO; Akiyoshi; (Komaki-shi,
JP) ; YAMADA; Naoki; (Iwakura-shi, JP) ;
FUJITA; Noboru; (Kuwana-shi, JP) ; TAKASE;
Takuya; (Inabe-shi, JP) |
Assignee: |
NGK SPARK PLUG CO., LTD.
Nagoya-shi
JP
|
Family ID: |
38047822 |
Appl. No.: |
13/244027 |
Filed: |
September 23, 2011 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
11604760 |
Nov 28, 2006 |
|
|
|
13244027 |
|
|
|
|
Current U.S.
Class: |
508/123 ;
508/150 |
Current CPC
Class: |
C10N 2010/10 20130101;
C10N 2010/06 20130101; C10M 2215/16 20130101; C10M 2209/1013
20130101; C10M 2201/0413 20130101; C10M 2201/053 20130101; C10N
2010/04 20130101; C10M 2201/066 20130101; C10M 2201/0663 20130101;
C10N 2030/06 20130101; C10M 2201/041 20130101; C10M 2201/061
20130101; C10M 2201/0613 20130101; C10M 2201/062 20130101; C10N
2010/02 20130101; C10N 2010/14 20130101; C10M 2215/02 20130101;
C10M 2219/044 20130101; C10M 103/00 20130101; C10M 2201/0623
20130101; C10N 2010/12 20130101 |
Class at
Publication: |
508/123 ;
508/150 |
International
Class: |
C10M 125/02 20060101
C10M125/02; C10M 125/04 20060101 C10M125/04 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 28, 2005 |
JP |
2005-341440 |
Sep 25, 2006 |
JP |
2006-259640 |
Claims
1. An anti-seizing agent comprising: a first solid lubricant
containing at least one of bismuth and a bismuth compound; and a
second solid lubricant containing at least one of graphite,
molybdenum disulfide and boron nitride, wherein the anti-seizing
agent satisfies 20 weight %.ltoreq.a.ltoreq.90 weight % and 10
weight %.ltoreq.d.ltoreq.80 weight %, in which a sum of the
contents of the first solid lubricant and the second solid
lubricant in the anti-seizing agent is taken as 100 weight %, and a
represents the content of the first solid lubricant and d
represents the content of the second solid lubricant.
2. The anti-seizing agent as claimed in claim 1, wherein the
contents of the first solid lubricant and the second solid
lubricant satisfy 0.8.ltoreq.a/d.ltoreq.8.
3. The anti-seizing agent as claimed in claim 1, wherein the first
solid lubricant is one of bismuth and a bismuth compound, the
anti-seizing agent further comprises an antioxidant comprising at
least one of copper oxide, thallium oxide, iridium oxide, osmium
oxide, rhodium oxide and ruthenium oxide, and when a sum of the
contents of the first solid lubricant and the second solid
lubricant is taken as 100 parts by weight, a content of the
antioxidant e satisfies 10 parts by weight.ltoreq.e.ltoreq.100
parts by weight.
4. The anti-seizing agent as claimed in claim 1, further comprising
a lubricant base oil, or further comprising a lubricant base oil
and a thickening agent, wherein, when a sum of the contents of the
first solid lubricant and the second solid lubricant is taken 100
parts by weight, a sum b of the contents of lubricant base oil and
the thickening agent which is optionally present satisfies 90 parts
by weight.ltoreq.b.ltoreq.400 parts by weight.
5. The anti-seizing agent as claimed in claim 1, further comprising
an organic resin, wherein, when a sum of the contents of the first
solid lubricant and the second solid lubricant is taken as 100
parts by weight, and a content of the organic resin is c, the
relationship 90 parts by weight.ltoreq.c.ltoreq.400 parts by weight
is satisfied.
6. (canceled)
7. (canceled)
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Rule 53(b) Divisional of U.S. patent
application Ser. No. 11/604,760 filed Nov. 28, 2006, which claims
benefit to Japanese Patent Application No. 2005-341440 filed Nov.
28, 2005 and Japanese Patent Application No. 2006-259640 filed Sep.
25, 2006. The above-noted applications are incorporated herein by
reference in their entirety.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to an anti-seizing agent.
Particularly, the present invention relates to an anti-seizing
agent for preventing seizing of parts that may be exposed to high
temperatures of 500.degree. C. or higher, and a sensor and an
assembly including the sensor, using the anti-seizing agent.
[0004] 2. Description of the Related Art
[0005] An anti-seizing agent is often applied to a screw portion of
a metal part to prevent seizing, and the part is then used for
fabrication. The metal part includes a metal shell of a gas sensor
fitted to an exhaust pipe or the like of an internal combustion
engine used to detect a specified gas component in a gas to be
measured, and a metal shell of a temperature sensor fitted to an
exhaust pipe or the like to detect the temperature of a gas to be
measured. Examples of the anti-seizing agent include a paste-like
anti-seizing agent comprising a lubricant base oil and a solid
lubricant contained therein, and a paste-like anti-seizing agent
comprising a grease obtained by semi-solidifying a lubricant base
oil with a thickening agent, and a solid lubricant contained
therein (for example, see Masahisa Matsunaga, et al., Handbooks of
Solid Lubrication, pp. 409-416, Saiwai Shobo Co., (1978)).
[0006] Conventionally, a solid lubricant comprising a metal such as
copper, aluminum or nickel, as a main component, and according to
need, molybdenum disulfide or graphite combined therewith, is
widely used in a paste-like anti-seizing agent that is applied to a
metal part that may be exposed to high temperatures of 500.degree.
C. or higher (for example, see JP-B-8-19435).
[0007] The mechanism which allows these metals to prevent seizing
is considered to be as follows. A paste-like anti-seizing agent
containing the above-noted metals is applied to the requisite
portion of a metal part to thereby form a uniform intervening film
on the metal part. When the metal part is fabricated with another
part, the intervening film is present between the metal part and
the other part. As a result, when the metal part is exposed to high
temperatures and then disassembled from the other part (when the
metal part and the other part slide), seizing between the metal
part and the other part is prevented by the lubricating action due
to the softness of the metals constituting the intervening
film.
[0008] 3. Problems to be Solved by the Invention
[0009] However, when the metal part is fabricated with another
part, the uniform intervening film formed on the metal part is
localized so as to be present on only one portion in between the
metal part and the other part. In such a case, a site at which the
metal part and the other part are in direct contact is present, and
as a result, the anti-seizing effect is not obtained.
[0010] For this reason, there is a need for an anti-seizing agent
which forms an intervening film over the entire surface between a
metal part and the other part even when the metal part and the
other part slide, thereby exhibiting the desired anti-seizing
effect.
[0011] In particular, an anti-seizing agent having sufficient
seizing preventing performance for a sensor used under severe
conditions at high temperature has hitherto not yet been
achieved.
SUMMARY OF THE INVENTION
[0012] It is therefore an object of the present invention to
provide an anti-seizing agent that can solve the above-noted
problems of the prior art, a sensor and an assembly including the
sensor. That is, an object of the present invention is to provide
an anti-seizing agent capable of forming an intervening film over
the entire contact area between a metal part and another part even
when the metal part and the other part slide, and where the metal
part is exposed to a high temperature of 500.degree. C. or higher,
and a sensor and an assembly including the sensor, using the
anti-seizing agent.
[0013] The above object of the present invention has been achieved
by providing an anti-seizing agent comprising a first solid
lubricant containing at least one of bismuth and a bismuth compound
and a second solid lubricant containing at least one of graphite,
molybdenum disulfide and boron nitride, wherein the anti-seizing
agent satisfies 20 weight %.ltoreq.a.ltoreq.90 weight % and 10
weight %.ltoreq.d.ltoreq.80 weight %, in which the sum of the
contents of the first solid lubricant and the second solid
lubricant in the anti-seizing agent is taken as 100 weight %, and a
represents the content of the first solid lubricant and d
represents the content of the second solid lubricant.
[0014] In a preferred embodiment, the contents of the first solid
lubricant and the second solid lubricant satisfy the relationship
0.8.ltoreq.a/d.ltoreq.8.
[0015] In yet another preferred embodiment, the first solid
lubricant is one of bismuth and a bismuth compound, the
anti-seizing agent further contains an antioxidant comprising at
least one of copper oxide, thallium oxide, iridium oxide, osmium
oxide, rhodium oxide and ruthenium oxide, and when the sum of the
contents of the first solid lubricant and the second solid
lubricant is taken as 100 parts by weight, the content of the
antioxidant is e satisfies 10 parts by weight.ltoreq.e.ltoreq.100
parts by weight.
[0016] In yet another preferred embodiment, the anti-seizing agent
further contains a lubricant base oil, or a lubricant base oil and
a thickening agent, and when a sum of the contents of the first
solid lubricant and the second solid lubricant is taken as 100
parts by weight, and the content b of the lubricant base oil, or
the sum b of the contents of the lubricant base oil and the
thickening agent when present satisfies 90 parts by
weight.ltoreq.b.ltoreq.400 parts by weight.
[0017] In yet another preferred embodiment, the anti-seizing agent
further contains an organic resin, wherein, when the sum of the
contents of the first solid lubricant and the second solid
lubricant is taken as 100 parts by weight, and the content of the
organic resin is c, the relationship 90 parts by
weight.ltoreq.c.ltoreq.400 parts by weight is satisfied.
[0018] The anti-seizing agent is preferably applied to a metal
part.
[0019] In particular, in a sensor having a detecting element that
detects the state of a gas to be measured, and a metal shell that
holds the detecting element, the metal shell having a fitting part
that fits the detecting element to an exhaust pipe when exposing
the detecting element to a gas to be measured, the anti-seizing
agent is preferably applied to an outer surface of at least the
fitting part of the metal shell.
[0020] Further, in an assembly including a sensor having a
detecting element that detects a state of gas to be measured, and a
metal shell that holds the detecting element; and an exhaust pipe
that fits a fitting part formed on the metal shell of the sensor to
expose the detecting element to a gas to be measured, the
anti-seizing agent is preferably present between an outer surface
of the fitting part of the metal shell and a surface of the exhaust
pipe that fits the fitting part when the sensor and the exhaust
pipe are assembled, and after heating the fitting part to a
temperature of 270.degree. C. or higher, a bismuth component of the
anti-seizing agent remains on a central portion of the outer
surface of the fitting part.
[0021] The anti-seizing agent of the invention provides an
excellent anti-seizing effect, particularly to a metal part that
may be exposed to a high temperature of 500.degree. C. or higher,
particularly to a fitting part of a metal shell of a sensor.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] The FIGURE is a cross sectional view of the gas sensor 1
according to an embodiment of the present invention.
DESCRIPTION OF REFERENCE NUMERALS
[0023] Reference numerals used to identify various structural
features in the drawings include the following. [0024] 1 Gas sensor
[0025] 2 Gas sensor element [0026] 3 Heater [0027] 4 Metal shell
[0028] 7 Supporting member [0029] 9 Filling member [0030] 100
Sleeve [0031] 120 Protector [0032] 130 Inner cylinder member [0033]
140 Filter [0034] 150 Outer cylinder member [0035] 160 Separator
[0036] 240 Sealing member [0037] 136 Filter part [0038] 200, 300
Filter covering member [0039] 201, 301 Covering part [0040] 202,
302 Opening [0041] 203, 303 Insertion portion
DETAILED DESCRIPTION OF THE INVENTION
[0042] The anti-seizing agent of the present invention contains a
first solid lubricant and a second solid lubricant.
[0043] The first solid lubricant comprises at least one of bismuth
and a bismuth compound, as a main component. The present inventors
consider that the anti-seizing agent can prevent seizing of a metal
part by the following mechanism. The anti-seizing agent is applied
to a requisite portion of the metal part, to thereby form a uniform
intervening film. When the metal part is fabricated with another
part, the anti-seizing agent is localized to one portion, and as a
result, becomes present on only one portion or in isolated portions
in between the metal part and the other part such that there is
direct contact at other portions. However, when the metal part is
exposed to a high temperature, bismuth in the anti-seizing agent
melts and permeates over the entire interface between the metal
part and the other part, thereby again forming an intervening film.
This makes it possible to prevent seizing by the lubricating action
of the intervening film when sliding the metal part against the
other part.
[0044] The bismuth compound of the first solid lubricant includes
bismuth oxides. These compounds are commercially available, and
have an average particle diameter of 100 .mu.m or less, and
preferably 30 .mu.m or less.
[0045] The second solid lubricant comprises at least one of
graphite, molybdenum disulfide and boron nitride. The present
inventors consider that by further introducing the second solid
lubricant, the second solid lubricant permeates simultaneously when
bismuth permeates between the metal part and the other part, such
that the second solid lubricant is present between the metal part
and the other part. This makes it possible to further improve
lubricating performance.
[0046] The content a of the first solid lubricant and the content d
of the second solid lubricant in the anti-seizing agent of the
present invention satisfy 20 weight %.ltoreq.a.ltoreq.90 weight %
and 10 weight %.ltoreq.d.ltoreq.80 weight % when a+d is taken as
100 weight %. When a is less than 20 weight % (d exceeds 80 weight
%), it becomes difficult to form the intervening film, and the
anti-seizing effect deteriorates. On the other hand, when a exceeds
90 weight % (d is less than 10 weight %), the amount of the second
solid lubricant in the intervening film is too small, and the
anti-seizing effect may not be obtained.
[0047] The content a of the first solid lubricant and the content d
of the second solid lubricant in the anti-seizing agent of the
present invention preferably satisfy the relationship
0.8.ltoreq.a/d.ltoreq.8. When a/d is less than 0.8, it is difficult
to form the intervening film, and the anti-seizing effect may
deteriorate. On the other hand, when a/d exceeds 8, the amount of
the second solid lubricant in the intervening film is too small,
and the anti-seizing effect may not be obtained.
[0048] Of the anti-seizing agents of the present invention, when
the anti-seizing agent containing bismuth or a bismuth compound as
the first solid lubricant is applied to a metal part, and such a
metal part is exposed to a high temperature (for example, a
temperature of 700.degree. C. or higher), the metal part is
oxidized, and in that case its strength deteriorates.
[0049] The present inventors consider that this is due to the
following mechanism. When exposed to a high temperature of
700.degree. C. or higher, bismuth (in a metallic state) is oxidized
to form a bismuth oxide (hereinafter also referred to as an
oxidation reaction). However, the space between the metal part and
the other part is an enclosed space, and bismuth oxide is easily
reduced. When the oxygen partial pressure in the enclosed space
decreases, the bismuth oxide that was the product of the oxidation
reaction is reduced to bismuth metal (hereinafter also referred to
as a reduction reaction). The bismuth resulting from the reduction
reaction reacts with a passive film formed on a surface of the
metal part to remove the passive film. As a result, the surface of
the metal part from which the passive film has been removed is
oxidized.
[0050] Therefore, when bismuth or a bismuth oxide is present as the
first solid lubricant, the anti-seizing agent of the present
invention preferably contains at least one of copper oxide,
thallium oxide, iridium oxide, osmium oxide, rhodium oxide and
ruthenium oxide. By employing such an oxide, an oxygen component is
supplied to the enclosed space, to thereby prevent the oxygen
partial pressure in the enclosed space from lowering. Consequently,
the reduction reaction can be suppressed. As a result, oxidation of
the metal part can be prevented. Considering safety in production,
cost and the like, the oxide is preferably copper oxide. The
content e of the oxide is preferably 10 parts by
weight.ltoreq.e.ltoreq.100 parts by weight when the sum of the
contents of the first solid lubricant and the second solid
lubricant is taken as 100 parts by weight. When e is less than 10
parts by weight, it is difficult to prevent the metal part from
becoming oxidized. On the other hand, when e exceeds 100 parts by
weight, the component ratio of the first solid lubricant and the
second solid lubricant decreases, and the anti-seizing effect may
deteriorate.
[0051] The anti-seizing agent of the invention can further contain
a lubricant base oil, or a lubricant base oil and a thickening
agent. Examples of the lubricant base oil include a mineral oil, a
synthetic hydrocarbon oil, a polyalkylene glycol, a polyol ester,
an alkyl-substituted diphenyl ether, and their mixed oils. However,
the invention is not limited thereto.
[0052] Examples of the thickening agent for use in the anti-seizing
agent of the present invention include a calcium sulfonate complex
soap, lithium complex soap, calcium complex soap, lithium soap,
calcium soap, organized bentonite, fine powdery silica, aliphatic
diurea compounds, alicyclic diurea compounds, aromatic diurea
compounds, triurea compounds and tetraurea compounds, suitable for
use as a thickening agent for grease.
[0053] The content b of the lubricant base oil, or the sum of the
contents of the lubricant base oil and the thickening agent is 90
parts by weight.ltoreq.b.ltoreq.400 parts by weight when the sum of
the contents of the first solid lubricant and the second solid
lubricant is taken as 100 parts by weight. When b is less than 90
parts by weight, fluidity of the anti-seizing agent is lost, and it
is difficult to apply to a sliding surface of a part. On the other
hand, when b exceeds 400 parts by weight, the effect of the solid
lubricant is not exhibited, and therefore, it is difficult to
obtain the anti-seizing effect.
[0054] Examples of other additives that may be contained in the
anti-seizing agent include antioxidants, extreme-pressure
additives, clean dispersants, rust preventives, putrefaction
preventives, defoaming agents and diluents.
[0055] The anti-seizing agent of the present invention can further
contain an organic resin. Examples of the organic resin include
bisphenol F epoxy resins, bisphenol A epoxy resins, silicone resins
and TYRANNO resins (trade name of Ube Industries, Ltd., comprising
titanocarbosilane and polyalkylphenylsiloxane). However, the
invention is not limited thereto.
[0056] The content c of the organic resin is 90 parts by
weight.ltoreq.c.ltoreq.400 parts by weight when the sum of the
contents of the first solid lubricant and the second solid
lubricant is taken as 100 parts by weight. When c is less than 90
parts by weight, fluidity of the anti-seizing agent is lost, and it
is difficult to apply to a sliding surface of a part. On the other
hand, when c exceeds 400 parts by weight, the effect of the solid
lubricant is not exhibited, and therefore, it is difficult to
obtain the anti-seizing effect.
[0057] Examples of other additives that may be contained in the
anti-seizing agent include ultraviolet absorbers, wetting
dispersants, surface modifiers and curing agents.
[0058] The anti-seizing agent of the present invention can be used
in a screw portion of a nut member for fitting a gas sensor to an
exhaust pipe as shown in JP-A-11-190720, or in a gas sensor 1
described hereinafter, as an anti-seizing agent. The gas sensor 1
of the present embodiment is an example of one embodiment, and the
invention should not be construed as being limited thereto. The gas
sensor 1 (oxygen sensor) is fitted to an exhaust pipe of
automobiles and detects concentration of oxygen in an exhaust gas.
The FIGURE is a sectional view showing the overall structure of the
gas sensor 1.
[0059] As shown in the FIGURE, the gas sensor 1 is provided with a
sensor element 2 that is formed into a bottomed cylindrical shape
having its leading end closed, a ceramic heater 3 inserted in the
sensor element 2, and a metal shell 4 that holds the sensor element
2 inside the metal shell 4. Of directions along the axis of the
sensor element 2 shown in the FIGURE, the side toward the leading
end to be exposed to a gas to be measured (exhaust gas) (closed
side, downside in the drawing) is called a "leading end side," and
the side toward the direction opposite the above side (upside in
the drawing) is called a "back-end side."
[0060] The sensor element 2 has a solid electrolyte body 21 having
oxygen ion conductivity, an internal electrode 22 made of Pt or a
Pt alloy formed on an inner surface of the solid electrolyte body
21, and an external electrode 23 formed on an outer surface of the
solid electrolyte body 21. A flange portion 24 projecting toward an
outer diameter direction is provided at a central position on an
axial line of the sensor element 2. The ceramic heater 3 is formed
in a rod shape, and is provided with a heating portion 31 having a
heating element inside thereof.
[0061] The metal shell 4 has a screw portion 41 (corresponding to
the fitting portion of the invention) for fitting the gas sensor 1
to the exhaust pipe, and a hexagonal portion 42 for engaging a
fitting tool when fitting to the exhaust pipe. A gasket 5 is
provided on the leading end side of the hexagonal portion 42. The
surface of the screw portion 41 is coated with the anti-seizing
agent of the present invention, thereby preventing seizing with the
exhaust pipe even when the screw portion is fitted to the exhaust
pipe and the metal shell 4 is exposed to a high temperature.
[0062] The metal shell 4 is provided with a fitting shoulder 43
projecting toward an inside diameter direction on an inner
circumference of the leading end side, and a supporting member 7
made of alumina is supported on the fitting shoulder 43 through a
packing 6. The flange portion 24 of the sensor element 2 is
supported on the supporting member 7 through a packing 8. A filling
member 9 is arranged between the inner surface of the metal shell 4
at the back-end side of the supporting member 7 and the outer
surface of the sensor element 2, and a sleeve 100 and a circular
ring 110 are successively interpolated on the back-end side of the
filling member 9.
[0063] A double protector 120 made of a metal, having plural gas
inlet holes 121, is fitted to the leading end side of the metal
shell 4.
[0064] A leading end side of an inner cylinder member 130 is
inserted in the inside of the back-end side of the metal shell 4.
The inner cylinder member 130 is fixed to the metal shell 4 by
crimping a back-end side 44 of the metal shell 4 in an inner
leading end direction so that the leading end side contacts the
circular ring 110. A structure in which the filling member 9 is
compressed and filled through the sleeve 100 is obtained by
crimping the back-end side 44 of the metal shell 4, and by means of
this structure, the sensor element 2 is held inside the cylindrical
metal shell 4 in an air-tight state.
[0065] Plural air introduction holes 131 are formed on the back-end
side of the inner cylinder member 130 with a predetermined distance
along a circumferential direction. A cylindrical filter 140 is
arranged so as to cover the air introduction holes 131 of the inner
cylinder member 130. Further, an outer cylinder member 150 is
arranged so as to cover the filter 140. Plural air introduction
holes 151 are formed on the position of the outer cylinder member
150 corresponding to the filter 140 with a predetermined distance
along a circumferential direction.
[0066] A separator 160 is arranged inside the inner cylinder member
130. The separator 160 has a separator lead line through-hole 161
for inserting element lead wires 170 and 180, and heater lead wires
190 and 200 penetrate from the leading end side to the back-end
side.
[0067] Further, each of the lead wires 170, 180, 190 and 200 (not
shown in detail) has a structure such that a conductive wire is
covered with an insulation coating film comprising a resin, and the
back-end side of the conductive wire is connected to a connector
terminal provided on a connector. The leading end side of the
conductive wire of the element lead wire 170 is crimped together
with the back-end side of a terminal fitting 210 outwardly fitted
to the outer surface of the sensor element 2, and the leading end
side of the conductive wire of the element lead wire 180 is crimped
together with the back-end side of the terminal fitting 220 press
fitted to the inner surface of the sensor element 2. In this
manner, the element lead wire 170 is electrically connected to the
external electrode 23 of the sensor element 2, and the element lead
wire 180 is electrically connected to the internal electrode 22. On
the other hand, the leading end sides of the conductive wires of
the heater lead wires 190 and 200 are connected to a pair of
terminal fittings 230, respectively, joined to a heating element of
the ceramic heater 3.
[0068] A sealing material 240 having excellent heat resistance
comprising a fluorine rubber or the like is fixed to the back-end
side of the separator 160 by crimping the outer cylinder member
150. Four lead wire insertion holes 241 are formed on the sealing
member 240 so as to penetrate in an axial line direction.
Examples
[0069] The present invention is described in greater detail by
reference to the following Examples and Comparative Examples, but
those are illustrative embodiments, and the invention should not be
construed as being limited thereto.
[0070] Test Examples 1 to 33 were prepared by blending a first
solid lubricant, a second solid lubricant, a lubricant base oil, a
lubricant base oil plus a thickening agent, an organic resin,
copper oxide, thallium oxide, iridium oxide, osmium oxide, rhodium
oxide and ruthenium oxide in the blending proportions shown in
Table 1. The preparation method of the Test Example is not
particularly limited. The Test Example can generally be prepared by
mixing and stirring a first solid lubricant, a second solid
lubricant, a lubricant base oil, a lubricant base oil+a thickening
agent, an organic resin, copper oxide, thallium oxide, iridium
oxide, osmium oxide, rhodium oxide and ruthenium oxide, and if
necessary, conducting dispersion treatment using a three-roll mill
or a homogenizer.
[0071] A first solid lubricant, a second solid lubricant, a
lubricant base oil, a lubricant base oil plus a thickening agent,
an organic resin, copper oxide, thallium oxide, iridium oxide,
osmium oxide, rhodium oxide and ruthenium oxide are all
commercially available, industrial products.
TABLE-US-00001 TABLE 1 Test Example 1 2 3 4 5 6 7 8 9 10 11
Bismuth*.sup.1 7 10 18 20 20 20 20 Bismuth oxide*.sup.2 20 20 0 20
Graphite*.sup.3 33 30 22 20 20 Molybdenum disulfide*.sup.4 20 20 20
Boron nitride*.sup.5 20 20 20 Mineral oil*.sup.6 45 45 45 45 45 45
45 Calcium sulfonate complex soap*.sup.7 5 5 5 5 5 5 5 Bisphenol F
epoxy resin*.sup.8 40.2 40.2 40.2 40.2 Amine adduct curing
agent*.sup.9 1.8 1.8 1.8 1.8 Dicyandiamide curing agent*.sup.10 2.7
2.7 2.7 2.7 Reactive diluent*.sup.11 5.3 5.3 5.3 5.3 Copper
oxide*.sup.12 10 10 10 10 10 10 10 10 10 10 10 Thallium
oxide*.sup.13 Iridium oxide*.sup.14 Osmium oxide*.sup.14 Rhodium
oxide*.sup.14 Ruthenium oxide*.sup.14 a 17.5 25 45 50 50 50 50 50
50 50 50 d 82.5 75 55 50 50 50 50 50 50 50 50 a/d 0.2 0.3 0.8 1.0
1.0 1.0 1.0 1.0 1.0 1.0 1.0 e 25 25 25 25 25 25 25 25 25 25 25 b
125 125 12 125 125 125 125 0 0 0 0 c 0 0 0 0 0 0 0 125 125 125 125
Test Example 12 13 14 15 16 17 18 19 20 21 22 Bismuth*.sup.1 30 35
36 37 16 16 16 16 16 Bismuth oxide*.sup.2 16 16 Graphite*.sup.3 10
5 4 3 16 16 16 16 16 Molybdenum disulfide*.sup.4 16 Boron
nitride*.sup.5 16 Mineral oil*.sup.6 45 45 45 45 57 56 53 53 34
Calcium sulfonate complex soap*.sup.7 5 5 5 5 8 7 7 7 4 Bisphenol F
epoxy resin*.sup.8 48.2 48.2 Amine adduct curing agent*.sup.9 2.2
2.2 Dicyandiamide curing agent*.sup.10 3.2 3.2 Reactive
diluent*.sup.11 6.4 6.4 Copper oxide*.sup.12 10 10 10 10 3 5 8 8 8
8 30 Thallium oxide*.sup.13 Iridium oxide*.sup.14 Osmium
oxide*.sup.14 Rhodium oxide*.sup.14 Ruthenium oxide*.sup.14 a 75
87.5 90 92.5 50 50 50 50 50 50 50 d 25 12.5 10 7.5 50 50 50 50 50
50 50 a/d 3.0 7.0 9.0 12.3 1.0 1.0 1.0 1.0 1.0 1.0 1.0 e 25 25 25
25 9.4 15.6 25 25 25 25 93.8 b 125 125 125 125 203.1 196.9 187.5
187.5 0 0 118.8 c 0 0 0 0 0 0 0 0 187.5 187.5 0 Test Example 23 24
25 26 27 28 29 30 31 32 33 Bismuth*.sup.1 16 25 23 10 8 8 25 23 10
9 8 Bismuth oxide*.sup.2 Graphite*.sup.3 16 25 23 10 9 8 25 23 10 9
8 Molybdenum disulfide*.sup.4 Boron nitride*.sup.5 Mineral
oil*.sup.6 30 35 39 62 64 65 Calcium sulfonate complex soap*.sup.7
3 5 5 8 8 8 Bisphenol F epoxy resin*.sup.8 32.5 35.5 56.3 57.9 59.5
Amine adduct curing agent*.sup.9 1.4 1.5 2.5 2.6 2.7 Dicyandiamide
curing agent*.sup.10 2.2 2.4 3.8 3.9 4 Reactive diluent*.sup.11 4.2
4.6 7.4 7.6 7.8 Copper oxide*.sup.12 35 10 10 10 10 10 10 10 10 10
10 Thallium oxide*.sup.13 Iridium oxide*.sup.14 Osmium
oxide*.sup.14 Rhodium oxide*.sup.14 Ruthenium oxide*.sup.14 a 50 50
50 50 50 50 50 50 50 50 50 d 50 50 50 50 50 50 50 50 50 50 50 a/d
1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 e 109.4 20 21.7 50 55.6
62.5 20 21.7 50 55.6 62.5 b 103.1 80 95.7 350 400 462.5 0 0 0 0 0 c
0 0 0 0 0 0 80 95.7 350 400 462.5 *.sup.1Product of Sumitomo Metal
Mining Co., Ltd. *.sup.2Product of Nissan Kagaku Sangyo Co., Ltd.
*.sup.3Scale-like graphite *.sup.4Product of IPROS Corporation
*.sup.5DENKA BORON NITRIDE HGP, a product of Denki Kagaku Kogyo
K.K. *.sup.6SNH-46, a product of Sankyo Yuka Kogyo K.K.
*.sup.7G-2000, a product of Krompton *.sup.8EPICRON 830S, a product
of Dainippon Ink and Chemicals, Incorporated *.sup.9AMICURE PN-23,
a product of Ajinomoto Fine-Techno Co., Inc. *.sup.10AMICURE
AH-154, a product of Ajinomoto Fine-Techno Co., Inc.
*.sup.11Alkylene monoglycidyl ether having viscosity at 25.degree.
C. of 6.5 to 9.0 mPa s and an epoxy equivalent of 280 to 320 g/eq.
*.sup.12Cupric oxide, a product of Nissan Kagaku Sangyo Co., Ltd.
*.sup.13Commercially available reagent (made in USA)
*.sup.14Commercially available reagent (made in Japan).
[0072] The numerical value in Table 1 shows a blending proportion
(weight % or part by weight). The average particle diameter of
graphite in Table 1 is 30 .mu.m or less.
[0073] (Evaluation of Workability)
[0074] An evaluation was conducted in which about 60 mg of each of
the anti-seizing agents of Test Examples 1 to 33 shown in Table 1
above were applied to the screw portion 41 of the metal shell 4
used in the gas sensor 1 described above. The evaluation results
are shown in Table 2.
[0075] (Evaluation of Anti-Seizing Effect)
[0076] About 60 mg of the anti-seizing agent was applied to the
screw portion 41 of the metal shell 4 used in the gas sensor 1
described above, and the metal shell 4 was screwed into a sample
nut with a torque of 60 Nm. The metal shell 4 is made of SUS 430,
and the sample nut is made of SUS 409L. This evaluation was
conducted using a metal shell 4 prior to fitting to the gas sensor
1, and by screwing the metal shell 4 (no gas sensor) into the nut.
The metal shell 4 and the nut thus unified were then heated in an
electric oven at 500.degree. C. or 700.degree. C. for 100 hours.
The unified product was cooled to room temperature, and the metal
shell 4 was loosened from the nut. This test procedure was applied
to ten test samples. The proportion of the number of metal shells 4
exhibiting seizing is expressed by percentage, and indicated as a
degree of seizing (%). The term "exhibiting seizing" indicates a
state in which when the metal shell 4 is loosened by hand using a
torque trench, the metal shell 4 is not unscrewed from the nut. In
this case, when the metal shell 4 is loosened with further strong
force, the thread of the screw portion 41 of the metal shell 4 is
crushed. The evaluation was conducted on the basis of the degree of
seizing as follows.
.circleincircle.: Degree of seizing is 0%. O: Degree of seizing
exceeds 0% but is 5% or less. .DELTA.: Degree of seizing exceeds 5%
but is 20% or less. X: Degree of seizing exceeds 20%.
[0077] The evaluation results of Test Examples 1 to 33 are shown in
Table 2.
[0078] (Evaluation of Corrosion Resistance)
[0079] About 60 mg of each of Test Examples 1 to 33 prepared as
shown in Table 1 was applied to the screw portion 41 of the metal
shell 4 used in the gas sensor 1 described above, and the metal
shell 4 was screwed into a sample nut with a torque of 60 Nm. The
metal shell 4 is made of SUS 430, and the sample nut is made of SUS
409L. This evaluation was conducted using a metal shell 4 prior to
fitting to the gas sensor 1, and by screwing the metal shell 4 (no
gas sensor) into the nut. The metal shell 4 and the nut thus
unified were then heated in an electric oven at 500.degree. C. or
700.degree. C. for 100 hours. The unified product was cooled to
room temperature, and the metal shell 4 was loosened from the nut.
The metal shell 4 was divided into halves, and a cross section of
the screw portion 41 was subjected to component mapping with EDS
(Energy Dispersive X-ray Spectroscopy). Of the component mappings,
a thickness from which oxygen was detected was calculated as an
oxide film thickness. An evaluation of an oxide film thickness of
20 .mu.m or greater was graded X, and an oxide film thickness of
less than 20 .mu.m was graded o. The evaluation results are shown
in Table 2.
TABLE-US-00002 TABLE 2 Test Example 1 2 3 4 5 6 7 8 9 10 11 Seizing
500.degree. C. .DELTA. .DELTA. .circleincircle. .circleincircle.
.largecircle. .largecircle. .largecircle. .circleincircle.
.largecircle. .circleincircle. .largecircle. Seizing 700.degree. C.
.DELTA. .largecircle. .circleincircle. .circleincircle.
.circleincircle. .largecircle. .largecircle. .circleincircle.
.circleincircle. .circleincircle. .circleincircle. Corrosion
resistance .largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. Workability .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. Example 12 13 14 15 16 17 18 19 20 21
22 Seizing 500.degree. C. .circleincircle. .largecircle. .DELTA.
.DELTA. .circleincircle. .circleincircle. .circleincircle.
.largecircle. .largecircle. .largecircle. .largecircle. Seizing
700.degree. C. .circleincircle. .circleincircle. .largecircle.
.DELTA. .circleincircle. .circleincircle. .circleincircle.
.largecircle. .circleincircle. .largecircle. .largecircle.
Corrosion resistance .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. Workability .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. Test Example 23 24 25 26 27 28 29 30 31
32 33 Seizing 500.degree. C. .DELTA. -- .largecircle. .largecircle.
.largecircle. .DELTA. -- .largecircle. .largecircle. .largecircle.
.DELTA. Seizing 700.degree. C. .largecircle. -- .largecircle.
.largecircle. .largecircle. .largecircle. -- .circleincircle.
.circleincircle. .largecircle. .largecircle. Corrosion resistance
.largecircle. -- .largecircle. .largecircle. .largecircle.
.largecircle. -- .largecircle. .largecircle. .largecircle.
.largecircle. Workability .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle.
[0080] In the seizing agents of Test Examples 1 to 33 of the
present invention using at least one of bismuth and bismuth oxide
as the first solid lubricant; graphite, molybdenum disulfide or
boron nitride as the second solid lubricant; a mineral oil as the
lubricant base oil, a grease obtained by thickening the mineral oil
with calcium sulfonate complex soap as a thickening agent, or
bisphenol F epoxy resin; and at least one of copper oxide, thallium
oxide, iridium oxide, osmium oxide, rhodium oxide and ruthenium
oxide, Test Example 1 having a graphite content of as large as
d=82.4, exhibited a poor anti-seizing effect. In Test Example 15
where the bismuth content was as large as a=92.5, the anti-seizing
effect was also found to be poor. In Test Example 2, the ratio of
graphite to bismuth was a/d=0.3, and the anti-seizing effect was
slightly poor. In Test Example 14 the ratio of graphite to bismuth
was a/d=9, and the anti-seizing effect was slightly poor. In Test
Example 16 the copper oxide content e was 9.4, and the corrosion
resistance was poor. In Test Example 23 the copper oxide content e
was 109, and the corrosion resistance was poor. In Test Example 24
the lubricant base oil content b was 80, and the workability was
poor. In Test Example 28 the lubricant base oil content b was 462,
and the corrosion resistance was poor. In Test Example 29 the
organic resin content c was 80, and the workability was poor. In
Test Example 33 the organic resin content c was 462, and the
corrosion resistance was poor.
[0081] When the screw portion of the gas sensor 1 was analyzed, the
bismuth component was found to be present on substantially the
entire outer surface thereof. Before the screw portion of the gas
sensor 1 and the nut were fastened, the anti-seizing agent evenly
covered the outer surface of the screw portion 41. However, when
the screw portion was fitted to the nut, the anti-seizing agent
covering the outer surface of the screw portion 41 became unevenly
distributed. That is, relatively large amounts of the anti-seizing
agent were present at the top of threads and at the bottom of the
valleys of the screw portion 41, while being scarce or lacking in
the middle between the top of the threads and the bottom of the
valleys of the screw portion 41. After being heated to a
temperature of 270.degree. C. or higher, i.e. 700.degree. C., the
bismuth in the anti-seizing agent melts and penetrates the entire
interface between the screw portion 41 and the nut, including the
middle between the top of the threads and the bottom of the valleys
of the screw portion 41. As a result, there is no area where the
screw portion 41 and the nut are in direct contact, thereby
preventing seizing between the screw portion 41 and the nut when
sliding one surface against the other. The term "the bismuth
component of the anti-seizing agent remains on a central portion of
the outer surface of the fitting part," as used herein means that
when the central portion surface of the outer surface (in the case
of the screw portion 41, the central portion on the surface between
thread and valley) is subjected to EDS analysis, a peak of bismuth
is observed, and therefore, the bismuth component is determined to
be present.
[0082] This application is based on Japanese Patent Application JP
2005-341440, filed Nov. 28, 2005, and Japanese Patent Application
JP 2006-259640, filed Sep. 25, 2006, the entire contents of which
are hereby incorporated by reference, the same as if set forth at
length.
* * * * *