CN1137330C - Preheating plug and spark plug and its producing method - Google Patents
Preheating plug and spark plug and its producing method Download PDFInfo
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- CN1137330C CN1137330C CNB001240390A CN00124039A CN1137330C CN 1137330 C CN1137330 C CN 1137330C CN B001240390 A CNB001240390 A CN B001240390A CN 00124039 A CN00124039 A CN 00124039A CN 1137330 C CN1137330 C CN 1137330C
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- main metal
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Abstract
The present invention is plated with a chromate film on the surface of a main metal casing in a preheating plug and a spark plug. The chromate film comprises trivalent chromium in the amount of 95 wt% or more of the contained chromium component, and has the thickness of 0.2 mu m to 0.5 mu m.
Description
Technical field
The present invention relates to be used for the heater plug of preheating diesel engine or analog, the spark plug and the manufacture method thereof of internal-combustion engine.
Background technique
In general, in the structure of heater plug, resistance heater is arranged in the main metal shell, and connecting thread part of the formation in appearance of this shell makes the front end heating part of resistance heater extend through arbitrary end face of main metal shell.This helical thread portion is used for heater plug is connected in engine head.
The spark plug that is used for the petrol engine igniting of automobile or analog is equipped with an insulating component and a metal shell that is arranged on the insulating component outside that is arranged on the contre electrode outside.In addition, be used for being connected in above-mentioned main metal shell with a ground electrode of contre electrode formation spark-discharge gap.The connecting thread of main metal shell outer surface setting partly is used for spark plug is connected in the cylinder head of motor.
Main metal shell is normally made as carbon steel with iron material, and its body plan must have the surface of zinc-plated corrosion protection.Though zinc coat has the fabulous anticorrosion ability for iron,, the zinc coat that forms on iron may be owing to well-known sacrificial corrsion is easy to consume.Worse, zinc coat fades and bleaches owing to the zinc oxidation, makes appearance quality become bad.Therefore, the major component body plan of heater plug and spark plug must make the surface coverage chromate film of zinc coat to prevent the corrosion of coating.
The chromate film that forms on the main metal shell of heater plug and spark plug is so-called yellow chromate film always.Because yellow chromate film has fabulous decay resistance, thereby yellow chromate film is widely used in various fields, comprises the coating of can internal surface and heater plug and spark plug.Because it is Cr VI that a part contains chromium component, thereby because protecting, global concern for the environment progressively bans use of yellow chromate film in recent years.For example, in heater plug and a large amount of auto industry fields that use of spark plug, considered that forbidding contains chromic chromate film.Bathe the Cr VI that contains high concentration owing to be used for forming the processing of yellow chromate film, thereby the problem that is produced is to need too high cost for dispose of wastewater.
Therefore, relatively early working out a kind of not chromyl chromate film period, that is, a kind of contained chromium component substantially all be chromic film.Therefore, having developed the chromic processing bath or the not chromyl processing that contain relatively low concentration bathes.Therefore, overcome the problem of waste water dis posal.But, adopt chromic chromate film and yellow chromate film relatively, problem is that Corrosion Protection is unsatisfactory.Therefore, the yellow chromate film of extensive use still is unrealized as the plated film of heater plug and spark plug.
In addition, the common issue with that comprises the traditional chromic acid salt film of yellow chromate film is that heat resistance is unsatisfactory.For example since motor car engine the cylinder head that is connecting spark plug is housed is with water-cooled, thereby make the temperature of spark plug can be not too high.When motor applying under the condition of big thermal load or when spark plug connect when gas exhaust manifold is nearer during continuous firing, the temperature of main metal shell is increased to about 200 ℃ to 300 ℃ sometimes.In said circumstances, it is bad that chromate film is easy to become.Therefore, caused problem is that change is bad rapidly for decay resistance.In addition, it is bad that the problem of traditional chromate film is that performance becomes, and this is because acid ingredient, for example carbon dioxide that contains in the acid rain, nitrogen oxides or sulfur oxide, and the invasion and attack of the acid water that motor produces in the situation of natural gas engine.
Summary of the invention
The purpose of this invention is to provide a kind of heater plug and spark plug with chromate film, described chromate film covers the surface of main metal shell, and contain in a small amount Cr VI, compare with the heater plug of traditional chromate film and spark plug and manufacture method thereof, have fabulous Corrosion Protection and resistance to heat.
In order to address the above problem, according to one aspect of the present invention, a kind of heater plug is provided, it comprises: a resistance heater that is arranged in the main metal shell, the front end of resistance heater extends through arbitrary end face of main metal shell, and wherein, the surface of main metal shell is coated with chromate film, this chromate film contains 95wt% or the more trivalent chromium that accounts for contained chromium component, and has the thickness of 0.2 μ m to 0.5 μ m.
In addition, according to another aspect of the present invention, provide a kind of spark plug, it comprises a contre electrode; An insulating component that is arranged on the contre electrode outside; A main metal shell that is arranged on the insulating component outside; And one be oppositely arranged to form the ground electrode of spark-discharge gap with contre electrode, wherein, the main metal shell surface is coated with chromate film, and this chromate film contains 95wt% or the more trivalent chromium that accounts for contained chromium component, and has the thickness of 0.2 μ m to 0.5 μ m.
Said structure is arranged to such an extent that make the main metal shell surface be coated with chromate film, and this chromate film contains and accounts for contained chromium component 95wt% or more trivalent chromium, and has the thickness of 0.2 μ m to 0.5 μ m.That is to say that common yellow chromate film contains about 25% to 35wt% the Cr VI that accounts for chromium component, yet contain the 5wt% that accounts for chromium component or a small amount of Cr VI still less according to film of the present invention.Therefore, can improve environmental protection effect.The chromate treatment solution that is adopted compares with the Treatment Solution that is used to form yellow chromate film, does not contain any Cr VI, or contains Cr VI in a small amount.Therefore, the waste water dis posal problem can not appear.
The present inventor considers, for example, the chromate film that is called the gloss of monochrome film (uni-chrome film) can not be realized needed gratifying corrosion resistance characteristic of main metal shell and heat resistance in heater plug and the main Environmental Conditions of spark plug with traditional trivalent chromium film such as blue chromate film with little thickness of 0.1 μ m.Therefore, once carry out the investigation of relevant thickness energetically.As a result, detected thickness range, thereby made the present invention for the recommendation of heater plug and spark plug.That is to say that when chromate film thickness is made 0.2 μ m or when bigger, mainly the decay resistance of the chromate film that is made of trivalent chromium can obtain sizable improvement.Therefore, the durability of opposing main metal shell corrosion can be improved fully.In the heater plug environment relevant with spark plug, temperature may be easy to promote exhaust gas constituents (CO
2And NO
x) acid etch that causes can't prevent that in this environment, the decay resistance of main metal shell can be kept satisfactorily.
In the structure of heater plug major component, make the wiring axle of resistance heater energising be provided with to such an extent that make the wiring shaft rear end extend through the other end of main metal shell.In addition, be used for nut and wiring shaft rear end that electricity cable is fixed on the wiring axle are partly gone up the male screw portion engagement that forms.In said circumstances, at least a portion on nut surface is coated with chromate film.Therefore, nut and main metal shell all can have gratifying decay resistance and resistance to heat.
The part of spark plug is equipped with a ring washer, and it must be contained on the bottom of engage threads part of outer surface of main metal shell.When the helical thread portion of main metal shell is tightened in the screw on the cylinder head, the packing ring compressive deformation, resemble it and between the periphery of flange shape gas seal part on the helical thread portion bottom and screw opening, be squeezed, so that the space between sealing screw and the gas hermetic unit.In said circumstances, at least a portion of washer face can be coated with above-mentioned chromate film.Therefore, packing ring and main metal shell all can have gratifying decay resistance and resistance to heat.
When the thickness of chromate film during, can not realize gratifying decay resistance and resistance to heat less than 0.2 μ m.When this thickness during greater than 0.5 μ m, film can the crack take place and/or film is peeled off easily, therefore, makes decay resistance undesirably become bad.The thickness of chromate film is preferably 0.3 μ m to 0.5 μ m.Chromate film does not preferably contain Cr VI substantially.
Chromate technology is conversion one of (conversion) treatment process, during just oxidized and wash-out, chromium component is substituted and accumulation when base metal.Therefore, must not use the metal that can be eluted in the chromate processing bath as base metal from the nothing electricity chromate technology of external world's power supply.The main metal shell of heater plug and spark plug, nut or packing ring generally all are that iron material constitutes as carbon steel.Therefore, the major metal composition is that the zinc class coating of zinc can form on the surface of main metal shell, nut or packing ring to prevent corrosion.Zinc coating is as the preferred base metals that forms chromate film.In said circumstances, the zinc composition of wash-out is brought into chromate film usually.It should be noted that by carrying out known electrogalvanising or molten zinc plating and can form zinc coat.When adopting the electrolytic chromate processing method,, also can form chromate film even be in the situation of nickeling layer of nickel at the major metal composition.
When base metal is a zinc coat, and on substrate metal layer, form when satisfying the chromate film of above-mentioned thickness range, the white rust that zinc-plated erosion causes (white rust) total surface about 20% or more on needed time occurs and can reach " the neutral brine spray test " of the chapter 5 of the coating corrosion resistance test of having carried out meeting JIS H8502 40 hours or longer afterwards.The needed above-mentioned decay resistance level of the main metal shell of heater plug and spark plug is gratifying level.
When substrate metal layer is to be made of zinc coat, and form when having the chromate film of above-mentioned thickness, even also can realize gratifying durability in the test that the temperature of heater plug and spark plug improves in supposition Environmental Conditions subsequently.That is to say, when in atmosphere, under 200 ℃ temperature, heating 30 minutes, and when meeting " the neutral brine spray test " of chapter 5 of coating corrosion resistance test of JIS H8502, the white rust that zinc-plated erosion causes total surface about 20% or more on the required time occurs and can be 40 hours or longer.
In addition, in supposition heater plug and spark plug are subjected to test subsequently in the Environmental Conditions of etch of acid, also can realize gratifying durability.That is to say, the white rust that zinc-plated erosion causes total surface about 20% or more on the required time appears for " the CASS test " of the chapter 7 of the coating corrosion resistance test of having carried out meeting JISH8502 20 hours or longer afterwards.
In method according to manufacturing heater plug of the present invention and spark plug, main metal shell (or nut, or packing ring) immerses in the chromate processing bath, this processing is bathed and is contained chromic salt and trivalent chromium and be blended in wherein complexant, thereby go up at main metal shell (or nut, or packing ring) and to form above-mentioned chromate film.
Chromate processing bath contains chromic salt and chromic complexant.Therefore, can form the chromate film of densification and the thick trivalent chromium class that can not form with common chromate processing method.Therefore, can easily form as chromate film key component, that have the trivalent chromium class of 0.2 μ m to 0.5 μ m thickness according to heater plug of the present invention and spark plug.A kind of method of above-mentioned chromate film has been disclosed among open text DE 19638176 A1 of D.B.P., will describe this method below.
As mentioned above, established a kind of theory, when chromate film forms, will make at first oxidized and wash-out in handling bath of base metal (for example, zinc).Eluted base metal member composition and the solution that contains chromate ion react to each other, because hydroxyl or oxo bridge (oxygen bridges), trivalent chromium forms polymer shape complex, thus on the base metal component surface complex of deposit glue.In said circumstances, chromate film just can generate when only the deposit of contained chromate ion takes place simultaneously in the wash-out of base metal and groove.When having big thickness when chromate film deposit, the elution of reactive of base metal member is suppressed, and therefore, the generation of film also is suppressed.
According to the open text of above-mentioned D.B.P., reduce the speed of the chromate film reverse dissolution of deposit, improve the speed of base metal member dissolving simultaneously and because the speed that the base metal member composition of dissolving and the reaction between the trivalent chromium make the film deposit, this thickness for the formed film of increase is very important.Can think that said method can make the thickness of film increase, this is to make the trivalent chromium coordination can promote the accumulation of film owing to add suitable complexant in groove.
Effectively complexant can be any (dicarboxylic acids, tricarboxylic acids, oxyacid (hydroxydicarboxylic acid or the hydroxyl tricarboxylic acids: for example in the various chelating agents, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, selenous acid, decanedioic acid, maleic acid (meleic acid), phthalic acid, terephthalic acids, tartaric acid (2, the 3-dyhydrobutanedioic acid), citric acid, malic acid (hydroxysuccinic acid) or ascorbic acid).Also can use other a kind of complexant.Operable complexant is disclosed in the open text of above-mentioned D.B.P..
In order to increase the thickness of film, it also is effective that the temperature of chromate processing bath is brought up to about 20 ℃ to about 80 ℃.When the temperature of handling bath is lower than 20 ℃,, temperature effect can not realize substantially because increasing the effect of thickness.When temperature is 80 ℃ or when higher, water is excessive vaporization from bathe.Therefore, handling the state of bathing can not easily control.The immersion time of the member (main metal construction and nut) that must handle in the chromic acid salt bath is 20 seconds to 80 seconds.When the immersion time is 20 seconds or more in short-term, the thickness that needs of chromate film can not be realized sometimes.When the immersion time surpassed 80 seconds, formed chromate film was blocked up.Therefore, crackle (for example, when connecting) can appear in film, and perhaps film easily peels off, and therefore, it is bad that decay resistance undesirably becomes sometimes.
In order to promote the dissolving of base metal member, effectively the practice is to reduce the pH value of chromate processing bath in following ranges, that is, in this scope, the dissolving once more of the film that forms owing to accumulation exceedingly takes place.For example, preferred pH value scope is about 1.5 to about 3.In order to prevent the dissolving again owing to the film of accumulation formation, effectively the practice is film to be contained be difficult for the dissolved again hydroxide as nickel, cobalt or copper.For accomplishing this point, the compound solubilized of above-mentioned metal, be blended in the chromate processing bath.
The investigation result repeatedly that the inventor did is described now.Sneak in the chromic acid salt bath when the sodium salt (for example, sodium nitrate) of prearranging quatity, when making the content of sodium composition in the chromate film be 2wt% to 7wt%, can form chromate film fine and close, that thickness is big.Though can not find detailed mechanism,, can think, in chromate film, contain sodium ion and can prevent that chromate film is dissolved in the processing bath again.When the content of the sodium composition in the chromate film did not satisfy the scope of 2wt% to 7wt%, the thickness of chromate film was difficult for reaching 0.2 μ m or bigger sometimes.The content of sodium composition in chromate film is preferably 2wt% to 6wt%.
When being nut or packing ring plated film, when carrying out above-mentioned processing, can substitute main metal shell with nut or packing ring.Therefore, certainly adopt identical method.
Description of drawings
Figure 1A is the sectional view of expression according to the heater plug of one embodiment of the invention;
Figure 1B is the partial enlarged drawing of Figure 1A;
Fig. 1 C is the sectional view of expression according to the spark plug of one embodiment of the invention;
Fig. 2 A is the schematic representation that the chromate of expression heater plug is handled;
Fig. 2 B is the schematic representation that the chromate of expression spark plug is handled;
Fig. 3 is the plotted curve (chromium (2 of photoelectron spectroscopy of expression according to the result of the X-ray photoelectron spectroscopic analysis of the chromate film of the sample (1) of example 1 and (2)
P2/3) the peak value part);
Fig. 4 is the chromium (2 that the photoelectron spectroscopy of the sample (2) of expression example 1 is analyzed
P2/3) the result that analyzes of the peak separation of peak value part;
Fig. 5 represents the result according to the neutral brine spray test that each sample bore of example 1;
Fig. 6 represents the result of the CASS test in the example 1;
Fig. 7 represents the result of the acid resistance test in the example 1;
Fig. 8 represents the result of the neutral brine spray test that carries out after the heating in the example 1;
Fig. 9 represents according to the relation between the thickness of amount of the Na in the chromate film of the sample of example 2 and chromate film;
Figure 10 represents according to the relation between the thickness of the chromate film of the test of example 3 and the salt solution spraying time;
The scanning electron microscopy that Figure 11 A to 11C is illustrated in the cross section of the sample that adopts in the example 1 resembles;
Figure 12 is the plotted curve (chromium (2 of photoelectron spectroscopy of expression according to the result of the X-ray photoelectron spectroscopic analysis of the chromate film of each sample (1) of example 4 and (2)
P2/3) the peak value part);
Figure 13 is the chromium (2 that the photoelectron spectroscopy of the sample (2) of expression example 4 is analyzed
P2/3) the result's that analyzes of the peak separation of peak value part plotted curve;
Figure 14 is the plotted curve of expression according to the result of the neutral brine spray test that each sample bore of example 4;
Figure 15 is the result's of the CASS test in the expression example 4 a plotted curve;
Figure 16 is the plotted curve of the acid resistance test in the example 4;
Figure 17 is the result's of the neutral brine spray test that carries out a plotted curve after the heating in the example 4;
Figure 18 represents according to the relation between Na amount and the chromate film thickness in the chromate film of the test of example 5;
Figure 19 represents according to the relation between the thickness of the chromate film of the sample of example 6 and the salt solution spraying time.
Embodiment
The contrast accompanying drawing is described embodiments of the invention now.
Heater plug shown in Figure 11 according to one embodiment of the invention has a shell type heater 2 and a main metal shell 3 that is arranged on shell type heater 2 outsides.Shown in Figure 1B, shell type heater 2 has a sleeve pipe 11, and this sleeve pipe has the front end of sealing, and two resistance coils are housed in the sleeve pipe, that is the control coil 23 that is connected in series of the heating coil 21 of adjacent front end setting and the rear end by welding or similar approach and heating coil 21.In addition, insulating material such as magnesium oxide also are housed.The body 11a that holds the sleeve pipe 11 of heating coil 21 and control coil 23 has a front end that extends through metal shell 3, forms a protuberance.Heating coil 21 is connected in sleeve pipe 11 at its front end.The internal surface of the outer surface of heating coil 21 and control coil 23 and sleeve pipe 11 is insulated from each other owing to there is magnesium oxide.Main metal shell 3 forms cylindrical shapes, at main metal shell 3 through hole 4 is arranged axially.Shell type heater 2 is inserted and secured in the through hole 4, makes the front end of sleeve pipe 11 stretch out a predetermined length.The outer surface of main metal shell 3 is provided with the tool engagement part 9 of one six square section, when being connected in heater plug 1 on the diesel engine with box lunch an instrument such as torque spanner is engaged on the tool engagement part 9.
The bottom of sleeve pipe 11 press fit in the through hole 4 of main metal shell 3 so that be fixed on the inside of through hole 4.A countersunk head partly is arranged on through hole 4 opening opposing, so that accommodate rubber o-ring 15 and the insulating bush 16 (for example, being made by nylon) that is assemblied on wiring axle 13 outer surfaces.A retaining ring 17 that prevents that insulating bush 16 from coming off is connected in wiring axle 13 at the rear portion of O shape circle 15 and insulating bush 16.Retaining ring 17 is fixed on the wiring axle 13.The surface corresponding to retaining ring 17 of wiring axle 13 is provided with the knurled portion 13b that strengthens snap-in force.The rear end part of wiring axle 13 is provided with female thread part 13a and is used for cable is fixed on nut 19 on the wiring axle 13 so that mesh one.
The whole outer surface of (for example being made by carbon steel) bottom of main metal shell 3 is coated with and prevents the zinc coat 41 that corrodes.In addition, the outer surface of zinc coat 41 is coated with chromate film 42.The outer surface of nut 19 also is coated with zinc coat 45 and chromate film 46.This zinc coat is to form with identical method with chromate film.Therefore, the part of main metal shell 3 will be done representational description.
Zinc coat 41 forms by known electrogalvanising method, has the thickness of about 3 μ m to 20 μ m.When this thickness during, can not guarantee gratifying corrosion resistance characteristic sometimes less than 3 μ m.When this thickness during greater than 20 μ m, from improving the viewpoint of corrosion resistance characteristic, thickness is too big.Therefore, peacetime in manufacture process, (peace time) was extended, and improved cost sometimes.Specifically, the thickness of the zinc coat 41 of main metal shell 3 is preferably 12 μ m to 20 μ m.The thickness of the zinc coat 45 of nut 19 is preferably 3 μ m to 8 μ m.
In chromate film 42 contained chromium components, chromic ratio is 95wt% or more, and chromate film 42 has the thickness of 0.2 μ m to 0.5 μ m.Chromium component recommends to contain the trivalent chromium of maximum flow, and preferably all chromium component is the trivalent chromium composition.
Fig. 2 A schematically represents to form the method for chromate film 42.That is to say, immerse main metal shell 3 in chromate processing bath 50, this main metal shell has formed the zinc coat of predetermined thickness by known electrogalvanising method or similar approach.The composition of chromic acid salt bath 50 was described.Therefore, shown in Figure 1A, on the surface of the coated coating 41 of main metal shell 3, form chromate film 42.Fig. 2 A is the schematic representation of the above-mentioned processing of expression.Though in the processing shown in this figure, main metal shell 3 just immerses in the chromic acid salt bath 50 simply, but in fact, can adopt known drum method (main metal shell of unpackaged state is introduced liquid container, handles a kind of method when container rotates in handling bath 50).
Bear main metal shell 3 waters that chromate handles and clean and be dried, then main metal shell 3 is introduced the heater plug 1 shown in Figure 1A, be connected on the diesel engine.Main metal shell 3 or nut 19 have the chromate film that forms on zinc coat, this chromate film has the chromate film that is far superior to traditional trivalent chromium class or the decay resistance and the resistance to heat of yellow chromate film.Therefore, the durability of the satisfaction of opposing corrosion can be endowed zinc coat.The present invention can be applicable to be equipped with the main metal shell or the nut of the heater plug of the ceramic heater that substitutes the shell type heater.
Embodiment about spark plug will be described below.
Has a cylindrical shape main metal shell 101 according to the spark plug with heater 100 shown in of the present invention and Fig. 1 C; An insulating component 102 that is contained in main metal shell 101 inside, the front end of this insulating component 102 extends through main metal shell 101; A contre electrode that is arranged in the insulating component 102, the front end of this contre electrode 103 extends through insulating component 102; And a ground electrode 104, it is provided with to such an extent that make an end of ground electrode be connected in main metal shell 101, and its other end is relative with contre electrode 103.Between ground electrode 104 and contre electrode 103, form a spark-discharge gap g.
Insulating component 102 for example is made of the stupalith of sintering such as aluminium oxide or aluminum nitrate, is shaped on a through hole 106 that forms on axially at insulating component 102, so that admit contre electrode 103.A metal connection post 113 is inserted and secured in arbitrary end of through hole 106, and contre electrode 103 is inserted and secured in the other end of through hole 106.In through hole 106, a diameter different piece 115 is arranged between metal connection post 113 and the contre electrode 103.The two ends of diameter different piece 115 are electrically connected on contre electrode 103 and metal connection post 113 by conductive glass seal layer 116 and 117 respectively.
The main metal shell made from metal such as carbon steel forms cylindrical shape.In addition, on the outer surface of main metal shell 101, form a helical thread portion 107, so that spark plug 100 is connected in the engine cylinder-body (not shown).Label 101e represents a tool engagement part, and when connecting main metal shell 101, instrument such as spanner or folding cramp joint are combined on this tool engagement part, and described tool engagement part forms the hexagonal shaped section in the axial direction.On the other hand, O-ring seal 116 that is used to be engaged in the rear portion circumference of flange shape protuberance 102e is arranged between the outer surface of the internal surface of rear aperture of main metal shell 101 and insulating component 102.In addition, the packing layer 161 made by a talcum or analog of O-ring seal 160 is arranged on the rear portion of seal ring 162.Insulating component 102 is pushed to main metal shell 101 forward.In aforementioned circumstances, an end of the opening of main metal shell 101 forms a bead portion 101d inwardly towards seal ring 160 crimpings.Therefore, main metal shell 101 is fixed on the insulating component 102.
Then, be used to prevent that the zinc coat 141 (zinc class coating) that corrodes is formed on whole outer surfaces of (for example being made of carbon steel) base layer of main metal shell 101.In addition, the outer surface of zinc coat 141 is coated with chromate film 142.Similarly, zinc coat 145 and chromate film 146 also form on the outer surface of packing ring 130.This zinc coat is to form with identical method with chromate film, therefore, will describe the part of main metal shell 101 typically.
In chromate film 142 contained chromium components, chromic than being 95wt% or more, chromate film 142 has the thickness of 0.2 μ m to 0.5 μ m.Chromium component recommends to contain the trivalent chromium of maximum flow, and preferably all chromium component is the trivalent chromium composition.
Fig. 2 B schematically represents to form the method for chromate film 142.That is to say main metal shell 101 " have zinc coat, this zinc coat forms by known electrogalvanising method, has preset thickness, with this main metal shell 101 " immerse in the chromic acid salt bath 150, the composition of chromic acid salt bath 150 was described.Therefore, shown in Fig. 1 C, chromate film 142 forms on the zinc coat surface of main metal shell 101.Fig. 2 B is the schematic representation of the above-mentioned processing of expression.Though the figure shows the method that main metal shell 101 immerses chromic acid salt bath 150 simply, but, in fact also can adopt known drum process (main metal shell of unpackaged state is introduced into liquid container, when this container is being handled the method for handling when rotating in 150 of bathing) or similar method.
Bear that main metal shell 101 waters that chromate handles clean and dry, the spark plug 100 shown in Fig. 1 C of then main metal shell 101 being packed into.Then, use packing ring 130 that main metal shell 101 is connected in motor.Main metal shell 101 or enclose 130 have the chromate film that forms on zinc coat has the decay resistance and the resistance to heat that are better than traditional trivalent chromium class chromate film or yellow chromate film.Therefore, the durability of gratifying opposing corrosion is endowed zinc coat.The result of experiment that is described as now confirming effect and carries out.
Example 1
The carbon steel wire SWCH8A that is used for cold forging that meets JIS G3539 makes the microscler main metal shell 101 with shape shown in Fig. 1 C as raw material by cold forging.The nominal size that note that the helical thread portion 107 of main metal shell 101 is 14mm, and axial length is about 19mm.Then, main metal shell 101 is bathed by known alkaline cyanide and is born the electrogalvanising processing, and forming thickness is the zinc coat of 6 μ m.
With respect to 1 liter of deionized water dissolving, 50 gram chromium chloride (III) (CrCl
36H
2O), 3 gram cobalt nitrate (II) (Co (NO
3)
2), 100 gram sodium nitrate (NaNO
3) and the 31.2g malonic acid, so that the chromic acid salt bath 50 shown in preparation Fig. 2 B.Then, by handling heater solution temperature is remained on 60 ℃.In addition, will handle the pH value of bathing by the interpolation soda lye and be adjusted to 2.0.The main metal shell that will have a zinc coat immersed in the chromate processing bath 50 60 seconds.Then, the main metal shell water is cleaned and drying.Then, be that 80 ℃ hot air carries out drying with temperature, thereby form chromate film (sample (1): example).
With the nitric acid dissolve of the chromic anhybride of 7 grams per liters, sulfuric acid that 3g/ rises and 3 grams per liters in deionized water, so that the preparation yellow chromatings is bathed.Handle the temperature of bathing and remain on 20 ℃.In handling bath, immerse main metal shell about 15 seconds, propose main metal shell and dry then, form yellow chromate film (sample (2): comparison example).Preparation gloss chromic acid salt bath, wherein, the nitric acid of the chromium potassium suplhate of 3 grams per liters (potassium chromium sulfate), 4 grams per liters and the hydrofluoric acid dissolution of 2 grams per liters are in deionized water.Handle the temperature of bathing and remain on 20 ℃.In handling bath, immerse main metal shell about 15 seconds, propose main metal shell and dry then, thereby form the chromate film (sample (3): comparison example) of gloss.The chromate film thickness of each sample is being measured on cross section by scanning electron microscopy.The thickness of sample (1) is 0.33 μ m, and the thickness of sample (2) is 0.31 μ m, and the thickness of sample (3) is 0.07 μ m.Cross-sectional scans electron microscopic (SEM) image that is used for measuring thickness is presented at Figure 11 A to Figure 11 C.Figure 11 A represents the SEM image of sample (1), and Figure 11 B represents the SEM image of sample (2), and Figure 11 C represents the SEM image of sample (3).For the ease of observing chromate film, on the surface of film, form a thin Au film by Vacuum Coating method.Compare with thin Au film with the substrate zinc coat with high conductivity, the chromate film with low electric conductivity forms dark image in the SEM image, can easily detect the chromate film image according to poor contrast.In each SEM image, according to the contrast ratio white line that on position, draws corresponding to the border between chromate film, zinc coat and the Au film.Can determine thickness according to the distance between the white line.
The state that chromium exists in each formed chromate film is by the inspection of X-ray spectral analysis (XPS) method.Fig. 3 is illustrated in chromium (2 in the spectrum of sample (1) and (2)
P2/3) peak value.Sample (1) (being represented by solid line) does not have peak value on corresponding to chromic position.Therefore, the major component of chromium component is a trivalent chromium.On the other hand, sample (2) has chromic peak value, overlapping thereon chromic peak value.Therefore, partly detect the part of raising at the high energy of peak value.
Fig. 4 represents the compartment analysis of the peak value shape of each peak value, and the intensity of supposing the photo-electron X ray is that (axis of ordinates: cps), binding energy (bond energy) is an X (axis of abscissas: eV) to I.Then, carry out calculus of approximation with following formula:
I＝exp{-(x-μ)
2/2σ
2} (1)
μ is the X coordinate of peak value in the formula, and σ is the half-breadth of peak curve.
According to the result, suppose that chromic peak height is I1, chromic peak height is 12, so, I2/ (I1+I2) is about 0.2 (I2/ (I1+12) is preferably 0.05 or littler, so that reduce hexavalent chromium amount).Heavy chromium sesquioxide (dichromic sesquioxide) standard reference material is used to form an analytic curve, so that metering chromic weight content in the total amount of chromium component.Detected situation is, approximately 15wt% is a Cr VI, and all the other are trivalent chromium.Similar analysis has also been done in sample (1) and (3), and the result is that whole chromium components are trivalent chromium.
" the neutral brine spray test " of chapter 5 that sample (1) to (3) is met the coating corrosion resistance test of JIS H8502.Like this, the white rust that zinc coat corrosion causes total surface about 20% or more on needed time to occur measured so that the assessment durability.In this manual, main metal shell is as sample.In addition, the part of tool engagement (six quadrate part branches) is the surface of sample.The result is illustrated among Fig. 5.That is to say, show 240 hours gratifying wear life according to main metal shell sample of the present invention (1).The result of sample (2) who bears yellow chromatings is similar.This result is about 8 times of result with sample (3) of traditional thin gloss chromate film.
Also carried out meeting " the CASS test " of chapter 7 of the coating corrosion resistance test of JIS H8502 for the sample that is similar to sample (1) to (3).Like this, the white rust that zinc-plated erosion causes total surface about 20% or more on needed time to occur measured so that the assessment durability.In addition, in the following manner, use sulfuric acid and nitric acid to carry out the durability test respectively: initial, pH2 sulfuric acid solution or salpeter solution are introduced exsiccator.Then each sample is encapsulated in the exsiccator, makes not contact acid solution directly of sample, but can contact the steam of solution.The temperature of exsiccator keeps in transferring to 90 ℃ thermostatic tank, so that assess according to testing similar standard with CASS.The result is illustrated in Fig. 6 and 7.In each test, the result who bears the sample (2) of yellow chromatings and bear the sample (3) that the gloss chromate handles is that wear life is lacked.On the other hand, the result according to the sample (1) of embodiments of the invention is that durability is satisfactory.
Then, carry out the as installed test, the spark plug shown in Fig. 1 C is to use above-mentioned main metal shell to make.Then, spark plug is installed on 6 cylinders and the 2000cc petrol engine.Motor is in continuous operation 10 hours under the state that throttle is opened fully under the rotating speed of 5600rpm.It should be noted that the temperature of main metal shell is about 200 ℃ at work.Each sample that carries out the as installed test bears and is similar to the neutral brine spray test of testing previously.The result is illustrated among Fig. 8.The result who bears the sample (2) of yellow chromatings and bear the sample (3) that the gloss chromate handles is the wear life of about 20 hours weak point.On the other hand, the result according to the sample (1) of embodiments of the invention is the wear life of 180 hours gratifying length after it is installed on the motor.
Each sample is heated to 200 ℃ in thermostatic tank in atmosphere, kept this temperature 30 minutes.Carry out similar neutral brine spray test then.The result who bears the sample (2) of yellow chromatings and bear the sample (3) that the gloss chromate handles is the wear life of about 20 hours weak point.On the other hand, the result according to the sample (1) of embodiments of the invention is the wear life of 200 hours gratifying length.
Example 2
Under identical condition, make the main metal shell that is similar to example 1, until carrying out the zinc processing procedure.Then, with respect to 1 liter of deionized water dissolving, 50 gram chromium chloride (III) (CrCl
36H
2O), 3 gram cobalt nitrate (II) (Co (NO
3)
2), 50 grams are to 100 gram sodium nitrate (NaNO
3) and 31.2 gram malonic acid.Then, by handling heater solution temperature is remained on 60 ℃.In addition, will handle the pH value of bathing by the interpolation soda lye and be adjusted to 2.0.In this chromate treatment solution, immerse main metal shell 60 seconds with zinc coat.Then, be 80 ℃ hot air drying with temperature, form chromate film with different-thickness.The thickness of resulting chromate film is measured in the SEM cross section that is similar to example 1 by observation.The content of Na is checked by X-ray photoelectron spectroscopic analysis method (XPS) and is measured.The result is illustrated among Fig. 9.That is to say, when the Na content in the film is 2wt% to 7wt%, particularly when Na content is 2wt% to 6wt%, obtained the big chromate film of thickness in the relatively short time.
Example 3
Under identical condition, make the main metal shell that is similar to example 1, until carrying out galvanizing process.Then, with respect to 1 liter of deionized water dissolving, 50 gram chromium chloride (III) (CrCl
36H
2O), 3 gram cobalt nitrate (II) (CO (NO
3)
2), 50 grams are to 150 gram sodium nitrate (NaNO
3) and 31.2 gram malonic acid.Then, by handling heater solution temperature is remained on 60 ℃.In addition, will handle the pH value of bathing by the interpolation soda lye and be adjusted to 2.0.In chromate treatment solution, immerse main metal shell 40 seconds to 80 seconds with zinc coat.Then, water cleans main metal shell and dry.Be that 80 ℃ hot air carries out drying with temperature then, form chromate film with all thickness.Each main metal shell with chromate film is similar to the neutral brine spray test of example 1, so that assess chromate film.The result is illustrated among Figure 10.When the thickness of film is 0.2 μ m to 0.5 μ m, particularly when thickness is 0.3 μ m to 0.5 μ m, realized gratifying durability.
Example 4
Material is the STKM13CE that meets JIS G3445, has the main metal shell 3 of shape shown in Figure 1A by the cold forging manufacturing.It should be noted that the nominal size of the helical thread portion 7 of main metal shell 3 is 10mm, axial length is about 51.5mm.Then, main metal shell 3 is born use the electrogalvanising of alkaline cyanide bath to handle, forming thickness is the zinc coat of 16 μ m.
By restraining chromium chloride (III) (CrCl with respect to 1 liter of deionized water dissolving 50
36H
2O), 3 gram cobalt nitrate (Co (NO
3)
2), 100 gram sodium nitrate (NaNO
3) and 31.2 gram malonic acid, thereby the chromic acid salt bath 50 of preparation shown in Fig. 2 A.By handling heater solution temperature is remained on 60 ℃ then.In addition, will handle the pH value of bathing by the interpolation soda lye and be adjusted to 2.0.Main metal shell 3 is immersed in the chromic acid salt bath 50 60 seconds.Then, be that 80 ℃ hot air carries out drying with temperature, form chromate film (sample (1): example).
Chromic anhybride, the sulfuric acid of 3 grams per liters and the nitric acid of 3 grams per liters of dissolving 7 grams per liters in deionized water.The temperature that this processing is bathed remains on 20 ℃.In this processing is bathed, immerse main metal shell about 15 seconds, propose main metal shell and dry then, form yellow chromate film (sample (2): comparison example).Chromium potassium suplhate (potassium chromiumsulfate), the nitric acid of 4 grams per liters and the hydrofluoric acid of 2 grams per liters of dissolving 3 grams per liters in deionized water, thereby preparation gloss chromate processing bath.The temperature that this processing is bathed remains on 20 ℃.During main metal shell immerse to handle bathed about 15 seconds, mention then and dry main metal shell, form gloss chromate film (sample (3): comparison example).At the thickness of on the cross section, measuring each sample by scanning electron microscopy.The thickness of sample (1) is 0.33 μ m, and the thickness of sample (2) is 0.31 μ m, and the thickness of sample (3) is 0.07 μ m.Thickness is to measure according to the same way as described in the example 1.
The state that chromium exists in each formed chromate film is checked by photo electron spectroscopy (XPS).Figure 12 is illustrated in chromium (2 in the spectrum of sample (1) and (2)
P2/3) peak value.Sample (1) (shown in the solid line) does not have peak value on corresponding to chromic position.Therefore, the major part of chromium component is a trivalent chromium.On the other hand, sample (2) has chromic peak value, overlapping thereon chromic peak value.Therefore, partly measure the part of a rising at the high energy of peak value.
Figure 13 represents that the intensity of supposing the photo-electron X ray is I (axis of ordinates: cps), be X (axis of abscissas: eV) in conjunction with energy to the result of the peak separation analysis of the shape of each formed peak value.Carry out calculus of approximation with following formula then:
I＝exp{-(x-μ)
2/2σ
2} (1)
μ is the y coordinate of peak value in the formula, and σ is the half-breadth of peak curve.
According to the result, suppose that chromic peak height is I1, chromic peak height is I2, so, I2/ (I1+I2) is about 0.2 (I2/ (I1+I2) is preferably 0.05 or littler, so that reduce hexavalent chromium amount).Heavy chromium sesquioxide (dichromic sesquioxide) standard reference material is used for forming an analytic curve, so that calculate chromic weight content in whole chromium components.Detected situation is, approximately 15wt% is a Cr VI, and all the other are trivalent chromium.Sample (1) and (3) have also been carried out similar analysis, and the result is that chromium component substantially all is a trivalent chromium.
" the neutral brine spray test " of chapter 5 that sample (1) to (3) is met the coating corrosion resistance test of JIS H8502.Measure like this white rust that zinc coat corrosion causes total surface about 20% or more on the required time appears so that the assessment durability.In this manual, main metal shell is as sample.In addition, instrument institute engaging portion (six quadrate part branches) is a specimen surface.The result is illustrated among Figure 14.That is to say, show 240 hours gratifying wear life according to the present invention and the main metal shell sample (1) that satisfies the heater plug requirement.This result is similar to the result of the sample (2) that bears yellow chromatings.This result is about 8 times of result with sample (3) of traditional thin gloss chromate film.
The sample that is similar to sample (1) to (3) has been carried out meeting " the CASS test " of chapter 7 of the coating corrosion resistance test of JIS H8502.Measured like this white rust that the zinc coat corrosion causes total surface about 20% or more on the required time appears so that the assessment durability.In addition, use sulfuric acid and nitric acid to carry out the durability test in the following manner respectively: initial, pH2 sulfuric acid solution or salpeter solution are introduced exsiccator.Then each sample is encapsulated in the exsiccator, makes not contact acid solution directly of sample, but can contact the steam of solution.The temperature of exsiccator can be set in 90 ℃ the thermostatic tank at one and keep, so that assess according to testing similar standard with CASS.The result is illustrated in Figure 15 and 16.In each test, the result who bears the sample (2) of yellow chromatings and bear the sample (3) of gloss chromate processing is the wear life of weak point unsatisfactory.On the other hand, the result according to the sample (1) of embodiments of the invention is gratifying durability.
Each sample is heated to 200 ℃ in atmosphere, carry out similar neutral brine spray test after 30 minutes.The result is illustrated among Figure 17.The result who bears the sample (2) of yellow chromatings and bear the sample (3) that the gloss chromate handles is the wear life of about 20 hours weak point.On the other hand, are wear lifes according to the result of the sample (1) of embodiments of the invention in the back 200 hours gratifying length of heating.
Example 5
Under identical condition, make the main metal shell that is similar to example 4, until carrying out zinc-plated processing procedure.Then, with respect to 1 liter of deionized water dissolving, 50 gram chromium chloride (III) (CrCl
36H
2O), 3 gram cobalt nitrate (II) (Co (NO
3)
2), 50 grams are to 150 gram sodium nitrate (NaNO
3) and 31.2 gram malonic acid.Then, by handling heater solution temperature is remained on 60 ℃.In addition, will handle the pH value of bathing by the interpolation soda lye and be adjusted to 2.0.In chromic acid salt bath 50, immerse main metal shell 60 seconds with zinc coat.Then, water cleans and dry main metal shell.Be that 80 ℃ hot air carries out drying with temperature then, form the chromate film of all thickness.The micro-section of electron scanning that is similar to example 1 by observation is measured the thickness of resulting chromate film.By ESCA measuring N a content.The result is illustrated among Figure 18.That is to say, when the Na content in the film is 2wt% to 7wt%, particularly when this content is 2wt% to 6wt%, in the relatively short time, obtained the chromate film of big thickness.
Example 6
Under identical condition, make the main metal shell that is similar to example 1, until carrying out zinc-plated processing.Then, with respect to 1 liter of deionized water dissolving, 50 gram chromium chloride (III) (CrCl
36H
2O), 3 gram sodium nitrate (NaNO
3) and 31.2 gram malonic acid.Then, by handling heater solution temperature is remained on 60 ℃.In addition, will handle the pH value of bathing by the interpolation soda lye and be adjusted to 2.0.In chromate treatment solution, immerse main metal shell 40 seconds to 80 seconds with zinc coat.Then, water cleans and dry main metal shell.Be that 80 ℃ hot air carries out drying with temperature then, form the chromate film of all thickness.Each main metal shell with chromate film is similar to neutral brine spray test in the example 4, so that the assessment chromate film.The result is illustrated among Figure 19.When thickness is 0.2 μ m to 0.5 μ m, particularly when thickness is 0.3 μ m to 0.5 μ m, realized gratifying durability.
Claims (18)
1. heater plug comprises:
A main metal shell;
A resistance heater, it is arranged in the main metal shell, and the front end of described resistance heater extends through arbitrary end face of described main metal shell, it is characterized in that:
Described main metal shell surface is coated with chromate film, and this chromate film contains 95wt% or the more trivalent chromium that accounts for contained chromium component, and has the thickness of 0.2 μ m to 0.5 μ m.
2. heater plug as claimed in claim 1 is characterized in that: described chromate film contains the 5wt% that accounts for chromium component or Cr VI still less.
3. heater plug as claimed in claim 1, it is characterized in that: be used to make the wiring axle of described resistance heater energising to be provided with to such an extent that make the rear end of described wiring axle extend through the other end of described main metal shell, one is used for the nut that electricity cable is fixed on the described wiring axle is meshed with the male screw portion that forms on described wiring shaft rear end part, and
At least a portion surface of described nut is coated with above-mentioned chromate film.
4. heater plug as claimed in claim 1 is characterized in that: the content of contained sodium composition is 2wt% to 7wt% in described chromate film.
5. heater plug as claimed in claim 1 is characterized in that: at least one in described main metal shell and the described nut is coated with zinc-plated film, and it is as the substrate metal layer of described chromate film.
6. method of making heater plug, described heater plug have the resistance heater that is arranged in the main metal shell, and the front end of this resistance heater extends through arbitrary end face of described main metal shell, and the method for described manufacturing heater plug may further comprise the steps:
Described main metal shell is immersed a chromate processing bath, the complexant that contains chromic salt and mix chromic salt is within it bathed in described processing, thereby on described main metal shell surface, form chromate film, this chromate film contains and accounts for contained chromium component 95wt% or more trivalent chromium, and has the thickness of 0.2 μ m to 0.5 μ m.
7. the method for manufacturing heater plug as claimed in claim 6 is characterized in that: when described chromate processing bath carried out, the temperature that described processing is bathed was set at 20 ℃ to 80 ℃.
8. the method for manufacturing heater plug as claimed in claim 6 is characterized in that: described main metal shell immersed described chromate processing bath 20 seconds to 80 seconds.
9. the method for manufacturing heater plug as claimed in claim 6 is characterized in that: the sodium salt of prearranging quatity is sneaked into described chromic acid salt bath, and the content that makes sodium composition contained in the resulting chromate film is 2wt% to 7wt%.
10. spark plug comprises:
A contre electrode;
An insulating component that is arranged on the described contre electrode outside;
A main metal shell that is arranged on the described insulating component outside; And
A ground electrode, it and described contre electrode are oppositely arranged, thereby form a spark-discharge gap; It is characterized in that:
The surface of described main metal shell is coated with chromate film, and described chromate film contains 95wt% or the more trivalent chromium that accounts for contained chromium component, and has the thickness of 0.2 μ m to 0.5 μ m.
11. spark plug as claimed in claim 10 is characterized in that: described chromate film contains the 5wt% that accounts for chromium component or Cr VI still less.
12. spark plug as claimed in claim 10 is characterized in that: also comprise a ring washer, be installed on the bottom of the connecting thread that forms on the described main metal shell outer surface;
Wherein, at least a portion of described packing ring is coated with above-mentioned chromate film.
13. spark plug as claimed in claim 10 is characterized in that: the content of contained sodium composition is 2wt% to 7wt% in described chromate film.
14. spark plug as claimed in claim 10 is characterized in that: described main metal shell or described main metal shell and described packing ring are coated with the zinc-plated film as the substrate metal layer of described chromate film.
15. method of making spark plug, described spark plug has that a contre electrode, one are arranged on that the insulating component in the described contre electrode outside, main metal shell that is arranged on the described insulating component outside and one are oppositely arranged with described contre electrode and the ground electrode that forms spark-discharge gap, and the method for described manufacturing spark plug may further comprise the steps:
Described main metal shell is immersed in the chromate processing bath, described chromate processing bath contains trivalent chromium and the described chromic complexant that is mixed in wherein, thereby on described main metal shell surface, form chromate film, described chromate film contains 95wt% or the more trivalent chromium that accounts for contained chromium component, and has the thickness of 0.2 μ m to 0.5 μ m.
16. the method for manufacturing spark plug as claimed in claim 15 is characterized in that: described chromic acid salt bath makes the temperature of described chromic acid salt bath be set at 20 ℃ to 80 ℃ when carrying out.
17. the method for manufacturing spark plug as claimed in claim 15 is characterized in that: described main metal shell immersed in the described chromate processing bath 20 seconds to 80 seconds.
18. the method for manufacturing spark plug as claimed in claim 15 is characterized in that: the sodium salt of prearranging quatity is sneaked in the described chromate processing bath, and the content that makes contained sodium composition in the described chromate film is 2wt% to 7wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001240390A CN1137330C (en) | 2000-08-24 | 2000-08-24 | Preheating plug and spark plug and its producing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001240390A CN1137330C (en) | 2000-08-24 | 2000-08-24 | Preheating plug and spark plug and its producing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1339653A CN1339653A (en) | 2002-03-13 |
| CN1137330C true CN1137330C (en) | 2004-02-04 |
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|---|---|---|---|
| CNB001240390A Expired - Lifetime CN1137330C (en) | 2000-08-24 | 2000-08-24 | Preheating plug and spark plug and its producing method |
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| Country | Link |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103081264A (en) * | 2010-08-26 | 2013-05-01 | 日本特殊陶业株式会社 | Spark plug |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005197206A (en) * | 2003-12-10 | 2005-07-21 | Denso Corp | Spark plug |
| US8319153B2 (en) * | 2008-11-17 | 2012-11-27 | Federal-Mogul Italy Srl. | Glow plug with metallic heater probe |
| JP4728437B1 (en) * | 2010-03-10 | 2011-07-20 | 日本特殊陶業株式会社 | Spark plug, metal shell for spark plug, and method for manufacturing spark plug |
| DE102010062443A1 (en) * | 2010-12-06 | 2012-06-06 | Robert Bosch Gmbh | Glow plug and method for its production |
| EP2730905B1 (en) * | 2012-11-12 | 2019-01-02 | Sensata Technologies, Inc. | A pressure-measuring plug for a combustion engine |
| DE102015200778A1 (en) * | 2015-01-20 | 2016-07-21 | Robert Bosch Gmbh | glow plug |
| CN111075629A (en) * | 2019-12-30 | 2020-04-28 | 安徽安鑫货叉有限公司 | Automatic preheating ignition mechanism for pallet fork |
-
2000
- 2000-08-24 CN CNB001240390A patent/CN1137330C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103081264A (en) * | 2010-08-26 | 2013-05-01 | 日本特殊陶业株式会社 | Spark plug |
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| CN1339653A (en) | 2002-03-13 |
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