CA1103810A - Process for depositing a conducting metal layer on an insulating support - Google Patents
Process for depositing a conducting metal layer on an insulating supportInfo
- Publication number
- CA1103810A CA1103810A CA297,857A CA297857A CA1103810A CA 1103810 A CA1103810 A CA 1103810A CA 297857 A CA297857 A CA 297857A CA 1103810 A CA1103810 A CA 1103810A
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- metal
- enamel
- composition
- containing powder
- enameled
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Abstract
ABSTRACT OF THE DISCLOSURE:
A method of manufacturing a pattern of electro-conductive metal deposited on an enameled substrate which comprises applying an ink composition to the enameled substrate in accordance with the pattern, the ink composition comprising a second enamel and a metal-containing powder receptive to electroless plating, the second enamel having a melting point no greater than the soften-ing point of the enamel of the enameled substrate and the metal-containing powder being present in an amount sufficient to pro-vide from 60 to 90% by weight of the ink composition after baking; baking the composition; treating the baked composition so as to expose particles of the metal containing powder; and subjecting the baked, exposed composition to electroless plating.
A method of manufacturing a pattern of electro-conductive metal deposited on an enameled substrate which comprises applying an ink composition to the enameled substrate in accordance with the pattern, the ink composition comprising a second enamel and a metal-containing powder receptive to electroless plating, the second enamel having a melting point no greater than the soften-ing point of the enamel of the enameled substrate and the metal-containing powder being present in an amount sufficient to pro-vide from 60 to 90% by weight of the ink composition after baking; baking the composition; treating the baked composition so as to expose particles of the metal containing powder; and subjecting the baked, exposed composition to electroless plating.
Description
The present i.nvention relates to a rnethod oE manufactu-rlng .ll~atl-~L~ l(c~ o~.:o~ cl.:iv~ t ~ll d~ o~ 1 ol-l an ellame:Led substrate.
A pl.ocess i.s a:l.ready knowll~ cl.i.sc:losecl in [).S. l?ateut No 3,~2~,256, iss~ c~ b~ 9~r~ lV.il~(3 1~ .LI1VC!I~ L S~ e, wllerc~:in a :I.avel: o:f^`l~oll conduct.ing .inl; :I.oadecl with a ~)owcler o~
me~al, a1.1oy or nleta:Ll:i.c: cler:i.vat:i.vc! .i.; appli.ed oll the support, thell heatecl in orcler to hardell the inlc, t.he ~urface oE the ink la~er be:i.lly treatecl so as to lay t~e parL-.i.cles for.rning sa:id powcler bare, and the support thus coated is immersedinto a bath contaillin(3, in the form o~ particles, the conclucting metal to be depositecl/ under conditions wh:ich are known per se anct such that said conducting rnetal. partlcles are c1eposited 011 the powcler parti.cles laid bare.
In the usual ways of performing this process, a glass and ;~
resin laminate is used as insulating support, the resin being a -thermostable resin sueh as s:ilicone orpolyimide, and the ink being also a therrno-s-table resin such as silicone or polyimide.
The use of plastic materials for the support limits how-2G ever the opera.ting temperatures of the circuit obtained and its resistanee to ageing. :
Moreover, it is desi.rable to be able to form printed cir-euits, resisting or not, on supports currently used in the :
branch of electric household appliances such as on steel or aluminium sheets r glass, etc.
According to the present invention, there is provided amethod of manufaeturing a pattern of eleetroeonductive metal deposited on an enamel.ed substrate~ which comprises applylng an ink composition to the enameled-substrate in accordance wi.th the pattern, the ink composition comprising a second enamel and a metal-eontaining powder reeeptive to eleetroless plating, the second enamel having a melting point no greater than the soften-ing point of the enamel of the enameled substrate and the metal-~3~LU
containing powder being p~esen~ in an amount ~;uEicient to pro-vide Erom 60 to 90~ by weight~o~ the ink cOMpositiOn after balcing; baking the composi~ion; treating the baked composition so as to expose partLc1ec ol: the meta:L containing powder; and sllbjectil~tJ the l)aked, e~posec~ compositiorl to elc~ctroless platiny.
T~lc ~Ise o an enalnel Eor Eorminy the inlc permits usiny as support ellamc:lled metal:Lic sheets or glasses or ~rlamelled cera-mics. Said supports exhiblt the ac1vantaye ot having a robust-ness, a resistance to ageing and a thermal stability which are obviously very hiyh.
The deposit of the conductillg metal is preferably carried out according to the so-called "electroless" chemical deposi-t process which is not using electricity.
The proportion of powdered metal in the inlc, after baking the enamel, is advantageously comprised between 60 and 90~ by weight, the proportioll of enamel being -then oE 10 - 40% by weight.
A high proportion of powdered metal is in Eact necessary for reaching a high density of the metallic particles said high density favouring a uniform deposit oE the conducting metal.
This high proportion, and the density generally high of the metals, lead to the fact that the outer layer of the sup-port coating has to have a softening point of the same order preferably slightly superior to the melting point of the ink enamel. In fact if the coating was getting soft in a notable manner while the ink was being baked, the powdered metal would penetrate into the coating and cause cracks, and the electrical insulation characteristics of the coatiny would be seriously impaired.
As reyards the carrier, an oil which is habitually used to this effect is employed, in a proportion such that the ink obtained is in the form oE a fluid compound usable with .
" ~3~3~3 the sil~-screen proce~s. This proportion depends on the specific surface of the powdered metal uqed, a high speci~lc surface requiring a large quantity o~ oil.
The powdered metal must exhibit a relatively high resis-tivity qo a~ not to modify the electrical characteri~tics o~ the ~inal. prlnted circui$. On the other hand, the metal o~ ~id powder has to be chosen such that the depo~it of oonducting metal through the "el~ctroless" proces~ i~
carried out ~Ider the mo3t favourable conditions~ In principle, a metal is chosen who~e electrolitlc potential E
is high relative to that of the conducting ~etalO ~owever, one may al~o use the same metal a~ the conducting metal, notably ln the case of nickel, A~ examples o~ powdered metals, o~e can mention in particular the powders of cobalt-nickel or iron, wlth particle size comprised between 1 and 10 ym.
Preferably, partiole~ of spongy or angular shape will be used~ since ~uc~ shape~ provide a good mutual bonding of the particles which provides them with a better resistance to the treatment neces~ary for laying the particles bare, oarried out through sand blasting, brushin~ or chemical attack. Moreover, said particle ~hapes favour the obtentio~
of a high den~ity ~hich, as has been seen, i~ advantageousc The conducting metal chosen for making the printed circult i9 selected of cour~e in relation with the conai-dered applicationO I~ the circuit has to ha~e a high re-.sistance, and is intended for u~e in heating, a hlgh re-sistivity metal will be chosen ~uch as nickelO I~ on the contrary a lo~ resistance circuit is required, intended for instance fsr establi~hing connections, a lo~ con-ductive metal will be chosen such as copper or silver.
The enamel coating applied on the support is of great importance since, further to its stanclarcl Eunetions of pro-teCtincJ the support alld giVinCJ it a yoocl appearanee, it has to permit the aclh~rellce o~ t~le inli layer and provicle the eleetrical lnsu1atioll betweell support alld prlntecl eircuit when the support ls ikselL eoncllle~ive.
OC course, the ellamel eoatillg is chosen primarily as a functioll of th~ support characteristics: meltin(3 point, thermal expansion eoefEicient, resistivity, surface state, ehemical nature.
A preferred embodiment will be deseribed hereinafter as an example having reference the attached drawings, wherein:
Figs. 1 to 6 illustrate differell-t steps of -the method of the present invelltioll.
The strueture and eharaeteristies of the enamel coating will is described hereinafter in the ease where the support is a steel (or eopper) sheet, an aluminum sheet, or a glass sheet ~or also a eeramie or a borosilieate sheet).
When the support is a normal steel sheet, a mass layer has 2n to be providecd with a very blistered strueture for easing the removal of gas from the sheet when being baked. Said mass being therefore little insulating, upper layers of very high resistivity have to be provided.
On the other har.d, the linear expansion coefficients have to decrease from the metal sheet to the eovering layer so that the eoating be in eompression relative to the sheet.
Sueh eonditions being taken into aeeount, there will be applied in suceession on the metal sheet, whieh has a linear expansion eoe~icient ~, measured between 20 and 320C, of 140.10 7, - a standard mass with a eoefficient ~= 100.10 7 and a - 4 ~
thicl~nc-ss o~ 10 to 12 ,um, - an insulal::in~J mass, ~irh a co~tEicien~ ~.= 85.10 7, and a thickness o~ 40 ,um, - an insu`l a tin~ coa t:in(3 enam~1 j wi th a coef ' ic~ en t .
, ,. , ~ .~
..
~ : - , .:
. . ~
:
' 3~
,~= 80.10 7 and a thic]cness between 100 and 150 ~m.
If a decarburized shee-t is used, one may advan-tageously omit -the first mass layer and apply only the insulating mass~and the covering enamel.
The man of the art wlll have no difficul-ty in selecting, considering the application in question, enamels having -the hereabove characteristics. It will be only mentioned that one can use as coa-ting enamel -the enamel sold under -the trademark MA~OLIQUl3 by the ''Procedes ~'erro'' Colnpany, with a softening point lylny between 600 and 650 C.
The enamel of the corresponding ink will have a melting point of the same order, that is of abou-t 600 C.
In the case of a stainless s-teel sheet, the mass layer becomes unnecessary, as in the case of the decarburized steel sheet, since there is no gaz to be removed.
What has just been mentioned for steel is equally valid in essence for copper.
The applications to consider for enamelled steel sheets carrying a printed circuit are numerous in the household appliances branch. Amongst Qthers coo]cers plates can be mentioned.
When the support is aluminium, a mass layer is no more necessary if an aluminium of the so-called ''enamelling'' - type is used.
Enamels have to be used which mel-t at a lower temperature since the melting point of alurminium is very low. Enamels will then be used wi-th a softening poin-t of about 460 C, the melting point of tlle ink enamel being then of about 480 C.
The expansion coefficient~ of aluminium being oE 240.10 7, a system will be used with two coating layers comprising a normal enamelling layer for aluminium, with a coefficient ~ =
185,10 7, and a thickness of about 15~um, and an insula-ting enamel ~i' layer wlth a coefficient /~ =180.10 7 and a thickness of abou-t 30 ,um, the latter beiny -the outer layer.
Aluminium exhibits a thermal conductibility higher than that of steel, and this ma]ces it interesting in a number of appLications.
The use of a glass sheet, of a borosilicate shee-t, or of a caramic sheet as support creates other problems as said materials are very insulating, very refractory and have expansion coefficients~ whlch are very Low, i.e. 32.10 7 in the case oE
Pyrex glass (registered trade-mark) and up to 8.10 7 in the case of ceramics.
In the case of Pyrex glass, a single layer will be used, formed of an enamel appropria-te for Pyrex glass, wi-th a coefficient A= 38.10 7. The evolution o~ t.he expansion coefficients is there-fore the reverse of that which is foreseen when the support is a metal,and it is glass which is in compression relative to the enamel.
As regards the selective application of the ink loaded with powdered metal onto the enamelled support, one may use the silk-screen process directly on the support, the pervious areas of the screen corresponding to the lay-out of the required printed circuit.
A more advantageous process consists however in making a transfer picture. For so.doing, a selective deposlt o~ the loaded ink is made on a tracing paper impregnated with starch, the deposit being carried out according to the silk-screen process.
After drying, at a temperature lower than 100 C, intended for fixing the drawing on the tracing paper, a continuous ~, film of varnish is appliecl above ~he ink The ink deposit is thereby trapped sanc1wich-like between the tracing paper and the varnish Eilln.
Ln orcler to provide trallsfer of: the inl; onto the sup-port, the tracing paper is removed by dipping it into water, the varnish Eilm playing thel- the role of support Eor the ink cleposlt, ancl the ink deposit is app1ied onto the support.
The matericll is thell baked. l`he varnish clisappears during bakiny through sublima-tion and there only remains the enamel loaded with the powdered metal which bonds together with the coating enamel oE the support.
This process offers the following advantages:
it provides the possibility of making deposits in areas which are not accessible with the direct silk-screen process, for instance at the ~ottom of a hollow support; it provides a regular deposit on bulging or irregular surfaces and it does away with the handling of the supports which was necessary with the direct silk-screen process.
Moreover, the method or process can be used for applying the enamel coating onto the support. In this case, it is enough to apply the enamel layer or layers onto the tracing paper and to dry tham without cooking them, then to provide the selective ink deposit on the dry coating and to proceed thereaEter as previously. The cookillg of the enamel load~d wi-th metal powder is carried out at the same time as the cooking of the enamel coating of the support, which consi-derably simplifies the operations.
EXAMPLE
Manufacture of a heated eatlnq plate a) Enamelling of the metal sheet ~Fig. 1) An eating plate made of a steel sheet 1 of the enamel-' r5-~ - 7 -' 1~38~
ling typet with a low carbon content and a thickness of 1,2 mm, is degreasec1 in a trichloroethylelle bath.
A first layer 2 oE 15C ~l in thickness ol-` refractory white~ made OIA a Erit at l.00 ~ COntailillg clay as suspensio agellt in tl-e l~roport:ion oE 4,5 ~ and sodiulm llitrate as electrolyte in the propor~ion oE 0,3 ~ is apuliecl by sprayiny Wittl a spray c~un according to the wet process.
The plate :i.5 clryecl at S0CC for 10 minutes and heated in a continuous enamel baking oven at 850C for 5 minutes.
Using the same process, a layer 3 of 300 ~l in the thick-ness of MAJOLIQUE enamel (a product of the "Procédés Ferro"
Company) containing also cla~ and sodium nitrate in the same proportions and a metallic oxide as eolorant in the proportion of l,5 ~ i.s appliecl accordiny ~o the same process. It is then dried at 80C and the baking is carried out under the same conditions as for -the first layer 2.
b) Deposit oE the drawing on the metal sheet.
A mixture is being preparecl which is composed of 80 % of niekel prismatie particles of a size oE 2 - 5,um, and of 20 %
of enamel frit with an expansion coefEicient ~ of 70.10 7, the mixture being kneaded with a screen-silk oil and a silk- - -screen solvent with a boiling point of about 100C. ~A com-pound is thereby obtained which is applied by the silk-screen process onto a transfer pict~re blotting paper 5 r according to the lay-out of the required circuit (Fig. 2).
The solvent is evaporated by heating at 100C and a film 6 of plas-tic material curing at 100C is applied again with the silk-screen process on the whole surface of the paper 5 over the compound 4, and the material is then heated between 100 and 120C for hardening the plastic film 6 (Fig.
3).
~3~
The paper tlIus coa~ed is dipped on to water :[.or removing the blotting paper 5 ~rom the plastic ~ilm 6 and from the compound 'I, and then the circuit is laid, on the side of the compound ~, on tIle enamellecI si.de o the eatincJ plate by expe~.ling the water stil:L tI:apped betweeIl the Eil.m 6 and the eircui.t ~ (F.ic~. ~I).
A dryin~3 operat:i.on :is carried out at 90C for 10 m:inutes, then a baki.Il(3 oL~erat.ioIl at ~5~ C foL 5 ~llillutes. The plastic filrn 6 is sublimatecI anc~ the lay-out oE the circuit 4 is integrated into the enamel 3 of the metal sheet.
c) Realization of the eircuit.
~ mechanical activation of the surface of the metal sheet is carried out for laying bal.e the nic~el particles 4 embedded into the enamel 3 (Fig. 5). For so doing, the metal sheet is subjected to a micro sand blasting using the wet process (water-blast) by utili~ing awater and silica bath containing 30 parts of silica by.weight for 100 parts of water. The water--blast is carried out at a projection distance o~ 20 cm and an air pressure of 3 bar.
The eating plate is then immersed into a hyclrochloric bath foL chemical ac-tivation~ then rinsed, then dipped finally into a chemical nickel bath of the Shipley type~ A heating circuit 7 deposited on.an enamelled steel sheet 1-3 is thereby obtained ~Fig. 6).
A pl.ocess i.s a:l.ready knowll~ cl.i.sc:losecl in [).S. l?ateut No 3,~2~,256, iss~ c~ b~ 9~r~ lV.il~(3 1~ .LI1VC!I~ L S~ e, wllerc~:in a :I.avel: o:f^`l~oll conduct.ing .inl; :I.oadecl with a ~)owcler o~
me~al, a1.1oy or nleta:Ll:i.c: cler:i.vat:i.vc! .i.; appli.ed oll the support, thell heatecl in orcler to hardell the inlc, t.he ~urface oE the ink la~er be:i.lly treatecl so as to lay t~e parL-.i.cles for.rning sa:id powcler bare, and the support thus coated is immersedinto a bath contaillin(3, in the form o~ particles, the conclucting metal to be depositecl/ under conditions wh:ich are known per se anct such that said conducting rnetal. partlcles are c1eposited 011 the powcler parti.cles laid bare.
In the usual ways of performing this process, a glass and ;~
resin laminate is used as insulating support, the resin being a -thermostable resin sueh as s:ilicone orpolyimide, and the ink being also a therrno-s-table resin such as silicone or polyimide.
The use of plastic materials for the support limits how-2G ever the opera.ting temperatures of the circuit obtained and its resistanee to ageing. :
Moreover, it is desi.rable to be able to form printed cir-euits, resisting or not, on supports currently used in the :
branch of electric household appliances such as on steel or aluminium sheets r glass, etc.
According to the present invention, there is provided amethod of manufaeturing a pattern of eleetroeonductive metal deposited on an enamel.ed substrate~ which comprises applylng an ink composition to the enameled-substrate in accordance wi.th the pattern, the ink composition comprising a second enamel and a metal-eontaining powder reeeptive to eleetroless plating, the second enamel having a melting point no greater than the soften-ing point of the enamel of the enameled substrate and the metal-~3~LU
containing powder being p~esen~ in an amount ~;uEicient to pro-vide Erom 60 to 90~ by weight~o~ the ink cOMpositiOn after balcing; baking the composi~ion; treating the baked composition so as to expose partLc1ec ol: the meta:L containing powder; and sllbjectil~tJ the l)aked, e~posec~ compositiorl to elc~ctroless platiny.
T~lc ~Ise o an enalnel Eor Eorminy the inlc permits usiny as support ellamc:lled metal:Lic sheets or glasses or ~rlamelled cera-mics. Said supports exhiblt the ac1vantaye ot having a robust-ness, a resistance to ageing and a thermal stability which are obviously very hiyh.
The deposit of the conductillg metal is preferably carried out according to the so-called "electroless" chemical deposi-t process which is not using electricity.
The proportion of powdered metal in the inlc, after baking the enamel, is advantageously comprised between 60 and 90~ by weight, the proportioll of enamel being -then oE 10 - 40% by weight.
A high proportion of powdered metal is in Eact necessary for reaching a high density of the metallic particles said high density favouring a uniform deposit oE the conducting metal.
This high proportion, and the density generally high of the metals, lead to the fact that the outer layer of the sup-port coating has to have a softening point of the same order preferably slightly superior to the melting point of the ink enamel. In fact if the coating was getting soft in a notable manner while the ink was being baked, the powdered metal would penetrate into the coating and cause cracks, and the electrical insulation characteristics of the coatiny would be seriously impaired.
As reyards the carrier, an oil which is habitually used to this effect is employed, in a proportion such that the ink obtained is in the form oE a fluid compound usable with .
" ~3~3~3 the sil~-screen proce~s. This proportion depends on the specific surface of the powdered metal uqed, a high speci~lc surface requiring a large quantity o~ oil.
The powdered metal must exhibit a relatively high resis-tivity qo a~ not to modify the electrical characteri~tics o~ the ~inal. prlnted circui$. On the other hand, the metal o~ ~id powder has to be chosen such that the depo~it of oonducting metal through the "el~ctroless" proces~ i~
carried out ~Ider the mo3t favourable conditions~ In principle, a metal is chosen who~e electrolitlc potential E
is high relative to that of the conducting ~etalO ~owever, one may al~o use the same metal a~ the conducting metal, notably ln the case of nickel, A~ examples o~ powdered metals, o~e can mention in particular the powders of cobalt-nickel or iron, wlth particle size comprised between 1 and 10 ym.
Preferably, partiole~ of spongy or angular shape will be used~ since ~uc~ shape~ provide a good mutual bonding of the particles which provides them with a better resistance to the treatment neces~ary for laying the particles bare, oarried out through sand blasting, brushin~ or chemical attack. Moreover, said particle ~hapes favour the obtentio~
of a high den~ity ~hich, as has been seen, i~ advantageousc The conducting metal chosen for making the printed circult i9 selected of cour~e in relation with the conai-dered applicationO I~ the circuit has to ha~e a high re-.sistance, and is intended for u~e in heating, a hlgh re-sistivity metal will be chosen ~uch as nickelO I~ on the contrary a lo~ resistance circuit is required, intended for instance fsr establi~hing connections, a lo~ con-ductive metal will be chosen such as copper or silver.
The enamel coating applied on the support is of great importance since, further to its stanclarcl Eunetions of pro-teCtincJ the support alld giVinCJ it a yoocl appearanee, it has to permit the aclh~rellce o~ t~le inli layer and provicle the eleetrical lnsu1atioll betweell support alld prlntecl eircuit when the support ls ikselL eoncllle~ive.
OC course, the ellamel eoatillg is chosen primarily as a functioll of th~ support characteristics: meltin(3 point, thermal expansion eoefEicient, resistivity, surface state, ehemical nature.
A preferred embodiment will be deseribed hereinafter as an example having reference the attached drawings, wherein:
Figs. 1 to 6 illustrate differell-t steps of -the method of the present invelltioll.
The strueture and eharaeteristies of the enamel coating will is described hereinafter in the ease where the support is a steel (or eopper) sheet, an aluminum sheet, or a glass sheet ~or also a eeramie or a borosilieate sheet).
When the support is a normal steel sheet, a mass layer has 2n to be providecd with a very blistered strueture for easing the removal of gas from the sheet when being baked. Said mass being therefore little insulating, upper layers of very high resistivity have to be provided.
On the other har.d, the linear expansion coefficients have to decrease from the metal sheet to the eovering layer so that the eoating be in eompression relative to the sheet.
Sueh eonditions being taken into aeeount, there will be applied in suceession on the metal sheet, whieh has a linear expansion eoe~icient ~, measured between 20 and 320C, of 140.10 7, - a standard mass with a eoefficient ~= 100.10 7 and a - 4 ~
thicl~nc-ss o~ 10 to 12 ,um, - an insulal::in~J mass, ~irh a co~tEicien~ ~.= 85.10 7, and a thickness o~ 40 ,um, - an insu`l a tin~ coa t:in(3 enam~1 j wi th a coef ' ic~ en t .
, ,. , ~ .~
..
~ : - , .:
. . ~
:
' 3~
,~= 80.10 7 and a thic]cness between 100 and 150 ~m.
If a decarburized shee-t is used, one may advan-tageously omit -the first mass layer and apply only the insulating mass~and the covering enamel.
The man of the art wlll have no difficul-ty in selecting, considering the application in question, enamels having -the hereabove characteristics. It will be only mentioned that one can use as coa-ting enamel -the enamel sold under -the trademark MA~OLIQUl3 by the ''Procedes ~'erro'' Colnpany, with a softening point lylny between 600 and 650 C.
The enamel of the corresponding ink will have a melting point of the same order, that is of abou-t 600 C.
In the case of a stainless s-teel sheet, the mass layer becomes unnecessary, as in the case of the decarburized steel sheet, since there is no gaz to be removed.
What has just been mentioned for steel is equally valid in essence for copper.
The applications to consider for enamelled steel sheets carrying a printed circuit are numerous in the household appliances branch. Amongst Qthers coo]cers plates can be mentioned.
When the support is aluminium, a mass layer is no more necessary if an aluminium of the so-called ''enamelling'' - type is used.
Enamels have to be used which mel-t at a lower temperature since the melting point of alurminium is very low. Enamels will then be used wi-th a softening poin-t of about 460 C, the melting point of tlle ink enamel being then of about 480 C.
The expansion coefficient~ of aluminium being oE 240.10 7, a system will be used with two coating layers comprising a normal enamelling layer for aluminium, with a coefficient ~ =
185,10 7, and a thickness of about 15~um, and an insula-ting enamel ~i' layer wlth a coefficient /~ =180.10 7 and a thickness of abou-t 30 ,um, the latter beiny -the outer layer.
Aluminium exhibits a thermal conductibility higher than that of steel, and this ma]ces it interesting in a number of appLications.
The use of a glass sheet, of a borosilicate shee-t, or of a caramic sheet as support creates other problems as said materials are very insulating, very refractory and have expansion coefficients~ whlch are very Low, i.e. 32.10 7 in the case oE
Pyrex glass (registered trade-mark) and up to 8.10 7 in the case of ceramics.
In the case of Pyrex glass, a single layer will be used, formed of an enamel appropria-te for Pyrex glass, wi-th a coefficient A= 38.10 7. The evolution o~ t.he expansion coefficients is there-fore the reverse of that which is foreseen when the support is a metal,and it is glass which is in compression relative to the enamel.
As regards the selective application of the ink loaded with powdered metal onto the enamelled support, one may use the silk-screen process directly on the support, the pervious areas of the screen corresponding to the lay-out of the required printed circuit.
A more advantageous process consists however in making a transfer picture. For so.doing, a selective deposlt o~ the loaded ink is made on a tracing paper impregnated with starch, the deposit being carried out according to the silk-screen process.
After drying, at a temperature lower than 100 C, intended for fixing the drawing on the tracing paper, a continuous ~, film of varnish is appliecl above ~he ink The ink deposit is thereby trapped sanc1wich-like between the tracing paper and the varnish Eilln.
Ln orcler to provide trallsfer of: the inl; onto the sup-port, the tracing paper is removed by dipping it into water, the varnish Eilm playing thel- the role of support Eor the ink cleposlt, ancl the ink deposit is app1ied onto the support.
The matericll is thell baked. l`he varnish clisappears during bakiny through sublima-tion and there only remains the enamel loaded with the powdered metal which bonds together with the coating enamel oE the support.
This process offers the following advantages:
it provides the possibility of making deposits in areas which are not accessible with the direct silk-screen process, for instance at the ~ottom of a hollow support; it provides a regular deposit on bulging or irregular surfaces and it does away with the handling of the supports which was necessary with the direct silk-screen process.
Moreover, the method or process can be used for applying the enamel coating onto the support. In this case, it is enough to apply the enamel layer or layers onto the tracing paper and to dry tham without cooking them, then to provide the selective ink deposit on the dry coating and to proceed thereaEter as previously. The cookillg of the enamel load~d wi-th metal powder is carried out at the same time as the cooking of the enamel coating of the support, which consi-derably simplifies the operations.
EXAMPLE
Manufacture of a heated eatlnq plate a) Enamelling of the metal sheet ~Fig. 1) An eating plate made of a steel sheet 1 of the enamel-' r5-~ - 7 -' 1~38~
ling typet with a low carbon content and a thickness of 1,2 mm, is degreasec1 in a trichloroethylelle bath.
A first layer 2 oE 15C ~l in thickness ol-` refractory white~ made OIA a Erit at l.00 ~ COntailillg clay as suspensio agellt in tl-e l~roport:ion oE 4,5 ~ and sodiulm llitrate as electrolyte in the propor~ion oE 0,3 ~ is apuliecl by sprayiny Wittl a spray c~un according to the wet process.
The plate :i.5 clryecl at S0CC for 10 minutes and heated in a continuous enamel baking oven at 850C for 5 minutes.
Using the same process, a layer 3 of 300 ~l in the thick-ness of MAJOLIQUE enamel (a product of the "Procédés Ferro"
Company) containing also cla~ and sodium nitrate in the same proportions and a metallic oxide as eolorant in the proportion of l,5 ~ i.s appliecl accordiny ~o the same process. It is then dried at 80C and the baking is carried out under the same conditions as for -the first layer 2.
b) Deposit oE the drawing on the metal sheet.
A mixture is being preparecl which is composed of 80 % of niekel prismatie particles of a size oE 2 - 5,um, and of 20 %
of enamel frit with an expansion coefEicient ~ of 70.10 7, the mixture being kneaded with a screen-silk oil and a silk- - -screen solvent with a boiling point of about 100C. ~A com-pound is thereby obtained which is applied by the silk-screen process onto a transfer pict~re blotting paper 5 r according to the lay-out of the required circuit (Fig. 2).
The solvent is evaporated by heating at 100C and a film 6 of plas-tic material curing at 100C is applied again with the silk-screen process on the whole surface of the paper 5 over the compound 4, and the material is then heated between 100 and 120C for hardening the plastic film 6 (Fig.
3).
~3~
The paper tlIus coa~ed is dipped on to water :[.or removing the blotting paper 5 ~rom the plastic ~ilm 6 and from the compound 'I, and then the circuit is laid, on the side of the compound ~, on tIle enamellecI si.de o the eatincJ plate by expe~.ling the water stil:L tI:apped betweeIl the Eil.m 6 and the eircui.t ~ (F.ic~. ~I).
A dryin~3 operat:i.on :is carried out at 90C for 10 m:inutes, then a baki.Il(3 oL~erat.ioIl at ~5~ C foL 5 ~llillutes. The plastic filrn 6 is sublimatecI anc~ the lay-out oE the circuit 4 is integrated into the enamel 3 of the metal sheet.
c) Realization of the eircuit.
~ mechanical activation of the surface of the metal sheet is carried out for laying bal.e the nic~el particles 4 embedded into the enamel 3 (Fig. 5). For so doing, the metal sheet is subjected to a micro sand blasting using the wet process (water-blast) by utili~ing awater and silica bath containing 30 parts of silica by.weight for 100 parts of water. The water--blast is carried out at a projection distance o~ 20 cm and an air pressure of 3 bar.
The eating plate is then immersed into a hyclrochloric bath foL chemical ac-tivation~ then rinsed, then dipped finally into a chemical nickel bath of the Shipley type~ A heating circuit 7 deposited on.an enamelled steel sheet 1-3 is thereby obtained ~Fig. 6).
Claims (5)
1. A method of manufacturing a pattern of electrocon-ductive metal deposited on an enameled substrate which com-prises applying an ink composition to said enameled substrate in accordance with said pattern, said ink composition com-prising a second enamel and a metal-containing powder recep-tive to electroless plating, said second enamel having a melting point no greater than the softening point of the enamel of said enameled substrate and said metal- containing powder being enameled substrate and said metal- containing powder 90 % by weight of said ink composition after baking; baking said composition; treating said baked composition so as to expose particles of said metal containing powder; and sub-jecting the baked, exposed composition th electroless plating.
2. The method according to claim 1 wherein the metal-containing powder is nickel-cobalt or iron.
3. The method according to claim 1 wherein the particles of powder are of a spongy or angular shape.
4. A method of manufacturing a pattern of electrocon-ductive metal deposited on an enameled substrate which comprises applying an ink composition to a water disintegrable surface in accordance with said pattern, said composition comprising a second enamel and a metal-containing powder receptive to electroless plating, said second enamel having a melting point no greater than the softening point of the enamel on said sub-strate and said metal-containing powder being present in an amount sufficient to provide from 60 to 90 % by weight of said composition after baking; drying said ink composition, coating said dried composition and said water disintegrable surface with a sublimable varnish film; disintegrating said water disintegrable surface whereby said dried composition remains on said film; applying said film to said enameled substrate;
baking said enameled substrate with the applied film whereby said film sublimes; treating said baked composition so as to expose particles of said metal-containing powder; and subjecting the baked exposed composition to electroless plating.
baking said enameled substrate with the applied film whereby said film sublimes; treating said baked composition so as to expose particles of said metal-containing powder; and subjecting the baked exposed composition to electroless plating.
5. A method of manufacturing a pattern of electrocon-ductive metal deposited on an enameled substrate which com-prises applying a first enamel on a water disintegrable surface to provide a first enameled coating; applying an ink compo-sition to said enameled coating in accordance with said pattern, said ink composition comprising a second enamel and a metal-containing powder receptive to electroless plating, said second enamel having a melting point no greater than the soften-ing point of said first enamel and said metal-containing powder being present in amount sufficient to provide from 60 to 90 % by weight of said composition after baking; drying said ink composition; coating said ink composition and said first enameled coating with a sublimable varnish film; dis-integrating said water disintegrable surface thereby leaving a laminate of said first enameled coating, said ink composi-tion and said film; applying said laminate to an unenameled substrate; baking said substrate and laminate; treating said baked composition so as to expose particles of said metal-containing powder; and subjecting the baked, exposed compo-sition to electroless plating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA297,857A CA1103810A (en) | 1978-02-28 | 1978-02-28 | Process for depositing a conducting metal layer on an insulating support |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA297,857A CA1103810A (en) | 1978-02-28 | 1978-02-28 | Process for depositing a conducting metal layer on an insulating support |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1103810A true CA1103810A (en) | 1981-06-23 |
Family
ID=4110875
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA297,857A Expired CA1103810A (en) | 1978-02-28 | 1978-02-28 | Process for depositing a conducting metal layer on an insulating support |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1103810A (en) |
-
1978
- 1978-02-28 CA CA297,857A patent/CA1103810A/en not_active Expired
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