CN1974737A - Anti-seizing agent, sensor and assembly including sensor - Google Patents
Anti-seizing agent, sensor and assembly including sensor Download PDFInfo
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- CN1974737A CN1974737A CN 200610160813 CN200610160813A CN1974737A CN 1974737 A CN1974737 A CN 1974737A CN 200610160813 CN200610160813 CN 200610160813 CN 200610160813 A CN200610160813 A CN 200610160813A CN 1974737 A CN1974737 A CN 1974737A
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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 %<=a<=90 weight % and 10 weight %<=d<=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.
Description
Technical field
The present invention relates to a kind of anti-seizing agent.In particular, the present invention relates to a kind ofly be used to prevent to be exposed to the anti-seizing agent of 500 ℃ or higher pyritous part hot joining (seizing) and adopt the transmitter of this anti-seizing agent and comprise the assembly of this transmitter.
Background technology
Anti-seizing agent is usually coated the threaded portion of metal parts to prevent hot joining, and this part is used to make then.This metal parts comprises the metal shell of gas sensor and the metal shell of temperature sensor, wherein this gas sensor vapor pipe of being mounted to oil engine etc. is used for surveying gas specific gas component to be measured, and this temperature sensor is mounted to the temperature that vapor pipe etc. is used to survey gas to be measured.The example of anti-seizing agent comprises the pasty state anti-seizing agent of the solid lubricant that comprises lubricant base oil and wherein comprise, and comprise by lubricating grease that obtains with thickening material semicure lubricant base oil and the solid lubricant that wherein comprises the pasty state anti-seizing agent (for example, referring to Masahisa Matsunaga etc., the solid lubrication handbook, the 409-416 page or leaf, Saiwai Shobo Co., 1978).
Traditionally, comprise as metals such as copper, aluminium or nickel as main component, and the solid lubricant that mixes molybdenumdisulphide or graphite as required is widely used in the pasty state anti-seizing agent, this anti-seizing agent is coated and can be exposed to 500 ℃ or higher pyritous metal parts (for example, referring to JP-B-8-19435).
Make these metals be used to prevent the machine-processed as described below of hot joining.The pasty state anti-seizing agent that comprises above-mentioned metal is applied in the required part of metal parts, thereby forms uniform intermediate coat (intervening film) on metal parts.When making metal parts with other part, intermediate coat is present between metal parts and other part.As a result, when metal parts is exposed to high temperature,, prevent hot joining between metal parts and other part owing to constitute the softening lubrication that causes of the metal of intermediate coat then by when other part is taken apart (when metal parts and other part slide).
The problem that the present invention need solve
Yet, when making metal parts, be formed on even intermediate coat on the metal parts and exist only on the part between metal parts and other part with other part.In this case, the position that exists metal parts and other part directly to contact, the result can not obtain heat resistanceheat resistant and connect effect.
For this reason,, also on the whole surface between metal parts and other part, form the anti-seizing agent of intermediate coat, connect effect thereby show required heat resistanceheat resistant even need be a kind of when metal parts and the slip of other part.
Especially, up to now, also obtain to be used for the transmitter that under the high temperature mal-condition, uses, have an anti-seizing agent that abundant heat resistanceheat resistant connects performance.
Summary of the invention
Therefore, the purpose of this invention is to provide a kind of anti-seizing agent of the problems referred to above of prior art, a kind of transmitter and a kind of assembly that comprises this transmitter of solving.That is to say, the purpose of this invention is to provide a kind of under metal parts is exposed to 500 ℃ or higher pyritous situation, even when metal parts and the slip of other part, also can on the whole contact area between metal parts and other part, form the anti-seizing agent of inteferometer coating, a kind of transmitter and a kind of assembly that comprises this transmitter that uses this anti-seizing agent.
By providing a kind of anti-seizing agent to realize above-mentioned purpose of the present invention, this anti-seizing agent comprises: first solid lubricant, and it comprises at least a in bismuth and the bismuth compound; With second solid lubricant, it comprises at least a in graphite, molybdenumdisulphide and the boron nitride, wherein, anti-seizing agent satisfies 20 weight %≤a≤90 weight % and 10 weight %≤d≤80 weight %, wherein, the content sum of getting first solid lubricant in the anti-seizing agent and second solid lubricant is as 100 weight %, and a represents the content of first solid lubricant, and d represents the content of second solid lubricant.
In preferred embodiments, the content of first solid lubricant and second solid lubricant satisfies relational expression 0.8≤a/d≤8.
In another preferred embodiment, first solid lubricant is one of bismuth and bismuth compound, anti-seizing agent also comprises antioxidant, this antioxidant comprises at least a in cupric oxide, thallium oxide, iridium oxide, osmium oxide, rhodium oxide and the ruthenium oxide, when the content sum of getting first solid lubricant and second solid lubricant during as 100 weight parts, the content e of antioxidant satisfies 10 weight parts≤e≤100 weight parts.
In another preferred embodiment, anti-seizing agent also comprises lubricant base oil, perhaps lubricant base oil and thickening material, when the content sum of getting first solid lubricant and second solid lubricant during as 100 weight parts, the content b of lubricant base oil, perhaps the content sum b of lubricant base oil and the thickening material when existing satisfies 90 weight parts≤b≤400 weight parts.
In another preferred embodiment, anti-seizing agent also comprises organic resin, wherein, and when the content sum of getting first solid lubricant and second solid lubricant during as 100 weight parts, the content of organic resin is c, and it satisfies relational expression 90 weight parts≤c≤400 weight parts.
Preferred anti-seizing agent is coated metal parts.
Distinguishingly, has the transmitter that is used for surveying the detecting element of gaseous phase to be measured and keeps the metal shell of this detecting element, this metal shell has the department of assembly that is used for this detecting element is assembled to vapor pipe when detecting element is exposed to gas to be measured, and preferably this anti-seizing agent is coated the outside surface of the department of assembly at least of metal shell.
In addition, in a kind of assembly, this assembly comprises having the transmitter that is used to survey the detecting element of gaseous phase to be measured and keeps the metal shell of this detecting element; Be formed on the transmitter metal housing so that detecting element is exposed to the vapor pipe of the department of assembly of gas to be measured with being used to assemble, when transmitter and vapor pipe assembling, preferred this anti-seizing agent be present in metal shell the department of assembly outside surface and assemble between the surface of vapor pipe of this department of assembly, after this department of assembly was heated to 270 ℃ or higher temperature, the bismuth composition of anti-seizing agent was retained on the central part of outside surface of department of assembly.
Anti-seizing agent of the present invention provides good heat resistanceheat resistant to connect effect, especially for being exposed to 500 ℃ or higher pyritous metal parts, particularly for the department of assembly of the metal shell of transmitter.
Description of drawings
Fig. 1 is the sectional view according to the gas sensor 1 of the embodiment of the invention.
The explanation of Reference numeral:
The Reference numeral that is used to distinguish various constitutional featuress among the figure comprises as follows.
1 gas sensor
2 gas sensor elements
3 well heaters
4 metal shells
7 bracing members
9 noggin pieces
100 sleeves
120 protectors
Barrel member in 130
140 strainers
150 outer barrel members
160 partition members (separator)
240 containment members
136 filter part
200,300 strainer covering members
201,301 covering portions
202,302 openings
203,303 insertion sections
Embodiment
Anti-seizing agent of the present invention comprises first solid lubricant and second solid lubricant.
First solid lubricant comprises at least a as main component in bismuth and the bismuth compound.The inventor thinks the hot joining that can prevent metal parts by following machine-processed anti-seizing agent.Anti-seizing agent is applied in the required part of metal parts, thereby forms even intermediate coat.When making metal parts with other part, anti-seizing agent is confined to a part, and the result exists only on the part between metal parts and other part or in the isolated part, makes other parts directly contact.Yet, when metal parts is exposed to high temperature, bismuth fusing in the anti-seizing agent and the whole interface between infiltration metal parts and other part, thus form intermediate coat once more.This makes when metal parts slides with respect to other part, can prevent hot joining by the lubrication of intermediate coat.
The bismuth compound of first solid lubricant comprises bismuth oxide.These compounds are commercially available, and have 100 μ m or littler, and preferred 30 μ m or littler median size.
Second solid lubricant comprises at least a in graphite, molybdenumdisulphide and the boron nitride.The inventor thinks that by further introducing second solid lubricant when the bismuth infiltration was between metal parts and other part, second solid lubricant permeated simultaneously, so second solid lubricant is present between metal parts and other part.This makes and can further improve lubricity.
In anti-seizing agent of the present invention, the content a of first solid lubricant and the content d of second solid lubricant satisfy: when getting a+d and be 100 weight %, and 20 weight %≤a≤90 weight % and 10 weight %≤d≤80 weight %.As a during less than 20 weight % (d is greater than 80 weight %), be difficult to form intermediate coat, heat resistanceheat resistant connects the effect deterioration.On the other hand, as a during greater than 90 weight % (d is less than 10 weight %), the amount of second solid lubricant is too little in the intermediate coat, can not obtain heat resistanceheat resistant and connect effect.
In anti-seizing agent of the present invention, the content a of first solid lubricant and the content d of second solid lubricant preferably satisfy relational expression: 0.8≤a/d≤8.When a/d less than 0.8 the time, be difficult to form intermediate coat, heat resistanceheat resistant connects effect with deterioration.On the other hand, when a/d greater than 8 the time, the amount of second solid lubricant in the intermediate coat is too little, can not obtain heat resistanceheat resistant and connect effect.
Among the anti-seizing agent of the present invention, coat metal parts when bismuth-containing or bismuth compound as the anti-seizing agent of first solid lubricant, this metal parts (for example is exposed to high temperature, 700 ℃ or higher temperature) time, metal parts is oxidized, in this case, and its strength deterioration.
The inventor thinks that this is because following mechanism.When being exposed to 700 ℃ or higher high temperature, the oxidized formation bismuth oxide of bismuth (metallic state) (below be also referred to as oxidizing reaction).Yet the space between metal parts and other part is an enclosed space, can easily reduce bismuth oxide.When the oxygen partial pressure in the enclosed space reduced, the product bismuth oxide of oxidizing reaction was reduced to bismuth metal (below be also referred to as reduction reaction).The bismuth that reduction reaction produces be formed on the lip-deep passive state film of metal parts (passive film) reaction to remove this passive state film.As a result, removed metal parts surperficial oxidized of passive state film.
Therefore, when bismuth or bismuth oxide existed as first solid lubricant, preferred anti-seizing agent of the present invention comprised at least a in cupric oxide, thallium oxide, iridium oxide, osmium oxide, rhodium oxide and the ruthenium oxide.By adopting such oxide compound, provide the oxygen composition to enclosed space, thereby prevent the reduction of oxygen partial pressure in the enclosed space.Therefore, can suppress reduction reaction.As a result, can prevent the oxidation of metal parts.Consider production safety, cost etc., preferred oxides is a cupric oxide.When the content sum of the content of getting first solid lubricant and second solid lubricant during as 100 weight parts, the content e of preferred oxides is 10 weight parts≤e≤100 weight parts.As e during, be difficult to prevent that metal parts is oxidized less than 10 weight parts.On the other hand, as e during greater than 100 weight parts, the component ratio of first solid lubricant and second solid lubricant reduces, and heat resistanceheat resistant connects effect with deterioration.
Anti-seizing agent of the present invention can further comprise lubricant base oil or lubricant base oil and thickening material.The example of lubricant base oil comprises mineral oil, synthetic hydrocarbon oil, polyalkylene glycol, multi-hydroxy ester (polyol ester), the phenyl ether of alkyl replacement and their mixing oil.Yet, the invention is not restricted to this.
The example of the thickening material that uses in anti-seizing agent of the present invention comprises calcium sulphonate compound soap, lithium compound soap, calcium compound soap, lithium soap, calcium soap, organobentonite, finely powdered silicon oxide, aliphatic double urea compound, alicyclic double urea compound, aromatic series double urea compound, three carbamide compounds and four carbamide compounds, is suitable as grease thickener.
When the content sum of the content of getting first solid lubricant and second solid lubricant during as 100 weight parts, the content b of lubricant base oil, perhaps the content sum of lubricant base oil and thickening material is 90 weight parts≤b≤400 weight parts.As b during less than 90 weight parts, the forfeiture of the flowability of anti-seizing agent is difficult to coat the sliding surface of part.On the other hand,, do not show the effect of solid lubricant, therefore, be difficult to obtain heat resistanceheat resistant and connect effect as b during greater than 400 weight parts.
The example of other additive that may comprise in the anti-seizing agent comprises antioxidant, extreme-pressure additive, detergent dispersant, rust-preventive agent, sanitas, defoamer and thinner.
Anti-seizing agent of the present invention can further comprise organic resin.The example of organic resin comprises bisphenol F epoxy resin, bisphenol A epoxide resin, silicone resin and TYRANN0 resin (Ube Industries, Ltd. trade name comprises titanium carbon silane (titanocarbosilane) and polyalkylphenylsilox,ne (polyalkylphenylsiloxane).Yet, the invention is not restricted to this.
When the content sum of the content of getting first solid lubricant and second solid lubricant during as 100 weight parts, the content c of organic resin is 90 weight parts≤c≤400 weight parts.As c during less than 90 weight parts, the forfeiture of the flowability of anti-seizing agent is difficult to coat the sliding surface of part.On the other hand,, do not show the effect of solid lubricant, therefore, be difficult to obtain heat resistanceheat resistant and connect effect as c during greater than 400 weight parts.
The example of other additive that may comprise in the anti-seizing agent comprises UV light absorber, wetting dispersing agent, surface-modifying agent and solidifying agent.
Anti-seizing agent of the present invention can be used in the threaded portion of the nut member that gas sensor is assembled to vapor pipe shown in JP-A-11-190720, perhaps can be used in the following gas sensor that will illustrate 1, as anti-seizing agent.The gas sensor 1 of the present embodiment is the embodiment of an embodiment, but the present invention should not be construed as limited to this.Gas sensor 1 (oxygen sensor) is mounted to automobile exhaust pipe and surveys oxygen concentration in the exhaust.Fig. 1 is the sectional view that the integral construction of gas sensor 1 is shown.
As shown in the figure, gas sensor 1 is provided with sensor element 2 in the band bottom tube-like that is formed into front end sealing, is inserted in the ceramic heater 3 in the sensor element 2 and sensor element 2 is remained on wherein metal shell 4.Shown in the figure among the direction of the axis of sensor element 2, towards a side (closed side that is exposed to the front end of gas to be measured (exhaust), downside among the figure) be called as " front ", a side (upside among the figure) of the direction that court is opposite with above-mentioned side is called as " rear end side ".
Outer electrode 23 on internal electrode of making by Pt or Pt alloy on the internal surface that gas sensor 2 comprises solid electrolyte body 21 with oxygen-ion conductive, be formed on solid electrolyte body 21 22 and the outside surface that is formed on solid electrolyte body 21.Be set at the middle position on the axis of sensor element 2 towards the outstanding flange part 24 of external diameter direction.Ceramic heater 3 is formed bar-shaped and is provided with heating part 31, has heating unit in this heating part 31.
The double protecting device 120 that is made of metal, have a plurality of air inlet ports 121 is mounted to the front of metal shell 4.
The front of interior barrel member 130 is inserted the inboard of the rear end side of metal shell 4.By rear end side 44 interior barrel member 130 is fixed to metal shell 4, makes front end side contact annulus 110 along Inner Front End direction crimping metal shell 4.Rear end side 44 by crimp metal shell 4 obtains the structure that noggin piece 9 is compressed and fills via sleeve 100, and by this structure, sensor element 2 is maintained at the inboard of tubular metal shell 4 with sealed state.
Rear end side at interior barrel member 130 along the circumferential direction forms a plurality of air entrance holes 131 with predetermined distance.The air entrance hole 131 of barrel member 130 in cartridge filter 140 is arranged to cover.In addition, outer barrel member 150 is arranged to precoat filter 140.Barrel member 150 along the circumferential direction forms a plurality of air entrance holes 151 with predetermined distance with strainer 140 corresponding positions outside.
Internal layout partition member 160 at interior barrel member 130.Partition member 160 has the partition member wire through-hole 161 that is used for insertion element lead-in wire 170 and 180, and heater lead 190 and 200 passes rear end side from front.
In addition, lead-in wire each in 170,180,190 and 200 (not the specifically illustrating) has lead and is comprised that the insulating coating film of resin covers and the rear end side of lead is connected to the structure that is arranged on the bonder terminal on the junctor.By to convex edge, the front of the lead of component lead 180 is assembled to the rear end side of clamped nipple 220 of sensor element 2 internal surfaces by to convex edge with pressure to the front of the lead of component lead 170 with the rear end side of the clamped nipple 210 that is assembled to sensor element 2 outside surfaces.Like this, component lead 170 is electrically connected with the outer electrode 23 of sensor element 2, and component lead 180 is electrically connected with internal electrode 22.On the other hand, the front of heater lead 190 and 200 lead is connected with a pair of clamped nipple 230 that engages with the heating unit of ceramic heater 3 respectively.
The sealing material with good heat resistance 240 that comprises viton etc. is fixed to the rear end side of partition member 160 by the outer barrel member 150 of crimp.On containment member 240, form four lead patchholes 241 that pass sealing member 240 along axis direction.
Embodiment
With reference to following embodiment and Comparative Examples the present invention is described in further detail, but these embodiment are exemplary embodiments, the present invention should not be construed as limited to this.
By mix first solid lubricant, second solid lubricant, lubricant base oil according to the ratio of mixture shown in the table 1, lubricant base oil adds thickening material, organic resin, cupric oxide, thallium oxide, iridium oxide, osmium oxide, rhodium oxide and ruthenium oxide and prepares test example 1 to 33.The preparation method of test example is not special restriction.The test example can and stir first solid lubricant, second solid lubricant, lubricant base oil by mixing usually, lubricant base oil adds thickening material, organic resin, cupric oxide, thallium oxide, iridium oxide, osmium oxide, rhodium oxide and ruthenium oxide and prepares, if desired, use three-roll mill or homogenizer to carry out dispersion treatment.
It all is commercially available Industrial products that first solid lubricant, second solid lubricant, lubricant base oil, lubricant base oil add thickening material, organic resin, cupric oxide, thallium oxide, iridium oxide, osmium oxide, rhodium oxide and ruthenium oxide.
Table 1
| The test example | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 |
| | 7 | 10 | 18 | 20 | 20 | 20 | 20 | ||||
| Bismuth oxide *2 | 20 | 20 | 20 | 20 | |||||||
| Graphite *3 | 33 | 30 | 22 | 20 | 20 | ||||||
| Molybdenumdisulphide *4 | 20 | 20 | 20 | ||||||||
| Boron nitride *5 | 20 | 20 | 20 | ||||||||
| Mineral oil *6 | 45 | 45 | 45 | 45 | 45 | 45 | 45 | ||||
| The calcium | 5 | 5 | 5 | 5 | 5 | 5 | 5 | ||||
| Bisphenol F epoxy resin *8 | 40.2 | 40.2 | 40.2 | 40.2 | |||||||
| The amine adduct solidifying agent *9 | 1.8 | 1.8 | 1.8 | 1.8 | |||||||
| Dicy-curing agent *10 | 2.7 | 2.7 | 2.7 | 2.7 | |||||||
| Reactive thinner *11 | 5.3 | 5.3 | 5.3 | 5.3 | |||||||
| Cupric oxide *12 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
| Thallium oxide *13 | |||||||||||
| Iridium oxide *14 | |||||||||||
| Osmium oxide *14 | |||||||||||
| Rhodium oxide *14 |
| Ruthenium oxide *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 |
Table 1 (continuing)
| The test example | 12 | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 | 21 | 22 |
| Bismuth *1 | 30 | 35 | 36 | 37 | 16 | 16 | 16 | 16 | 16 | ||
| Bismuth oxide *2 | 16 | 16 | |||||||||
| Graphite *3 | 10 | 5 | 4 | 3 | 16 | 16 | 16 | 16 | 16 | ||
| Molybdenumdisulphide *4 | 16 | ||||||||||
| Boron nitride *5 | 16 | ||||||||||
| Mineral oil *6 | 45 | 45 | 45 | 45 | 57 | 56 | 53 | 53 | 34 | ||
| The calcium | 5 | 5 | 5 | 5 | 8 | 7 | 7 | 7 | 4 | ||
| Bisphenol F epoxy resin *8 | 48.2 | 48.2 | |||||||||
| The amine adduct solidifying agent *9 | 2.2 | 2.2 | |||||||||
| Dicy-curing agent *10 | 3.2 | 3.2 | |||||||||
| Reactive thinner *11 | 6.4 | 6.4 | |||||||||
| Cupric oxide *12 | 10 | 10 | 10 | 10 | 3 | 5 | 8 | 8 | 8 | 8 | 30 |
| Thallium oxide *13 | |||||||||||
| Iridium oxide *14 | |||||||||||
| Osmium oxide *14 | |||||||||||
| Rhodium oxide *14 | |||||||||||
| Ruthenium oxide *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 |
Table 1 (continuing)
| The test example | 23 | 24 | 25 | 26 | 27 | 28 | 29 | 30 | 31 | 32 | 33 |
| Bismuth *1 | 16 | 25 | 23 | 10 | 8 | 8 | 25 | 23 | 10 | 9 | 8 |
| Bismuth oxide *2 | |||||||||||
| Graphite *3 | 16 | 25 | 23 | 10 | 9 | 8 | 25 | 23 | 10 | 9 | 8 |
| Molybdenumdisulphide *4 |
| Boron nitride *5 | |||||||||||
| Mineral oil *6 | 30 | 35 | 39 | 62 | 64 | 65 | |||||
| The calcium | 3 | 5 | 5 | 8 | 8 | 8 | |||||
| Bisphenol F epoxy resin *8 | 32.5 | 35.5 | 56.3 | 57.9 | 59.5 | ||||||
| The amine adduct solidifying agent *9 | 1.4 | 1.5 | 2.5 | 2.6 | 2.7 | ||||||
| Dicy-curing agent *10 | 2.2 | 2.4 | 3.8 | 3.9 | 4 | ||||||
| Reactive thinner *11 | 4.2 | 4.6 | 7.4 | 7.6 | 7.8 | ||||||
| Cupric oxide *12 | 35 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
| Thallium oxide *13 | |||||||||||
| Iridium oxide *14 | |||||||||||
| Osmium oxide *14 | |||||||||||
| Rhodium oxide *14 | |||||||||||
| Ruthenium oxide *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 |
*1:Sumitomo Metal Mining Co., the Ltd. product
*2:Nissan Kagaku Sangyo Co., the Ltd. product
*3: flaky graphite
*4:IPROS Corporation product
*5:DENKA BORON NITRIDE HGP, Denki Kagaku KogyoK.K. product
*6:SNH-46, Sankyo Yuka Kogyo K.K. product
*7:G-2000, the Krompton product
*8:EPICRON 830S, Dainippon Ink and Chemicals, Incorporated product
*9:AMICURE PN-23, Ajinomoto Fine-Techno Co., Inc. product
*10:AMICURE AH-154, Ajinomoto Fine-Techno Co., Inc. product
*The alkylidene group that has 6.5 to 9.0mPas viscosity and epoxy equivalent (weight) 280 to 320g/eq in the time of the 11:25 ℃ single glyceryl ether (alkylene monoglycidyl ether) that shrinks
*12: cupric oxide, Nissan Kagaku Sangyo Co., Ltd. product
*13: commercial obtainable reagent (Americanized)
*14: commercial obtainable reagent (Japan makes)
Numerical value in the table 1 illustrates mixing ratio (weight % or weight part).The median size of graphite is 30 μ m or littler in the table 1.
(usability evaluation)
Above the threaded portion 41 of the applied metal shell 4 that in above-mentioned gas transmitter 1, uses of the about 60mg of every kind of anti-seizing agent of the test example 1 to 33 shown in the table 1, it is estimated.Evaluation result is as shown in table 2.
(heat resistanceheat resistant connects effect assessment)
The threaded portion 41 of the applied metal shell 4 that in above-mentioned gas transmitter 1, uses of the anti-seizing agent of about 60mg, and metal shell 4 is by in the moment of torsion precession sample nut with 60Nm.Metal shell 4 is made by SUS 430, and the sample nut is made by SUS 409L.Before being assembled to gas sensor 1, use metal shell 4 also by carrying out this evaluation in metal shell 4 (no gas sensor) the precession nut.Then, the heating 100 hours in the electric furnace of 500 ℃ or 700 ℃ of metal shell 4 that so becomes one and nut.This one product is cooled to room temperature, and metal shell 4 is unclamped from nut.This test process is applied to ten test examples.The number ratio of the metal shell 4 of performance hot joining is represented with per-cent, and is represented as hot joining degree (%).The state that metal shell 4 is not unscrewed from nut represented by use moment of torsion ditch (torque trench) when manually unclamping metal shell 4 in term " performance hot joining ".In this case, when more powerful the unclamping of metal shell 4 quilts, the screw of the threaded portion 41 of metal shell 4 is crushed.Carry out following evaluation based on the hot joining degree.
◎: the hot joining degree is 0%
Zero: the hot joining degree is greater than 0% but smaller or equal to 5%
△: the hot joining degree is greater than 5% but smaller or equal to 20%
X: the hot joining degree is greater than 20%
The evaluation result of test example 1 to 33 is as shown in table 2.
(erosion resistance evaluation)
The threaded portion 41 of the applied metal shell 4 that in above-mentioned gas transmitter 1, uses of each test example 1 to 33 about 60mg of preparation as shown in table 1, and metal shell 4 is by in the moment of torsion precession sample nut with 60Nm.Metal shell 4 is made by SUS 430, and the sample nut is made by SUS 409L.Before being assembled to gas sensor 1, use metal shell 4 also by carrying out this evaluation in metal shell 4 (no gas sensor) the precession nut.Then, the heating 100 hours in the electric furnace of 500 ℃ or 700 ℃ of metal shell 4 that so becomes one and nut.This one product is cooled to room temperature, and metal shell 4 is unclamped from nut.Metal shell 4 is divided into two halves, utilizes the cross section of EDS (energy dispersive X-ray spectrum) double thread portion 41 to carry out the composition drawing.Among the composition drawing, calculate and therefrom detect the thickness of oxygen as oxide film thickness.The evaluation of 20 μ m or bigger oxide film thickness is cited as grade X, is cited as grade zero less than the evaluation of the oxide film thickness of 20 μ m.Evaluation result is as shown in table 2.
Table 2
| The test example | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | |
| Hot joining | 500℃ | △ | △ | ◎ | ◎ | ○ | ○ | ○ | ◎ | ○ | ◎ | ○ |
| Hot joining | 700℃ | △ | ○ | ◎ | ◎ | ◎ | ○ | ○ | ◎ | ◎ | ◎ | ◎ |
| Erosion resistance | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
| Workability | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
| The test example | 12 | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 | 21 | 22 | |
| Hot joining | 500℃ | ◎ | ○ | △ | △ | ◎ | ◎ | ◎ | ○ | ○ | ○ | ○ |
| Hot joining | 700℃ | ◎ | ◎ | ○ | △ | ◎ | ◎ | ◎ | ○ | ◎ | ○ | ○ |
| Erosion resistance | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ||
| Workability | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
| The test example | 23 | 24 | 25 | 26 | 27 | 28 | 29 | 30 | 31 | 32 | 33 | |
| Hot joining | 500℃ | △ | - | ○ | ○ | ○ | △ | - | ○ | ○ | ○ | △ |
| Hot joining | 700℃ | ○ | - | ○ | ○ | ○ | ○ | - | ◎ | ◎ | ○ | ○ |
| Erosion resistance | ○ | - | ○ | ○ | ○ | ○ | - | ○ | ○ | ○ | ○ | |
| Workability | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |||
In the anti-seizing agent of test example 1 to 33 of the present invention, wherein use in bismuth and the bismuth oxide at least a as first solid lubricant; Graphite, molybdenumdisulphide or boron nitride are as second solid lubricant; Mineral oil is as lubricant base oil, by the lubricating grease that is obtained as the thickening material thickening of mineral oil with the calcium sulphonate compound soap, or bisphenol F epoxy resin; At least a with in cupric oxide, thallium oxide, iridium oxide, osmium oxide, rhodium oxide and the ruthenium oxide, the heat resistanceheat resistant of test example 1 performance difference with content of graphite of d=82.4 connects effect.At bi content is in the test example 15 of a=92.5, finds that equally heat resistanceheat resistant connects weak effect.In test example 2, the ratio of graphite and bismuth is a/d=0.3, and it is poor slightly that heat resistanceheat resistant connects effect.In test example 14, the ratio of graphite and bismuth is a/d=9, and it is poor slightly that heat resistanceheat resistant connects effect.In test example 16, cupric oxide content e is 9.4, and erosion resistance is poor.In test example 23, cupric oxide content e is 109, and erosion resistance is poor.In test example 24, lubricant base oil content b is 80, and workability is poor.In test example 28, lubricant base oil content b is 462, and erosion resistance is poor.In test example 29, organic resin content c is 80, and workability is poor.In test example 33, organic resin content c is 462, and erosion resistance is poor.
When the threaded portion of analytical gas transmitter 1, find to have the bismuth composition on the entire exterior surface basically at it.Before the threaded portion of gas sensor 1 and nut portions were fastened, anti-seizing agent evenly covered the outside surface of threaded portion 41.Yet when the threaded portion was assembled to nut, the anti-seizing agent that covers threaded portion 41 outside surfaces became uneven distribution.That is to say that quite a large amount of anti-seizing agents appears at the threaded top and the valley portions of threaded portion 41, and rare or lack at the threaded top of threaded portion 41 and the middle portion between the valley portions.After being heated to 270 ℃ or higher i.e. 700 ℃ temperature, bismuth fusing in the anti-seizing agent and the whole interface between infiltration threaded portion 41 and the nut comprise the threaded top of threaded portion 41 and the middle portion between the valley portions.As a result, the zone that does not exist threaded portion 41 and nut directly to contact, thus prevent when slide in a surface hot joining between threaded portion 41 and the nut on another surface.Herein the term of Shi Yonging " the bismuth composition of anti-seizing agent is retained in the central part of the department of assembly's outside surface " meaning be when to the central part surface of outside surface (under the situation of threaded portion 41, when lip-deep central part between screw thread and the lowest point) carrying out the EDS analysis, observe the bismuth peak, therefore determine to exist the bismuth composition.
The application is based on the Japanese patent application JP2006-259640 of Japanese patent application JP2005-341440 that submitted on November 28th, 2005 and submission on September 25th, 2006, and its full content is incorporated herein for your guidance, elaborates identical.
Claims (7)
1. anti-seizing agent, it comprises:
First solid lubricant, it comprises at least a in bismuth and the bismuth compound; With
Second solid lubricant, it comprises at least a in graphite, molybdenumdisulphide and the boron nitride,
Wherein, described anti-seizing agent satisfies 20 weight %≤a≤90 weight % and 10 weight %≤d≤80 weight %, wherein, the content sum of getting described first solid lubricant in the described anti-seizing agent and described second solid lubricant is as 100 weight %, a represents the content of described first solid lubricant, and d represents the content of described second solid lubricant.
2. anti-seizing agent according to claim 1 is characterized in that, the content of described first solid lubricant and described second solid lubricant satisfies 0.8≤a/d≤8.
3. anti-seizing agent according to claim 1 and 2, it is characterized in that, described first solid lubricant is one of bismuth and bismuth compound, described anti-seizing agent also comprises antioxidant, described antioxidant comprises at least a in cupric oxide, thallium oxide, iridium oxide, osmium oxide, rhodium oxide and the ruthenium oxide, when the content sum of getting described first solid lubricant and described second solid lubricant during as 100 weight parts, the content e of described antioxidant satisfies 10 weight parts≤e≤100 weight parts.
4. anti-seizing agent according to claim 1 and 2, it is characterized in that, also comprise lubricant base oil, perhaps also comprise lubricant base oil and thickening material, wherein, when the content sum of getting described first solid lubricant and described second solid lubricant was 100 weight parts, the content sum b of described lubricant base oil and the described thickening material that can select to exist satisfied 90 weight parts≤b≤400 weight parts.
5. anti-seizing agent according to claim 1 and 2, it is characterized in that, also comprise organic resin, wherein, when the content sum of getting described first solid lubricant and described second solid lubricant during as 100 weight parts, the content of described organic resin is c, and it satisfies relational expression 90 weight parts≤c≤400 weight parts.
6. transmitter, described transmitter comprises the metal shell that is used to survey the detecting element of gaseous phase to be measured and keeps described detecting element, described metal shell comprises the department of assembly that is used for described detecting element is assembled to vapor pipe when described detecting element is exposed to gas to be measured, wherein, anti-seizing agent as claimed in claim 1 or 2 is present in the outside surface of described department of assembly at least.
7. assembly, it comprises: transmitter, described transmitter comprise the metal shell that is used to survey the detecting element of gaseous phase to be measured and keeps described detecting element; And vapor pipe, described vapor pipe is used to assemble and is formed on the described metal shell so that described detecting element is exposed to the department of assembly of gas to be measured, wherein,
When the assembling of described transmitter and described vapor pipe, anti-seizing agent as claimed in claim 1 or 2 is present between the surface of outside surface and the described vapor pipe that assembles described department of assembly of described department of assembly of described metal shell, and
After described department of assembly was heated to the temperature that is not less than 270 ℃, the bismuth composition of described anti-seizing agent was retained on the central part of described outside surface of described department of assembly.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005341440 | 2005-11-28 | ||
| JP2005341440 | 2005-11-28 | ||
| JP2006259640 | 2006-09-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1974737A true CN1974737A (en) | 2007-06-06 |
| CN100580067C CN100580067C (en) | 2010-01-13 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103930530A (en) * | 2011-09-30 | 2014-07-16 | 日本特殊陶业株式会社 | Lubricating coating composition and attachment component for internal combustion engine |
| US9410468B2 (en) | 2013-04-30 | 2016-08-09 | Ngk Spark Plug Co., Ltd. | Temperature sensor attachment member treated with dry film lubricant |
| CN112480993A (en) * | 2020-12-02 | 2021-03-12 | 成都先进金属材料产业技术研究院有限公司 | High-temperature lubricant for thermal simulation experiment and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE112018007369T5 (en) * | 2018-03-28 | 2020-12-10 | Hitachi Automotive Systems, Ltd. | Cylinder device and method for making a rod |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1078249A (en) * | 1988-12-31 | 1993-11-10 | 中国科学院兰州化学物理研究所 | Polyphenyl-thioether dry film lubricant |
| JP2000282259A (en) * | 1999-03-30 | 2000-10-10 | Toyota Central Res & Dev Lab Inc | Production of metallic member having low friction coating film |
| JP4262668B2 (en) * | 2004-02-09 | 2009-05-13 | Ｎｔｎ株式会社 | Grease composition and rolling bearing |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103930530A (en) * | 2011-09-30 | 2014-07-16 | 日本特殊陶业株式会社 | Lubricating coating composition and attachment component for internal combustion engine |
| US9428708B2 (en) | 2011-09-30 | 2016-08-30 | Ngk Spark Plug Co., Ltd. | Lubricating coating composition and attachment component for internal combustion engine |
| US9410468B2 (en) | 2013-04-30 | 2016-08-09 | Ngk Spark Plug Co., Ltd. | Temperature sensor attachment member treated with dry film lubricant |
| CN112480993A (en) * | 2020-12-02 | 2021-03-12 | 成都先进金属材料产业技术研究院有限公司 | High-temperature lubricant for thermal simulation experiment and preparation method thereof |
| CN112480993B (en) * | 2020-12-02 | 2022-05-24 | 成都先进金属材料产业技术研究院有限公司 | High-temperature lubricant for thermal simulation experiment and preparation method thereof |
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| CN100580067C (en) | 2010-01-13 |
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