CN100474719C - Spark plug - Google Patents
Spark plug Download PDFInfo
- Publication number
- CN100474719C CN100474719C CNB2005100911320A CN200510091132A CN100474719C CN 100474719 C CN100474719 C CN 100474719C CN B2005100911320 A CNB2005100911320 A CN B2005100911320A CN 200510091132 A CN200510091132 A CN 200510091132A CN 100474719 C CN100474719 C CN 100474719C
- Authority
- CN
- China
- Prior art keywords
- glaze
- glaze layer
- spark plug
- insulator
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- Spark Plugs (AREA)
Abstract
A glaze layer 2d of a spark plug has the following compositions: 1mol percent or less lead composition in the form of PbO; 25-45mol percent silicon composition in the form of silicone dioxide (SiO2); 20-40mol percent boron composition in the form of boron trioxide (B2O3); 5-25mol percent zinc composition in the form of zinc oxide (ZnO); 0.5-15mol percent barium composition in the form of barium oxide (BaO) and/or strontium composition in the form of strontia (SrO); at least one of the three alkali metals of sodium, kalium and lithium, wherein the total amount of the alkali metal composition being 5-10mol percent respectively in the forms of Na2O, K2O and Li2O, and kalium being the most fundamental composition; further one or two or many of the metals of molybdenum, tungsten, nickel, cobalt, iron and manganese respectively in the forms of MoO3, WO3, Ni3O4, Co3O4, Fe2O3 and MnO2, wherein the total amount being 0.5-5mol percent.
Description
The application is that application number is 01122888.1, the applying date is May 31 calendar year 2001, denomination of invention is divided an application for the Chinese invention patent application of " spark plug ".
Technical field
The present invention relates to a kind of spark plug.
Background technology
The spark plug that is used for car engine ignition generally includes a metal-back, and earth electrode is fixed on the described metal-back; The insulator that aluminium oxide ceramics is made and a contre electrode that is positioned in insulator inside.Insulator is outstanding vertically from the after-opening of metal-back.One terminal metal anchor clamps (terminal) are inserted into the ledge of insulator, and are connected to contre electrode by the glass sealing layer or a resistor of a conduction, and described glass sealing layer is formed in a glass sealing operation.One high voltage is applied on the terminal metal anchor clamps, causes the gap location between earth electrode and contre electrode to produce spark.
Under some mixing conditions, for example spark plug temperature and ambient humidity are increased, high voltage may occur and fail to produce at gap location the situation of spark, opposite a kind of discharge that is known as arcing take place between terminal metal anchor clamps and metal-back, described discharge is round outstanding insulator.For fear of discharge, most of spark plugs have a glaze layer on the surface of insulator.Glaze layer also makes the smooth surface of insulator, therefore stops and pollutes the chemistry of reinforced insulation body and mechanical strength.
When the alumina insulation body was used for spark plug, the lead silicate glass glaze was widely used, and this moment, silicate glass mixed with a large amount of PbO, with the reduction softening temperature.In recent years, people more and more were concerned about environmental problem, comprised plumbous glaze and were out of favour.For example,, consider the adverse influence of discarded spark plug, studying always at progressively superseded leaded glaze in future to environment in the auto industry that spark plug is had great demand.
The Pyrex base glaze of unleaded Pyrex base glaze or alkalescence is studied the substitute as common lead glaze material always, but they have inevitable defective, and for example high glass becomes or not enough insulation resistance.In order to address this problem, Japan Patent JP-A-11-43351 has proposed a kind of constituent of unleaded glaze, this constituent contains zinc, be used to improve stability, glass and do not increase viscosity simultaneously, Japan Patent JP-A-11-106234 has introduced a kind of constituent of unleaded glaze, by adding alkaline components, improved insulation resistance.
Incidentally, be attached at engine, compare, cause that easily temperature raises with common insulating ceramics owing to be used for the glaze of spark plug.In addition, in the last few years, along with the raising of engine performance, the voltage that is applied on the spark plug was enhanced.For this reason, require employed glaze to have the insulation property that to resist rigor condition.Yet the glaze constituent that Japan Patent JP-A-11-106234 is introduced can not always satisfy the insulating requirements under the high temperature, particularly can not satisfy high temperature as the glaze layer on the insulator that is formed on the spark plug and require (for example anti-arcing performance).
Japan Patent JP-A-11-106234 relates to and comprises silicon or boron by use and improve insulation resistance as the alkaline glaze of glass skeleton, but failing to recognize needs to keep a close eye on the difference of eliminating as between the thermal coefficient of expansion of the thermal coefficient of expansion of the alumina-based ceramic of the composition pottery of insulator and glaze, and the improvement level of insulation resistance is not always satisfactory.
Summary of the invention
First purpose of the present invention provides a kind of like this spark plug, and it has the glaze layer that lead composition is reduced, and described glaze layer can be toasted under a relatively low temperature, has shown a good insulation performance performance, obtains smooth surface, a baking back easily.
The present invention's second purpose provides a kind of like this spark plug, be reduced as the difference between the thermal coefficient of expansion of the thermal coefficient of expansion of the alumina-based ceramic of forming insulator and glaze, or by adjusting the alkali metal component in the glaze, make in the glaze layer defective for example crackle or be full of cracks be reduced, increase resistance value.
Description of drawings
Fig. 1 is the front view and the viewgraph of cross-section of an integral body, has shown spark plug according to the invention;
Fig. 2 is a front view, has shown an external form with insulator of glaze layer;
Fig. 3 A is vertical viewgraph of cross-section with 3B, has shown the embodiment of some spark plugs;
Fig. 4 is the front view of an integral body, has shown another kind of spark plug according to the invention;
Fig. 5 is a whole front view, has shown another kind of spark plug according to the invention;
Fig. 6 has shown the method for measuring the insulating resistance value of spark plug;
Fig. 7 has shown the step of coating glaze slurry;
Fig. 8 A～8D has shown airtight step;
The step that Fig. 9 A and 9B show is the subsequent step of step shown in Fig. 8 A～8D.
The meaning of reference number and code is as follows among the figure:
1: metal-back
2: insulator
2d: glaze layer
2d ': glaze slurry coating layer
3: contre electrode
4: grounding electrode
5: the glaze slurry
Embodiment
Spark plug according to the invention comprises an alumina-based ceramic insulator that is positioned between contre electrode and the metal shell, and the part surface of described at least insulator is covered by a glaze layer that comprises oxide.
The characteristic of first kind of constituent is: glaze layer comprises the lead composition of 1mol% or lead oxide still less (PbO) form, the silicon dioxide (SiO of 25～45mol%
2) the silicon composition of form, the diboron trioxide (B of 20～40mol%
2O
3) boron component of form; The zinc composition of the zinc oxide of 5～25mol% (ZnO) form, the strontium composition of the barium composition of the barium monoxide of 0.5～15mol% (BaO) form and/or strontium oxide strontia (SrO) form.
At least a in sodium, potassium and three kinds of alkali metal components of lithium, wherein total content is 5～10mol%, they adopt Na respectively
2O, K
2O and Li
2The form of O, wherein potassium is necessary composition.
In addition, also comprise in molybdenum, tungsten, nickel, cobalt, iron and the manganese one or both or multiple, these metal ingredients adopt MoO respectively
3, WO
3, Ni
3O
4, Co
3O
4, Fe
2O
3And MnO
2Form, total content is 0.5～5mol%.
Hereinafter will introduce the effect of first kind of constituent of spark plug of the present invention.
(work ﹠amp; Effect A)
In order to solve environmental problem, preferably the glaze that will use comprises the lead composition (hereinafter with the leaded composition glaze that reduces to this level be called " unleaded glaze ") of 1mol% or lead oxide form still less.When lead composition with low chemical valence (Pb for example
2+) ionic species when appearing in the glaze, by corona discharge, it is oxidized to high valent ion (Pb for example
3+).If above-mentioned situation takes place, the insulation characterisitic of glaze layer is lowered, and may destroy anti-arcing performance.From this viewpoint, the lead of limited quantity is useful.A kind of selection preferably is that plumbous content is 0.1mol% or still less.Best glaze not leaded (except sneaking into inevitably the lead in the glaze raw material of trace).
(effect B)
When reducing plumbous content, glaze used in the present invention has specially designed composition, is used for the reinforced insulation characteristic, optimizes the glaze baking temperature, improves the surface smoothness of toasting the back glaze.In common glaze, lead composition plays an important role for adjusting softening temperature (specifically, when the baking glaze, suitably reduced the softening temperature of glaze, it is mobile to be used for protection), in unleaded glaze, and boron component (B
2O
3) and alkali metal component play a big part for adjusting softening temperature.The inventor has been found that, the content of one particular range boron component and relevant silicon composition is suitable for improving baking fineness, with above-mentioned composition range is prerequisite, if one or both in interpolation molybdenum, tungsten, nickel, cobalt, iron and the manganese or multiple can provide the spark plug with a glaze layer, when the baking glaze, can guarantee flowability, this spark plug can show the good insulation performance performance at lower temperature down-firing, obtain smooth surface easily, therefore realized goal of the invention.Here it is, and first problem is solved.
(effect C)
In common glaze; when the baking glaze; lead composition plays a part very important for flowability; but in unleaded glaze of the present invention; comprise alkali metal component; be used for protection flowability when the baking glaze,, can provide high insulating resistance value by determining the content range of silicon composition as mentioned above like that.Here it is when the baking glaze, and the alkali metal component in the glaze has reduced the softening temperature of glaze, and protection is mobile.If the alkali metal component that comprises is in above-mentioned scope, this result is demonstrated, and promptly in appearance, glaze layer is difficult to produce pin hole or glaze shrinkage.
If alkali-metal content is less than above-mentioned scope, when the baking glaze, flowability may be lowered.Yet,, can suppose that this glaze layer can be provided if select whole content of above-mentioned alkali metal component, promptly have homogeneous thickness, because bubble is included in the glaze slurry, glaze shrinkage or pin hole are arranged seldom in appearance.
(effect D)
In addition, first kind of constituent of the present invention has a characteristic, promptly also with potassium as alkali metal.When baking during glaze, keep mobile, improved the smooth of the glaze layer that will be formed, can greatly improve insulation property.Reason is, for example receives with other alkali metal and compares with lithium, although same molar content and same cation quantity, potassium has bigger atomic weight, and it occupies very big weight ratio.In order to strengthen this effect more, expectation determines in glaze layer that in alkali metal component potassium has high-load.
The characteristic of second kind of constituent of spark plug according to the invention is that glaze layer comprises the lead composition of 1mol% or lead oxide still less (PbO) form, the silicon dioxide (SiO of 25～45mol%
2) the silicon composition of form, the diboron trioxide (B of 20～40mol%
2O
3) boron component of form; The zinc composition of the zinc oxide of 5～25mol% (ZnO) form, the strontium composition of the barium composition of the barium monoxide of 0.5～15mol% (BaO) form and/or strontium oxide strontia (SrO) form.
At least a in sodium, potassium and three kinds of alkali metal components of lithium, its total content is 5～10mol%, they adopt Na respectively
2O, K
2O and Li
2The form of O.
In titanium, zirconium and three kinds of compositions of hafnium one or both or whole, its total content is 0.5～5mol%, adopts TiO respectively
2, ZrO
2And HfO
2Form.
In molybdenum, tungsten, nickel, cobalt, iron and the manganese one or both or multiple, its total content are 0.5～5mol%, adopt MoO respectively
3, WO
3, Ni
3O
4, Co
3O
4, Fe
2O
3And MnO
2Form.
Except glaze layer needn't adopt alkali metal potassium as in neccessary composition and titanium, zirconium and three kinds of compositions of hafnium one or both or all be included in the above-mentioned scope, second kind of component is identical on other glaze composition with first kind of component.Therefore, effect A～C is obtained equally.In other respects, if comprise in titanium, zirconium and three kinds of compositions of hafnium one or both, the new effect that shows below.
(effect E)
Add titanium, zirconium or hafnium, improved resistance to water.Add as zirconium or hafnium, the resistance to water of glaze layer improve most pronounced effects.Incidentally, " resistance to water is good " mean, for example, the powdery starting material of glaze and a kind of solvent for example water mix, and are retained for a long time as a kind of glaze slurry.Because the wash-out of composition causes the increase of the viscosity of glaze slurry, this not being difficult to takes place.Therefore, when being coated on this glaze slurry on the insulator, the thickness of easy optimized coatings, inhomogeneous being reduced on the thickness.Therefore described optimization and described minimizing can be obtained effectively.When if the interpolation quantity of these compositions is less than 0.5mol%, it is not enough optimizing effect, by increasing thickness, may reduce the insulating resistance value of glaze layer.
For glaze layer, can select and the consistent constituent of the first and second constituent sums, therefore can realize effect A～E simultaneously.
The characteristic of the 3rd constituent of spark plug according to the invention is: glaze layer comprises the lead composition of 1mol% or lead oxide still less (PbO) form; Comprise in silicon or the boron one or both as the glass skeleton structure, glaze layer comprises sodium, potassium and three kinds of compositions of lithium as alkali metal component, and the composition relation satisfies following formula:
NNa
2O＜NLi
2O＜NK
2O
NLi
2O is with Li
2The molar content of the lithium composition that the O form occurs, NNa
2O is with Na
2The molar content of the sodium composition that the O form occurs, NK
2O is with K
2The molar content of the potassium composition that the O form occurs.
The identical point of the glaze layer of the spark plug of this constituent and first and second constituents is that the content of the lead composition that occurs with lead oxide (PbO) form is 1mol% or still less.Therefore, can obtain the A effect.Comprise in silicon or the boron one or both simultaneously, adjust the quantity of sodium, potassium and three kinds of compositions of lithium, to satisfy above-mentioned relation, so show a kind of new effect.
(effect F)
The height of alkali-metal ionic conductivity nature reduces insulation property in a glass glaze layer.On the other hand, silicon or boron component constitute the glass skeleton, if suitably determine their content, the size of skeleton mesh is manufactured is convenient to block alkali-metal ionic conduction, can guarantee the good insulation performance performance.Because silicon or boron component form skeleton easily, when the baking glaze, they play and reduce mobile effect.If but comprise the alkali metal component of above-mentioned scope, because the interaction of silicon ion and oxonium ion owing to escaped reaction and complicated, has reduced melting point, when toasting glaze, flowability is enhanced.
As mentioned above, owing to compare with lithium with sodium, potassium has bigger atomic weight, when the total content of alkali metal component be set have identical mol% the time, potassium does not resemble and can improve liquidity sodium and the lithium, but compares (particularly comparing with lithium) with lithium with sodium, because in glass glaze layer, the motility of potassium ion is lower, comprises quantity though increased, and potassium is difficult to reduce the insulation property of glaze layer.On the other hand,, compare, more can improve liquidity with potassium because the atomic weight of lithium is little, but because the ion motion height, extra interpolation causes the decreasing insulating of glaze layer easily.Yet different with potassium, lithium has the performance that reduces thermal coefficient of expansion.
Therefore, by making potassium have maximum content, the decline of the insulation property of glaze layer is stoped effectively, by adding lithium, make its content be lower than the content of potassium, when baking, can guarantee flowability, by adding potassium, can check the increase of the thermal coefficient of expansion of glaze layer simultaneously, make its thermal coefficient of expansion identical with the substrate aluminium oxide.By adding three kinds of compositions (will introduce hereinafter) simultaneously, this moment, the content of sodium was lower than the content of potassium and lithium, and the downward trend of the insulation property that cause by adding lithium is checked effectively.Therefore, a kind of desirable glaze constituent is implemented, and it has high insulation property, and is when baking the time has good flowability, very little with difference as the thermal coefficient of expansion of the aluminium oxide of the insulator that comprises pottery.Second problem just of the present invention solved.
The glaze layer of the third constituent can have consistent constituent with above-mentioned first and/or second glaze.
Hereinafter will be explained in the constituent of above-mentioned spark plug, every kind of glaze layer comprises the key issue of scope.When if one or both in molybdenum, tungsten, nickel, cobalt, iron and the manganese (hereinafter will be known as " flowability is improved transiting metal component ") that occur with oxide form or multiple whole content are lower than 0.5mol%, may occur that, when the baking glaze, can not always provide the effect that improves liquidity, so that obtain smooth glaze layer easily.On the other hand,, may occur that promptly because the softening temperature of glaze is too high, being difficult to maybe can not the baking glaze if surpass 5mol%.
Existing problem when improving the content overproof of transiting metal component as flowability, this situation may occur, and the color of promptly not expecting appears on the glaze layer.For example, visual information for example letter, image or product numeral is printed on insulator in appearance with colored glaze, is used to illustrate the producer or other information, if the color of glaze layer is too heavy, may be difficult to read the visual information that is printed.Another realistic problem is, regarded as " being familiar with irrational change of color in appearance " by the buyer by the variation of the caused color of change of the constituent of glaze, so the trouble of generation, because visual conflict, product can not be accepted soon.
The insulator that forms the substrate of glaze layer comprises that looking is the pottery of white alumina base, in order to stop or to retrain painted, expectation is formed on observed apparent painted 0～6 chrominance C s and 7.5～10 brightness Vs of being adjusted to of glaze layer on the insulator, for example, the quantity of above-mentioned transiting metal component is adjusted.If colourity surpasses 6, grey or black can be differentiated easily.For another kind of mode, the problem that the sensation of appearance " significantly painted " can not be eliminated.Colourity preferably 8～10, the best is 9～10.In this application, the method for measurement of brightness and colourity can adopt " the method for measurement 4.3A of reflecting object " of " 4 spectrum colorimetric method " in " the color measuring method " of JIS-Z8721.As a kind of simple method, utilize range estimation, by with the Standard Colors epiphase ratio that meets JIS-Z8721, brightness and colourity can be known.
Be less than the content of molybdenum and iron by the content that makes tungsten, flowability improves most pronounced effects when the baking glaze.For example, can make all necessary transiting metal components is molybdenum, iron or tungsten.In order to improve the effect of improving of the flowability of baking during glaze, preferably the content of molybdenum is the 50mol% of necessary transition metal or more.
Secondly, the total content of desirable alkali metal component is 5～10mol%.When being lower than 5mol%, the softening temperature of glaze raises, and it is impossible that the baking glaze may become.When greater than 10mol%, insulation property may descend, and may not have the ability of anti-arcing.The content of alkali metal component is preferably 5～8mol%.For alkali metal, do not rely on a kind of alkali metal, but from sodium, potassium, lithium, add two kinds or whole, more effectively stop the reduction of the insulation property of glaze layer.Therefore, can when increasing alkali metal component, not reduce insulation property, therefore, can obtain two kinds of effects simultaneously, promptly guaranteed flowability and and energy anti-arcing (the common additive effect of so-called alkali metal) when baking.
For sodium, potassium, lithium alkali metal component, expectation determines that the ratio with the potassium of oxide form appearance is 0.4≤K/ (Na+K+Li)≤0.8
Therefore, the effect of increase insulation property is enhanced.If but the value of K/ (Na+K+Li) less than 0.4, this effect may be not remarkable.
On the other hand, it is flowability when guaranteeing the baking glaze that the value of K/ (Na+K+Li) is equal to or less than 0.8 reason, this means that other alkali metal component outside the potassium is added in following ranges simultaneously, is 0.2 or greater than (0.6 or less than).Preferably the value of K/ (Na+K+Li) is adjusted to 0.5～0.7.
In this external alkali metal component, if feasible, lithium also is added, so that improve thermal coefficient of expansion, flowability, the enhance mechanical strength when guaranteeing the baking glaze of insulation property, adjustment glaze layer.
Expectation is 0.2≤Li/ (Na+K+Li)≤0.5 with the mol% of the lithium that oxide form occurs.
If lithium less than 0.2, is compared with alumina substrate, thermal coefficient of expansion is too big, so defective for example chaps easily and to produce the fineness on the glaze surface after therefore being not enough to guarantee to toast.If opposite lithium is greater than 0.5, because in alkali metal ion, the motility of lithium ion is high relatively, may bring bad influence to insulation property.Preferably the value of Li/ (Na+K+Li) is adjusted to 0.3～0.45.For further the reinforced insulation performance except the third composition sodium, can be added other alkali metal component by adding multiple alkali metal, other tenor scope is so determined, can not cause the conductivity variation owing to the alkali metal total amount exceeds standard.Specifically, preferably sodium, potassium, three kinds of metals of lithium are all involved.
For the silicon composition,, then be difficult to guarantee enough insulation property if less than 25mol%.If greater than 45mol%, then be difficult to toast glaze.The content of silicon is preferably 30～40mol%.
If the quantity of boron is lower than 20mol%, the softening temperature of glaze rises, the difficulty that the baking of glaze will become.On the other hand, if content greater than 40mol%, causes glaze fold easily.According to the quantity of other composition, this worry may be to lose that glassy lustre, insulation property reduce or to occur with the inconsistent form of the thermal coefficient of expansion of substrate.If possible, preferably the content of boron is determined in 25～35mol% scope.
If the content of zinc is lower than 5mol%, the thermal coefficient of expansion of glaze layer is too big, occurs for example defective of fold easily on glaze layer.Because zinc plays the effect that reduces the glaze softening temperature, if lack zinc, the baking of glaze will be very difficult.If the content of zinc surpasses 25mol%,, be easy on glaze layer, occur opaque phenomenon owing to lose glassy lustre.Preferably the content of zinc is determined in 10～20mol% scope.
Barium and strontium help to strengthen the insulation property of glaze layer, can gain in strength effectively.If total content is lower than 0.5mol%, the insulation property variation of glaze layer may not resist arcing.If surpass 20mol%, the thermal coefficient of expansion of glaze layer is too big, occurs for example defective of fold easily on glaze layer.In addition, be easy on glaze layer, occur opaque phenomenon.From the angle of reinforced insulation performance and adjustment thermal coefficient of expansion, preferably the total content of barium and strontium zinc is determined in 0.5～10mol% scope.Can comprise in barium and the strontium one or both, but the cost of raw material of barium composition is low.
According to employed raw material, barium and strontium can appear in the glaze with the form outside the oxide form.BaSO for example
4The source that is used as barium, sulphur composition may be remaining in the glaze layer, and when when baking layer, this sulfur component is concentrated on the surface of glaze layer, are used to reduce the superficial expansion of the glaze of fusing, strengthen the smoothness of the glaze layer that is obtained.
It is 8～30mol% that the total content of zinc, barium and/or the strontium that occurs with above-mentioned oxide form is supposed to.If surpass 30mol%, be easy on glaze layer, occur opaque phenomenon.For example visual information for example uses colored glaze that letter, image or product is digital printed at insulator in appearance, be used for determining the producer and other information, since this opaque, may be difficult to read printed information.If be less than 8mol%, softening temperature sharply raises, and the baking of glaze is difficult, causes a kind of bad outward appearance, and preferably total content is 10～20mol%.
With Al
2O
3The magnesium of the calcium of the aluminium of 1～10mol% that form occurs, 1～10mol% of occurring with the CaO form and 0.1～10mol% of occurring with the MgO form, one or both in these three kinds of metals or whole total contents are 1～15mol%.Aluminium can be checked opaque phenomenon effectively, and calcium and magnesium can strengthen the insulation property of glaze layer.Specifically, occur from the angle of the insulation property of improving glaze layer, calcium is only second to barium or zinc.If the quantity of adding is less than the lower limit of every kind of composition, effect is insufficient, if the quantity of adding is greater than the upper limit of every kind of composition or greater than the upper limit of total content, because the rapid increase of softening temperature, being difficult to maybe can not the baking glaze.
From the viewpoint of thermal coefficient of expansion, with B
2O
3Boron that occurs and the zinc that occurs with the ZnO form, both total molar content are N (B
2O
3+ ZnO), alkaline-earth metal composition RE (RE be in barium, magnesium, calcium and the strontium one or both or more kinds of) occur with compound R EO form, alkali metal component R (R be in sodium, potassium and the lithium one or both or all) with compound R
2The O form occurs, and all molar content is N (REO+R
2O), preferably meet following formula
1.5≤N(B
2O
3+ZnO)/N(REO+R
2O)≤3.0
This means B
2O
3With the effect of ZnO landing low thermal coefficient of expansion, while alkaline earth oxide REO and alkali metal oxide R
2O works to increase thermal coefficient of expansion, so, thermal coefficient of expansion is conformed to the thermal coefficient of expansion of alumina substrate.Therefore, can avoid the glaze layer outward appearance fold, be full of cracks or peeling phenomenon to occur.If above-mentioned scope less than 1.5, is compared with alumina substrate, the thermal coefficient of expansion of glaze layer is too big, occurs for example such defective of fold easily, so may not guarantee to toast the fineness on glaze surface, back.On the contrary, if greater than 3.0, compare with alumina substrate, the thermal coefficient of expansion of glaze layer is too little, and the easy appearance of glaze layer is for example chapped or peeled off such defective.For making this more remarkable effect, preferably meet following formula
1.7≤N(B
2O
3+ZnO)/N(REO+R
2O)≤2.5
In auxiliary element bismuth, tin, antimony, phosphorus, copper, cerium and the chromium one or both are comprised in the glaze layer, and total content is 5mol% or is less than 5mol% that these metals are respectively with Bi
2O
3, SnO
2, Sb
2O
5, P
2O
5, CuO, CeO
2And Cr
2O
3Form occur, can initiatively add these compositions according to purpose, or often be included in inevitably in the raw material of glaze (otherwise mentioned hereinafter when preparing the glaze slurry, the mixed clay mineral of these auxiliary elements) or in the impurity (otherwise pollutant), described impurity comes from the refractory material of the melting process that is used for producing the glaze frit.Each composition in these compositions all can strengthen during glaze mobile in baking, checks the lip-deep material of glaze layer after the formation of bubble in the glaze layer or removing stick to baking, to stop abnormal projection.Bismuth and antimony are effective especially.
In the compound of spark plug of the present invention, the various compositions that comprised in the glaze occur with oxide form, owing to form the factor of noncrystal and vitreousness, can not often be distinguished as the existence form of oxide.In the case, if the value of the content of the composition that occurs with oxide form drops in the above-mentioned scope, think that they belong to scope of the present invention.
By using well-known ontoanalysis method, for example EPMA (electron microprobe ontoanalysis) or XPS (X-ray photoelectron spectroscopy), the content that is formed on the various compositions in the glaze layer on the insulator can be differentiated.If for example use EPMA, perhaps wavelength dispersion system or energy decentralized system all are enough to the characteristic of measured X ray.In addition, also have a kind of method, be about to glaze layer and peel off, make its experience chemical analysis and gas analysis, be used to differentiate composition from insulator
Form spark plug with glaze layer of the present invention by assembling, the terminal metal anchor clamps that are about to an axial moulding and contre electrode are as an object or to have an adhesive phase between the two be that described metal fixture separates with contre electrode, and both are assemblied in the through hole on the insulator.At this moment, whole spark plug is maintained at about 500 ℃, makes between terminal metal anchor clamps and the metal shell and can conduct electricity, and guarantees the measurement insulation resistance value.In order at high temperature to keep long-term insulation, the expectation insulating resistance value is 200M Ω or bigger, is preferably 400M Ω or bigger, to stop discharge.
Fig. 6 has shown a kind of measuring system, DC power supply (for example 1000V power supply) be connected to spark plug 100 the side of terminal metal 13, simultaneously, the side ground connection of metal shell 1, the spark plug 100 that is arranged in the heating furnace is heated to 500 ℃, and this moment, electric current passed through.For example hypothesis utilizes one to measure current resistor (resistance value Rm), when voltage is VS, the current value of measuring is Im, want the measured insulating resistance value Rx can be obtained, its the value for (VS/Im)-Rm (in the drawings, the output of the differential amplifier by a voltage difference that is used for amplified current measuring resistance two ends, current value I m is measured).
Insulator can comprise the alumina insulation material, described insulating material comprise 85～98mol% with Al
2O
3The aluminium that form occurs.When being easy to act as most temperature and being 20～350 ℃, the mean thermal expansion coefficients of glaze is 5 * 10
-6/ ℃～8.5 * 10
-6/ ℃, if less than lower limit, then on glaze layer, occur easily breaking or the glaze omission.On the other hand, if surpass the upper limit, occur crack performance on the glaze layer easily, thermal coefficient of expansion is preferably 6 * 10
-6/ ℃～8 * 10
-6/ ℃.
The thermal coefficient of expansion of glaze layer can be measured like this, from cutting out sample by the glass glaze body that mixes and the fusing raw material form, the composition of sample is almost identical with the composition of glaze layer, uses well-known dilatometer method, measures thermal coefficient of expansion.Can use laser interferometer for example or atomic force microscope to measure the thermal coefficient of expansion of the glaze layer on the insulator.
At place, axial centre position, on the circumferencial direction, insulator has a projection outside.Axially to go up a side towards the contre electrode front end as the front side, as the front side, the outer peripheral face of the bottom of insulator body is one cylindrical, and this moment, the outer peripheral face of bottom was coated the glaze layer that thickness is 7～50 μ m.
In an automobile engine, utilize leather cup, spark plug is connected on the electric equipment of engine, in order to strengthen anti-flash-over capacity, emphasis is adhering between insulator and the leather cup inside.The inventor conscientiously studies and finds, in the unleaded glaze of the unleaded glaze of Pyrex or alkali borosilicate hydrochlorate, importantly adjust the thickness of glaze layer, be used to obtain to toast the smooth surface of back glaze, the excircle special requirement of the bottom of insulator body and adhering to of leather cup, unless suitably adjust the thickness of glaze layer, otherwise can not guarantee to have sufficient anti-flash-over capacity.Therefore, on the insulator of the leadless glaze bed of material with the third constituent that meets spark plug of the present invention, if the thickness of the glaze layer of covering insulator bottom excircle is set in the above-mentioned number range, baking back glaze and can being enhanced adhering to of leather cup, under the prerequisite of the insulation property that do not reduce glaze layer, anti-flash-over capacity is enhanced simultaneously
Be less than 7 μ m if cover the thickness of the glaze layer of insulator bottom excircle, the glaze of above-mentioned constituent is difficult to form smooth baking surface, so adhering to of baking back glaze and leather cup is destroyed, and can not anti-effectively arcing.If but the thickness of glaze layer greater than 50 μ m, conduction transverse cross-sectional area increase, the glaze of above-mentioned constituent is difficult to guarantee insulation property, may cause anti-flash-over capacity to descend.
For the thickness that makes glaze layer evenly or controlled (or special) thick glaze layer, as mentioned above, it is useful adding titanium, zirconium and hafnium.
The method of producing spark plug of the present invention comprises the steps:
Prepare raw material and press the glaze powder that estimated rate mixes, mixture is heated to 1000～1500 ℃ and fusing, the material of fusing is cooled off apace, become vitrifying and pulverize;
The glaze powder piled up on the surface of insulator form glaze layer;
Insulator is heated the baking glaze layer.The powdery starting material of every kind of composition not only comprises oxide (very complicated oxide), and comprises other inorganic matter, for example hydroxide, carbonate, chloride, sulfate, nitrate or phosphate.By heating and fusing, these inorganic matters can be transformed into oxide.Obtain thin slice and cooling apace by melt being put into water or melt being sprayed onto on the surface of chill roll.
The glaze powder is placed in water or the solution, so can be used as the glaze slurry.If for example slurry is coated on the surface of insulator and makes it dry, the piling up layer and can be formed coat or glaze slurry of glaze powder.By the way, as the lip-deep method that the glaze slurry is coated on insulator, if adopt the method for nozzle spray, the glaze powder with uniform thickness is piled up layer and can be formed easily, and the adjustment of coat thickness is easy to.
The glaze slurry can comprise the clay mineral or the organic bond of right quantity, is used to strengthen the shape retention of piling up layer of glaze powder.For clay mineral, those mainly can be used by the material that the alumino-silicate hydrate is formed, and for example those one or both or multiple (or mixtures) that comprise in allophane, her hair pick stone, canbyite, montmorillonite, kaolinite, galapectite, montmorillonite, vermiculite and the dolomite can be used.For oxide, except SiO
2And Al
2O
3Outside, those mainly comprise Fe
2O
3, TiO
2, CaO, MgO, Na
2O and K
2Among the O one or both or multiple material can be used.
Spark plug of the present invention is by constituting with lower member, and the terminal metal anchor clamps and that an insulator, with axially extending bore is assembled in described through hole one end are assembled in the contre electrode of the described through hole other end.By the conduction sintered body (for example electro-conductive glass sealing-in or resistor) that mainly comprises the mixture of being made up of glass and electric conducting material, contre electrode and terminal metal anchor clamps are electrically connected.It is made to have the technology that the spark plug of this spline structure can be comprised the steps.
One installation step: assembling one comprises insulator with through hole, the terminal metal anchor clamps at described through hole one end, a step in the structure of the contre electrode of the described through hole other end and the packed layer between terminal metal anchor clamps and contre electrode, and described packed layer comprises glass powder and conducting material powder.
One glaze baking procedure: in the structure after being assembled, on the surface of insulator, form the layer of piling up by the glaze powder constituent, then this structure is heated to 800～950 ℃, the formed layer of piling up by the glaze powder constituent toasts to form glaze layer on the surface to insulator, the glass powder in the softening simultaneously described packed layer.
One step of exerting pressure: contre electrode is closely contacted in through hole with the terminal metal anchor clamps, therefore the packed layer between contre electrode and the terminal metal anchor clamps is pressed into the sintered body of conduction.
At this moment, by the sintered body of conduction, contre electrode and terminal metal anchor clamps are electrically connected, and described sintered body also blocks the gap between through hole inboard and contre electrode and the terminal metal anchor clamps simultaneously.Therefore, the glass baking step also is used as the glass sealing step.Glass sealing and glaze baking are carried out simultaneously, and this operation is effective.Because it is 800～950 ℃ that above-mentioned glaze allows baking temperature, contre electrode and the oxidated hardly influence of terminal metal anchor clamps, so the output of spark plug is enhanced, the glaze baking procedure also is feasible prior to the glass sealing step.
The softening temperature of glaze layer preferably is adjusted to 520～700 ℃.When softening temperature during, need to toast and glass sealing, may quicken the oxidation of contre electrode and terminal metal anchor clamps greater than 950 ℃ baking temperature greater than 700 ℃.When softening temperature was lower than 520 ℃, what the glaze baking temperature may be set was lower than 800 ℃.The glass of sintered body of being used to conduct electricity this moment must have a low softening temperature, so that the glass sealing of satisfaction guaranted.Therefore, when the spark plug after the processing uses under a hot environment for a long time, the easy sex change of glass in the conduction sintered body, for example, the conduction sintered body comprises a resistor, the sex change of glass causes performance decrease, for example the useful life under the load.Sometimes, the softening temperature of glaze layer is adjusted to 520～620 ℃.
By the glaze layer under coming off from insulator is carried out differential thermal analysis, the softening temperature of glaze layer can be measured, and this temperature is a sag point as obtained inferior to the peak temperature (second endothermic peak) of first endothermic peak.Being formed in the value that the softening temperature of the glaze layer on the insulator surface can be obtained from a glass sample estimation comes out, by mixed raw material and melt raw material and apace the cooling, and make described sample, the constituent of described sample is identical with the constituent of wanting measured glaze layer.
Hereinafter will introduce in conjunction with the accompanying drawings and be used to implement pattern of the present invention.Fig. 1 has shown the first kind of structure that meets spark plug of the present invention.Spark plug 100 has a cylindrical metal shell 1; One is assemblied in the insulator 2 of metal shell 1 inside, and its end 21 is outstanding from the front end of metal shell 1; One is set at the contre electrode 3 of insulator 2 inside, and its ignition section 31 is formed on the end; One grounding electrode 4, its end is welded on metal shell 1, and the other end curves inwardly, and makes the end of a side of this end in the face of contre electrode 3.Grounding electrode 4 has the ignition section 32 facing to ignition section 31, forms gap between opposed facing ignition section.
Except aluminium, specific composition is as follows.
With SiO
2The silicon composition that form occurs: 1.50～5.00mol%
Calcium component with the appearance of CaO form: 1.20～4.00mol%
Magnesium component with the appearance of MgO form: 0.05～0.17mol%
Barium composition with the appearance of BaO form: 0.15～0.50mol%
With B
2O
3The boron component that form occurs: 0.15～0.50mol%
On the other hand, the diameter of contre electrode 3 is littler than the diameter of resistance 15.The through hole 6 of insulator 2 is divided into the second portion 6b (rear portion) that the 6a of first (front portion) and with a circular cross section has a circular cross section, contre electrode 3 is installed in the circular cross section of first, and the diameter of the circular cross section of second portion is bigger than the diameter of the circular cross section of first.Terminal metal anchor clamps 13 and resistance 15 are set in the second portion 6b, and contre electrode 3 is inserted in the 6a of first, and the rear end of contre electrode 3 has the periphery of an outside protruding 3c around it, utilizes fixedly contre electrode of described projection.The 6a of first of through hole 6 and second portion 6b are connected with each other at the first anterior 2g as shown in Figure 3A like that, and in the coupling part, it is that tilt or round that a projection is accepted face 6c, is used to accept protruding 3c, is used for fixing contre electrode 3.
The first anterior 2g of insulator 2 is connected at coupling part 2h with the second anterior 2i, difference occurs on the outer surface of insulator herein.Metal shell 1 has a protruding 1c at its inwall in the position of the coupling part 2h that meets, cooperates with protruding 1c so coupling part 2h passes through a packing ring 63, to stop slip in the axial direction.Packing ring 62 is set between the outside of the inwall of metal shell 1 and insulator 2, and at the rear portion of the bossing 2e of flange shape, packing ring 60 is set at the rear portion of packing ring 62.Space between the packing ring 60 and 62 is full of for example talcum of filler.Insulator is inserted into metal shell 1 and towards the nose motion of shell 1, with this understanding, the after-opening edge of metal shell 1 is pressed towards packing ring 60, and in order to form a sealing lip 1d, metal shell 1 is fastened on the insulator 2.
Fig. 3 A and 3B have shown the specific embodiment of insulator 2.The dimensions of insulator is as follows:
Total length L 1:30～75mm;
The length L 2:0 of the first anterior 2g～30mm (except with coupling part 2f that bossing 2e links to each other but comprise the part 2h that links to each other with the second anterior 2i);
The length L 3:2 of the second anterior 2i～27mm;
The outer diameter D 1:9 of rear portion 2b～13mm;
The outer diameter D 2:11 of bossing 2e～16mm;
The outer diameter D 3:5 of the first anterior 2g～11mm;
The outer diameter D 4:3 of the second anterior 2i～8mm;
The terminal external diameter of the second anterior 2i (end was circular or tilted this moment, measured external diameter from the bottom of part circle or that tilt in a cross section) D5:2.5～7mm;
Inside diameter D 6:2～5mm of the second portion 6b of through hole 6;
Inside diameter D 7:1～3.5mm of the 6a of first of through hole 6;
The thickness t 1:0.5 of the first anterior 2g～4.5mm;
The bottom thickness t2 of the second anterior 2i (thickness on perpendicular to the direction of central axial line 0): 0.3～3.5mm;
The end thickness t3 of the second anterior 2i (thickness on perpendicular to the direction of central axial line 0; This moment terminal profile be circle or tilt, comprise in the cross section of central axial line 0 one, measure thickness in the bottom of end circle or that tilt): 0.2～3mm;
The average thickness tA of the second anterior 2i ((t2+t3)/2): 0.25～3.25mm;
In Fig. 1, the length L Q of the 2k of insulator 2 part is 23～27mm (just about 25mm), and this part projects upwards from the rear end of metal shell 1.In the vertical cross-section of a central axial line 0 that comprises insulator, on the outline of the ledge 2k of insulator 2, length L P along the measured 2k part of the profile of insulator 2 is 26～32mm (for example about 29mm), from position corresponding to the rear end of metal shell 1, by wrinkling part 2c, arrive the rear end of insulator 2.
As shown in Figure 3A, insulator 2 has the about 60mm of following size: L1=, the about 10mm of L2=, the about 14mm of L3=, the about 11mm of D1=, the about 13mm of D2=, the about 7.3mm of D3=, D4=5.3mm, D5=4.3mm, D6=3.9mm, D7=2.6mm, t1=3.3mm, t2=1.4mm, t3=0.9mm, tA=1.15mm.
As shown in Figure 2, glaze layer 2d is formed on the outer surface of insulator 2, more particularly, is formed on the outer surface of the rear portion 2b that comprises wrinkling part 2c.The thickness of glaze layer 2d is 7～150 μ m, preferably 10～50 μ m.As shown in Figure 1, the glaze layer 2d that is formed on the 2b of rear portion extends predetermined length along direction forward from the rear end of metal shell 1, and rear side extends to the rear end of rear portion 2b simultaneously.
The core 3a of earth electrode 4 and contre electrode is made by nickel alloy.The core 3a of contre electrode is embedded in the inside by core 3b, and described core 3 comprises copper or copper alloy, is used to quicken distributing of heat.Ignition section 31 and opposite ignition section 32 are mainly made by noble metal alloy, and described noble metal alloy comprises iridium, platinum and rhodium.The diameter of the core 3 of contre electrode is reduced at front end, its front is formed flat, one dish of being made by alloy that comprises ignition section is overlapping with it, use laser welding, electron beam welding or method for resistance welding that lap is welded to form a soldered part W, therefore, constitute ignition section 31.Relative ignition section 32 is positioned at the end of earth electrode 4, and facing to the position of ignition section 31, joint peripheral soldered forms a similar soldered part W along outer edge part.Described end is made by a deposite metal, and described deposite metal comprises the alloying component of estimated rate, or makes described end by moulding and sintered alloy powder or mixed metal powder with estimated rate.At least in ignition section 31 and relative ignition section 32 can be omitted.
Slurry is spray dried to graininess and is used to form a base substrate, form the base substrate particle and be sent to the prototype that a rubber die is pressed into insulator, by grinding the profile of insulator shown in Figure 12, the outside to formed prototype processes, at 1400～1600 ℃ of following sintering, obtain insulator 2 then.
Make the glaze slurry as follows.
The raw material powder of silicon, boron, zinc, barium and alkali metal (sodium, potassium, lithium) is (for example with SiO
2The silicon composition that form occurs is with H
3BO
3The boron component that form occurs is with the zinc composition of ZnO form appearance, with BaCO
3The barium composition that form occurs is with Na
2CO
3The sodium composition that form occurs is with K
2CO
3The potassium composition that form occurs is with Li
2CO
3The lithium composition that form occurs) mixed, with the constituent that obtains to be scheduled to.Under 1000～1500 ℃, the powder of mixing is heated and melts, and is placed on then to cool off apace in the water to be used for vitrifying, grinds subsequently to make glaze glass dust.The clay mineral of glaze glass dust and predetermined quantity for example kaolinton or frog order clay and organic bond mixes, and adds entry and make the glaze slurry.
As shown in Figure 7, glaze slurry S is used to cover insulator 2 desired surfaces from nozzle N ejection, therefore, forms the cover layer 2d ' of a glaze slurry, as the layer of piling up of glaze powder.
A kind of assembly structure PA is formed, and this moment, terminal metal anchor clamps 13 shown in Fig. 9 A were inserted into through hole 6 from top.Be assembled structure PA and be positioned in the heating furnace, be heated being higher than under 800～950 ℃ the temperature of softening temperature, terminal metal anchor clamps 13 are pressed into through hole 6 from contre electrode 3 opposition sides, thereby, press superimposed layer 25～27 in the axial direction.Therefore, shown in Fig. 9 B, each layer is compressed and sintering, becomes an electro-conductive glass sealing layer 16, a resistance 15 and an electro-conductive glass sealing layer 17 (above-mentioned is the glass sealing operation).
Be set at 600～700 ℃ if be included in the softening temperature of the glaze powder among the glaze slurry cover layer 2d ', a layer 2d ' can be toasted shown in Fig. 9 A and 9B like that, and be identical with stoving time in the above-mentioned glass sealing operation, becomes glaze layer 2d.Because the heating-up temperature of glass sealing operation is selected from 800～950 ℃ of relatively low temperature, the surface oxidation of contre electrode and terminal metal anchor clamps can be reduced.
If a kind of air jet furnace of incendiary type is used as heating furnace (also can be used as the glaze oven), comprise many relatively steam in the heating atmosphere as combustion product.Be used if comprise the glaze of 40mol% or boron component still less,, be guaranteed, can form smooth and glaze layer and have good insulation performance uniformly in this atmosphere current downflow when when baking.
After the glass sealing operation, earth electrode 4 and other parts are installed on the structure PA, to finish spark plug shown in Figure 1 100.Use screw thread 7 that spark plug 100 is screwed into engine section, be used as spark source to light the air/fuel mixture that is provided to combustion chamber.By serum cap RC (comprising for example silicon rubber), an a kind of high-tension cable or an ignition coil are connected to spark plug 100.Serum cap RC has the aperture of a diameter than the little about 0.5～1.0mm of outer diameter D 1 (Fig. 3) of rear portion 2b.Rear portion 2b is pressed into serum cap, and elasticity expanded hole has simultaneously covered the base portion at rear portion up to serum cap.
Therefore, serum cap RC contacts with the intimate at rear portion 2, and the function that plays insulating lid is to stop discharge.
By the way, spark plug of the present invention is not limited to type shown in Figure 1, and can be as shown in Figure 4, and earth electrode 4 terminal manufactured in the face of contre electrode 3 is to form ignition gap.In addition, as shown in Figure 5, half plane discharge type spark plug also is useful, and this moment, the front end of insulator 2 entered the side of contre electrode 3 and the front end of earth electrode 4.
Embodiment
In order to determine effect of the present invention, carried out the following example.
(embodiment 1)
Thus obtained slurry is made spherical particles by spray drying, and they are sieved to obtain 50～100 μ m particles.Use well-known rubber suppression method, under 50MP pressure, be shaped.The outer surface of gained formed body is processed into predetermined shape by grinding machine and toasts down at 1550 ℃, to obtain pure edge body 2.X-ray fluorescence analysis discloses, and insulator 2 has following constituent.
Aluminium component (Al
2O
3): 94.9mol%;
Silicon composition (SiO
2): 2.4mol%;
Calcium component (CaO): 1.9mol%;
Magnesium component (MgO): 0.1mol%;
Barium composition (BaO): 0.4mol%;
Boron component (B
2O
3): 0.3mol%
SiO
299.5%), H powder (purity:
3BO
398.5%), Na powder (purity:
2CO
398.5%), K powder (purity:
2CO
399%), Li powder (purity:
2CO
399%), BaSO powder (purity:
499.5%), SrCO powder (purity:
399%), ZnO powder (purity: 99.5%), MoO powder (purity:
399%), Fe powder (purity:
2O
399%), WO powder (purity:
399%), Ni powder (purity:
3O
499%), Co powder (purity:
3O
499%), MnO powder (purity:
299%), CaO powder (purity: 99.5%), TiO powder (purity:
299.5%), ZrO powder (purity:
298.5%), HfO powder (purity:
299%), MgO powder (purity: 99.5%), Sb powder (purity:
2O
599%), Bi powder (purity:
2O
399%), SnO powder (purity:
299.5%), P powder (purity:
2O
599%), CuO powder (purity: 99%), CeO powder (purity:
299.5%) and Cr powder (purity:
2O
3Powder (purity: 99.5%) mixed.Mixture is 1000～1500 ℃ of fusings, and melt is poured in the water, and cooling is used for vitrifying apace, and grinding to form particle size subsequently on an alumina balls mushroom machine is 50 μ m or littler powder.New Zealand's china clay of 3 weight portions and 2 parts of PVA as common adhesive sneak into 100 parts glaze powder, and mixture and 100 water kneadings are to make the glaze slurry.
As shown in Figure 7, the glaze slurry is directed onto on the insulator 2 from nozzle, and dry is the glaze slurry cover layer 2d ' of 100 μ m to form coating thickness.In conjunction with Figure 11 and 12,, use insulator 2 can produce the spark plug 100 of several types by above-mentioned operation.The external diameter of screw thread 7 is 14.By comprising B
2O
3-SiO
2-BaO-Li
2O glass powder, ZrO
2Powder, carbon black powders, TiO
2The mixed-powder of powder and metallic aluminium powder is made resistor 15. Glass sealing layer 16 and 17 is by comprising B
2O
3-SiO
2-Na
2The mixed-powder of O glass powder, copper powders may, iron powder and Fe-B powder is made.Be used for glass-sealed heating-up temperature just the glaze baking temperature be set to 900 ℃.
On the other hand, this glaze is produced, do not pulverized, but in block by crystallization.Determine with X-ray diffraction whether block is vitrifying (noncrystalline) state.
Experimentize as follows
(1) chemical composition analysis
Carry out x-ray fluorescence analysis.The assay value of every kind of sample (oxide form) is displayed in table 1～6.By the EPMA method to be formed on glaze layer 2 on the insulator analyze the value that obtained with to the measurement result of bulk sample much at one.
(2) thermal coefficient of expansion
Downcut the sample of 5mm * 5mm * 5mm size from block, be 20～350 ℃ in temperature and measure with well-known dilatometer method down.Sample to the same size of downcutting from insulator 2 carries out same measurement.The result is 73 * 10
-7/ ℃.
(3) softening temperature
To weight is that the powder sample of 50mg carries out different heat analyses, begins to add thermal measurement from room temperature, and second endothermic peak is taken as softening temperature.
At different spark plugs, in conjunction with the operation that Fig. 8 A～8D is introduced, when applying 1000V voltage, the insulating resistance value in the time of 500 ℃ is estimated.In addition, detect by an unaided eye and be formed on the outward appearance of the glaze layer 2d on the insulator 2.Use the SEM observational technique on cross section, the thickness of the glaze layer on the outline of insulator-base end parts is measured.Metamorphosis is not found in gloss and transparent aspect, is excellent (00), though in an acceptable scope, have slight shrinkage and opaque, belongs to good (0).Outward appearance metamorphosis be displayed in the table each row in.The above results is shown in table 1～6
Table 1
Com.: constituent
* show and drop on outside the present invention
Table 2
Com.: constituent
* show and drop on beyond the scope of the invention
Table 3
Com.: constituent, A: be full of cracks, B: the inadequate fusing of glaze
* show and drop on beyond the scope of the invention
Table 4
Com.: constituent, A; Be full of cracks, D: opaque
* show and drop on outside the scope of the invention
Table 5
Com.: constituent, D*: opaque, E*: bubble
* show and drop on beyond the scope of the invention
Table 6
Com.: constituent, B: the insufficient fusing of glaze, F: be full of cracks occurs, G: keep bubble
* show and drop on outside the scope of the invention
According to the result, according to glaze constituent of the present invention, though do not comprise lead basically, glaze can be toasted under low relatively temperature, can guarantee enough insulation property, and the outward appearance on the surface of baking back glaze layer is an acceptable.
All require the foreign patent application of foreign priority all to be combined as reference.
Claims (10)
1. spark plug comprises:
One contre electrode;
One metal-back;
One is positioned in the aluminium oxide ceramics insulator between contre electrode and the metal-back, and the part surface of insulator is covered by a glaze layer that comprises oxide at least,
Described glaze layer comprises: the lead composition of 1mol% or PbO form still less; At least a kind of in two kinds of metals of silicon or boron is as the glass skeleton structure; Sodium, potassium and three kinds of compositions of lithium are as alkali metal component, and constituent satisfies following formula:
NNa
2O<NLi
2O<NK
2O
Wherein, NLi
2O is with Li
2The molar content of the lithium composition that the O form occurs, NNa
2O is with Na
2The molar content of the sodium that the O form occurs, NK
2O is with K
2The molar content of the potassium that the O form occurs.
2. a spark plug according to claim 1, it is characterized in that: the alkali metal in the glaze layer satisfies such relation:
4＜NK
2O/NR
2O＜0.8, NR
2O is with compound R
2Alkali-metal all molar content that the O form occurs, NK
2O is with K
2The molar content of the potassium that the O form occurs.
3. spark plug according to claim 1 is characterized in that: the alkali metal in the glaze layer satisfies such relation:
2＜NLi
2O/NR
2O＜0.5, NR
2O is with compound R
2Alkali-metal all molar content that the O form occurs, NLi
2O is with Li
2The molar content of the lithium that the O form occurs.
4. spark plug according to claim 1, it is characterized in that: glaze layer comprises zinc, also comprise a kind of composition in two kinds of compositions of barium and strontium at least, the quantity of above-mentioned all the components that glaze layer comprises is 10～30mol%, and they occur with ZnO, BaO and SrO form respectively.
5. spark plug according to claim 1 is characterized in that: glaze layer comprises a kind of in aluminium, calcium and three kinds of compositions of magnesium at least, and its total content is 0.1～15mol%, wherein, and with Al
2O
3Aluminium 0.1～10mol% that form occurs is with the calcium 0.1～10mol% of CaO form appearance, with the magnesium 0.1～10mol% of MgO form appearance.
6. spark plug according to claim 1 is characterized in that: glaze layer comprises that at least total content is 5mol% or bismuth, tin, antimony, phosphorus, copper, cerium and the chromium that is less than 5mol%, and wherein, these metals are respectively with Bi
2O
3, SnO
2, Sb
2O
5, P
2O
5, CuO, CeO
2And Cr
2O
3Form occur.
7. spark plug according to claim 1, it is characterized in that: described insulator axially has a bossing on place, the centre position excircle direction, as the front side, promptly in the axial direction towards a side of the front end of contre electrode, near the rear side relative with bossing, one cylindrical surface is formed on the outer peripheral face of insulator body cardinal extremity part, and the outer peripheral face of cardinal extremity part is covered by glaze layer, and the thickness of described glaze layer is 7～50 μ m.
8. spark plug according to claim 1, it is characterized in that: terminal metal anchor clamps and contre electrode are set in the through hole of insulator as one, the terminal metal anchor clamps separate with contre electrode by the binder course of a conduction, insulating resistance value is 400M Ω or bigger, making the temperature of whole spark plug is 500 ℃, electric current is flow through by insulator measure described insulating resistance value between terminal metal anchor clamps and the metal shell.
9. spark plug according to claim 1 is characterized in that: described insulator comprises and contains 85～98mol% with Al
2O
3The alumina insulation material of the aluminium component that form occurs, when temperature was 20～350 ℃, the mean thermal expansion coefficients of glaze layer was 5 * 10
-6/ ℃～8.5 * 10
-6/ ℃.
10. spark plug according to claim 1 is characterized in that: the softening temperature of described glaze layer is 520～620 ℃.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000163846 | 2000-05-31 | ||
| JP163846/2000 | 2000-05-31 | ||
| JP099528/2001 | 2001-03-30 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011228881A Division CN1246944C (en) | 2000-05-31 | 2001-05-31 | Spark plug |
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| Publication Number | Publication Date |
|---|---|
| CN1728480A CN1728480A (en) | 2006-02-01 |
| CN100474719C true CN100474719C (en) | 2009-04-01 |
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ID=35927579
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|---|---|---|---|
| CNB2005100911320A Expired - Fee Related CN100474719C (en) | 2000-05-31 | 2001-05-31 | Spark plug |
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| EP3588705A1 (en) * | 2018-06-22 | 2020-01-01 | Robert Bosch GmbH | Spark plug and method for marking same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1976079B1 (en) | 2007-03-30 | 2014-03-05 | NGK Spark Plug Co., Ltd. | Spark plug of internal combustion engine |
| JP4369980B2 (en) * | 2007-03-30 | 2009-11-25 | 日本特殊陶業株式会社 | Spark plug for internal combustion engine |
| US20130300278A1 (en) * | 2012-05-11 | 2013-11-14 | Uci/Fram Group | Fouling resistant spark plug |
| US10992112B2 (en) | 2018-01-05 | 2021-04-27 | Fram Group Ip Llc | Fouling resistant spark plugs |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0390065A1 (en) * | 1989-03-28 | 1990-10-03 | NGK Spark Plug Co. Ltd. | Spark plug for internal combustion engine |
| CN1245356A (en) * | 1998-05-22 | 2000-02-23 | 日本特殊陶业株式会社 | Sparking plug and producing method thereof |
-
2001
- 2001-05-31 CN CNB2005100911320A patent/CN100474719C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0390065A1 (en) * | 1989-03-28 | 1990-10-03 | NGK Spark Plug Co. Ltd. | Spark plug for internal combustion engine |
| CN1245356A (en) * | 1998-05-22 | 2000-02-23 | 日本特殊陶业株式会社 | Sparking plug and producing method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3588705A1 (en) * | 2018-06-22 | 2020-01-01 | Robert Bosch GmbH | Spark plug and method for marking same |
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