CN1633521A - Precious metal recovery - Google Patents
Precious metal recovery Download PDFInfo
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- CN1633521A CN1633521A CNA028188861A CN02818886A CN1633521A CN 1633521 A CN1633521 A CN 1633521A CN A028188861 A CNA028188861 A CN A028188861A CN 02818886 A CN02818886 A CN 02818886A CN 1633521 A CN1633521 A CN 1633521A
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- liquid
- ceramic membrane
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- palladium
- solution
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1617—Purification and regeneration of coating baths
Abstract
Various methods have been proposed to separate precious metal from a fluid utilized for plating. The known methods and devices are complicated and expensive. To overcome this problem, a method and a device for plating work pieces with a fluid containing at least one precious metal are provided. According to the invention the work pieces are contacted with the fluid and the fluid is filtered, after use, through at least one ceramic membrane filter in order to separate the at least one precious metal from the fluid. According to the invention a ceramic membrane filter having an exclusion pore size in excess of 10,000 Dalton is utilized.
Description
Technical field
The present invention relates to method and device that a kind of usefulness contains the liquid plating workpiece of precious metal.The present invention is specially adapted to produce the operation of circuit carrier.
When the plating workpiece, if conductive processing non-conductively then at first must be carried out to its surface in its surface.For this reason, the workpiece immersion is contained in the solution of ion, ionization or pallamine.More specifically, the form that ionic palladium can salt exists, Palladous chloride for example, and it is dissolved in the hydrochloric acid soln usually.The ionization palladium exists with complex form, for example the ammonium pyridine complex.Pallamine can contain multiple protective colloid, as protective colloid that is formed by tin chloride (II) or the protective colloid of being made up of organic polymer.The palladium that is adsorbed on workpiece surface as activator for example causing electroless metal deposition, thereby form one deck conductive layer from the teeth outwards, after this can electroplate any metal from the teeth outwards.Utilize this manufactured printed circuit board (PCB) and other circuit carriers and the metallizing part in sanitation, automobile and the furniture industry for example, for example chromium plating plastic cement part more specifically.
Contain palladium solution and also can be used for forming conductive layer.In described Direct Electroplating method, handle back other metals of electroplating deposition at palladium, and do not form metal level with no electric metal coating method in advance.
Have in the process of workpiece of non-conductive surfaces in processing, when formerly flooding workpiece and being taken out by solution, part contains palladium solution still attached on the workpiece.The solution that adheres to generally cleans with water.
Known activation method for example uses pallamine, the general solution that contains 50-400 mg/litre palladium that uses.When processing has one square metre the plastic cement part of geometric jacquard patterning unit surface, absorb the palladium of about 5-10 milligram usually.This amount is necessary for the activation on plastic cement surface.When pending workpiece left corresponding processing stand, about 0.2 liter/square metre activated solution was taken away and is still stayed on the workpiece surface from bathe.Therefore, bathed because the solution that adheres to takes out of processing, cause the palladium of about 10-50 milligram to lose to body lotion, these solution are washed and are transferred to off the wastewater treatment operation afterwards.
Do not have the electric metal plating to the Direct Electroplating of Nonconductor surface in also can utilize and contain palladium solution.In these situations, need the palladium (as 400 mg/litre) of high density in the solution.
When adopting known direct metal solution and coating method, the amount of the palladium of being taken away by process solutions is about 50 milligrams/square metre.50 milligrams of/square metre workpiece surface that the palladium particle that absorbs by pursue the proper method (as absorb the polyelectrolyte compound in advance on Nonconductor surface) can be increased to by extremely low value.Even so, the palladium that is used for the 60-70% of solution loses because of taking out of.Has only the actual metal lining of 40-30% as workpiece surface.
The known example that reclaims palladium by process solutions.As United States Patent (USP) the 4th, 078, No. 918 a kind of recovery method has been described, as by reclaiming palladium in the multiple material that contains dissolving or non-dissolved palladium.At first with the described material of oxidizer treatment to destroy possible organic constituent, handle to form amine complex with ammonium hydroxide then.Then the palladium complex that will so obtain reduces with xitix, with palladium by in the working fluid with metallic forms deposition and can filter.
In addition, at Chemical Abstracts, described in 1990:462908 HCAPLUS " reclaiming palladium " (" Reclamation of Palladium from colloidal seedersolutions ") by colloidal state kind solution a kind of before no electric metal plating by colloidal state Pd/SnCl
2In reclaim palladium as pretreated method, wherein in solution blowing air 24 hours so that the palladium flocculation.With settling separation, dry and further processing.
At Chemical Abstracts, in 1985:580341 HCAPLUS " reclaiming palladium and tin chloride " a kind of method by adding metallic tin precipitation palladium at 90 ℃ has been described by the waste liquid of pallamine in tin chloride.
United States Patent (USP) the 4th, 435 has disclosed for No. 258 from being used for activating subsequently the other method that body lotion reclaims palladium that exhausts as the non-conductive surfaces of no electric metal solution and coating method.As follows described activation solution is reprocessed: add oxygenant (as hydrogen peroxide) pallamine is oxidized to solution, postheating solution destroys residual hydrogen peroxide, then with the palladium galvanic deposit in this solution to negative electrode.
At Chemical Abstracts, in 1976:481575 HCAPLUS " being used for the recovery of the activation solution waste liquid pallamine of no current metal coated resin surface ", described a kind of at last by Pd/SnCl
2Obtain the method for palladium, wherein palladium is by adding the concentrated nitric acid precipitation and filtering.
DE 100 24 239 C1 have described a kind of by workpiece contact method with palladium colloidal solution plating workpiece with colloidal solution, and root palladium is accordingly afterwards isolated the palladium colloidal solid by film filter in by colloidal solution in the colloidal solution use and reclaimed palladium.Can use the material of for example making to filter by pottery.The evacuation aperture of film is of a size of 200 to 10,000 dalton.Wherein mention, when the evacuation aperture size of film exceeded 10,000 dalton, the palladium particle can pass through film filter.
Use the art methods of palladium colloidal solution plating workpiece complicated and expensive.
The basic problem that the present invention faced is the shortcoming that overcomes currently known methods, and finds out with contain the liquid plating workpiece of at least a precious metal and the method that can carry out under low cost.Use described method should only need to add a spot of pharmaceutical chemicals.In addition, described method power consumption seldom need the time also very short, and maintenance requirement is low especially.
This problem has obtained overcoming by the method for claim 1 and the device of claim 15.The preferred embodiments of the invention provide in appended claims.
The method according to this invention is with liquid plating workpiece, and described liquid contains at least a precious metal, and this method comprises workpiece is contacted with liquid.In order from liquid, to reclaim precious metal, after with described liquid plating workpiece, described liquid is filtered by at least a ceramic membrane filter device, separate precious metal from liquid, the evacuation aperture size of ceramic membrane filter device surpasses 10,000 dalton.By filtering precious metal is separated from liquid.
Plating refers to the processing that use that liquid carries out any is intended to change the surface of workpiece, and described liquid must contain precious metal.Do not comprise method therein with the method, particularly enamel ccating of polymeric coating coating workpiece.
Workpiece to be plated comprises metal works, non-metal workpiece and the workpiece of being made up of metal and non-metallic material.Described workpiece can have all conceivable forms and can be used as all conceivable purposes.Preferred workpiece is the work in-process that are used to produce circuit carrier, produces printed circuit board (PCB) and hybrid circuit carrier more specifically, as polycrystalline sheet module.
Can by the precious metal of separating in the corresponding liquid all elements of the 1st and group VIII of the periodic table of elements, i.e. particularly Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag and Au.The present invention preferably relates to by using and contains the method that palladium liquid plating is handled workpiece.
More particularly, described liquid can be solution.It is especially true when precious metal exists with ion or ionized form.For the precious metal of ionic species, more specifically be meant to be dissolved in the water or to be dissolved in the precious metal salt that promotes in this another solvent of salt dissociative.Precious metal for ionized form refers to noble metal complexes, has the noble metal complexes of machine complex coordination base more specifically.Described complex compound can neutral or is existed with ionic species.Described liquid can exist by colloidal form, particularly the colloid of simple substance precious metal.
The liquid that contains precious metal can be working fluid or the scavenging solution of handling workpiece.Working liquids refers to the liquid that changes workpiece surface character, as coating fluid, comprises activation solution, scavenging solution, etching solution or analogue.Contrast with it, the effect of scavenging solution only is: remove still the working fluid attached to workpiece surface after handling workpiece with working fluid.
After using described liquid plating workpiece, filter precious metal by at least one ceramic membrane filter device.In other words, at first described liquid is used for the plating workpiece, filtration subsequently only is the precious metal that wherein contains in order to reclaim.Described liquid can be collected by the workpiece dripping by for example spraying, spray, flood or mode such as explosion being come contact workpiece, at once it is handled with film filter then.Yet the liquid of collecting also can at first be stayed in the storage tanks, sends workpiece thus back to.In the case, liquid can be imported film filter (interruption method) after collecting for some time, or partially liq is shunted out and be transferred to film filter (continuous processing) continuously by storage tanks.In this case, be in stable full state in order to make storage tanks, the amount that keeps introducing the fresh working fluid of storage tanks in the unit time equals the interior amount of passing through the liquid of film filter of unit time.Also can described workpiece be contacted with working fluid by described workpiece is immersed in the processing vessel that fills working fluid.In this case, the exhausted working fluid can be imported film filter (interruption method) after collecting for some time, or partially liq is shunted out and be transferred to film filter (continuous processing) continuously by storage tanks.
Of the present invention method is simple, and its chemical cost and energy expenditure are all very little, save time, also very low to the requirement of safeguarding, uses the inventive method to isolate precious metal continuously from the working fluid waste liquid.More particularly it allows after isolating the part that contains palladium, and with the regeneration of exhausted working fluid, all like this palladiums are capable of circulation to treatment process.
With Chemical Abstracts, describe among the 1990:462908 HCAPLUS from colloidal state Pd/SnCl
2The middle method that reclaims palladium is compared, the advantage of the inventive method is that the part that contains palladium is thoroughly told, yet the palladium that a part be can not ignore in the precipitator method of describing among the Chemical Abstracts is oxidized to divalent state (the solvable state of palladium), so palladium can not be fully by filtering by separating in the solution.Therefore, this part palladium can not reclaim and can lose.
The inventive method is better than Chemical Abstracts, and another advantage of the method that 1985:580341 HCAPLUS describes is not need to resemble in the currently known methods in order to heat colloidal solution to consume a large amount of other chemical (as metallic tin), energy and time desired.
The method according to this invention and United States Patent (USP) are compared also tangible advantage the 4th, 435, No. 258, palladium almost can remove from solution fully, yet according to United States Patent (USP) the 4th, 435, No. 258, only can reach extremely low current efficiency, particularly when palladium concentration is low (through after the long-term electrolysis).Therefore, it is very complicated or impossible at all using prior art to remove palladium fully.
With Chemical Abstracts, the method for describing among the 1976:481575 HCAPLUS is compared, and the method according to this invention and device are particularly suitable for operate continuously, and in addition, the method in described the disclosing must be used other pharmaceutical chemicals.
Mention among German Patent 100 24 239 C1; when the evacuation aperture size of film filter obviously surpasses 10; during 000 dalton; palladium particle in the pallamine colloidal solution can pass through strainer; surprisingly; the evacuation aperture size for example is that 20,000 daltonian porcelain filters still have excellent separation performance to pallamine in the present invention.About this point, the test 1 and 2 of reference example 1.
The method according to this invention is compared with known method and apparatus with device has following advantage:
A. can only use a device from ion, ionization and colloidal solution, to reclaim precious metal (particularly palladium).It does not need to use several devices that match.As a result, solution can mix before regeneration and collect.This is equally applicable to working fluid and scavenging solution: contain high density precious metal working fluid can with the cleaning liquid-phase mixing of the precious metal that contains extremely low concentration, afterwards together processing.
B. because the ceramic membrane filter device that can be suitable for macropore comes successfully separate precious metal, so can adopt the ceramic membrane filter device that pharmaceutical chemicals and temperature effective is had better patience.Because strainer does not need frequent cleaning, maintenance requirement reduces greatly.The ceramic membrane filter device also has the long life.In addition, precious metal does not adsorb on mould material.
C. the reprocessing of pending liquid is simple.For example, it need not carry out under protective atmosphere to prevent that colloidal particles is dissolved in the liquid.
Colloidal state activator based on palladium comprises the palladium particle that protected coating (protection glue) centers on.Use the detection of high resolution transmission electron microscopy (HTEM) and atomic force microscope (AFM) to show that palladium particulate diameter is at least 2.5nm.Average particulate diameter is 4nm, and is consistent with the particulate Gaussian distribution.By detecting, find from overall dimension 18nm particle to more short grained wide particle size distribution (2 to 18nm) with the scavenging solution that obtains behind the colloidal state Treatment with activating agent workpiece.
In actual applications, colloidal solution is tart (often containing a large amount of hydrochloric acid), contains chlorion, and may also contain tin ((II) and (IV)) or organic, the polymer stabilizer (as gelatin or polyvinyl pyrrolidone) and the reductive agent of oxidation state.Except polymkeric substance (consumption is little), be ionic at this contained every other material.Assert that these ion components are more much smaller than palladium particle.
Surprisingly, though (tin (generally surpass palladium concentration 70 times) that promptly contains high density simultaneously) and known tin compound form and be difficult for filtering colloidal solution under the situation of stanniferous colloidal solution, the suitable membrane strainer that the palladium particle still can comprise the different aperture degree by use is selectivity and fully removing from these colloidal solution very.
For ultra-filtration, the multiple film that is made of a variety of materials is tested.Importantly selected film filter was enough stable to the liquid that contains precious metal when test was presented at the selective membrane strainer, can contain for example hydrochloric acid of 15 weight % in the described liquid.
For the separate palladium colloidal solid, can utilize the evacuation aperture size to be about 15,000 dalton is to about 25,000 daltonian ceramic membrane filter device, preferred evacuation aperture size is about 17,500 dalton to about 22,500 daltonian ceramic membrane filter devices, and it is the most preferred to be about 20,000 daltonian ceramic membrane filter devices with the evacuation aperture size.
Preferred used ceramic membrane filter device is by salic (α-Al particularly
2O
3), titanium dioxide and the possible white stupalith of titanium dioxide make.In theory, also can use other filter materials.Usually, filter material is deposited on for strainer and provides on the highly porous supporter of required mechanical stability.Described supporter can be by for example α-Al
2O
3Or SiC (silicon carbide) forms.
Filter profile can be dish type or tubulose.In first kind of situation, liquid flow is directed to described dish, is basically perpendicular to its surface, and described liquid flow breaks away from along radial direction.Between two panel surface, there is pressure reduction, should dish so penetrating fluid is permeable.If strainer be shaped as tubulose, liquid transports vertically by this pipe, has pressure between the interior space of pipe and the external space.As a result, a penetrating fluid permeable tube ancient piece of jade, round, flat and with a hole in its centre is as entering the external space of pipe from the interior space of pipe.This in second method be called dynamic filtration.In this case, precious metal is retained in the interior space of pipe, and the liquid that is substantially free of precious metal is infiltrated into the external space of pipe by the interior space of pipe through tube wall.
But some fluid direct filtration do not need any extra pre-treatment.In this case, use the ceramic membrane filter device to obtain fabulous result.
In some cases, the fluid of at first needs being reprocessed carries out Chemical Pretreatment.For this reason, doing the plating use after before the film filter filtration, described liquid is mixed with suitable chemical substance with the wherein contained at least a precious metal of change, thereby this precious metal is stayed when filtering basically fully.Suppose that change has taken place the granular size of precious metal by adding these chemical substances so that contain the particle of precious metal can not be again hole by film filter.For this reason, it should be enough to adjust mean particle size to the value that surpasses about 10nm when granular size meets Gaussian distribution.In this case, the evacuation aperture size can be stayed most precious metal in the concentrated solution above 10,000 daltonian film filters.Therefore when making the film filter of the big evacuation aperture size of apparatus, can prepare bigger particle by adding these chemical substances.
If palladium exists in solution with ion and/or ionized form, described liquid can mix with the chemical substance that is selected from reductive agent, sulphur compound, selenium compound and hoof compound.The chemical substance that pre-treatment is used is preferably selected from dimethyl dithiocarbamate, sulfide, hydroborons (as tetraphydro-borate) and the hypophosphite of hydroborons, amine borine, hypophosphite, inorganic sulphide and organosulfur compound, particularly basic metal and ammonium.Described organosulfur compound more specifically wherein sulfide linkage knot form the organic compound of singly-bound or two keys to one or two carbon atoms, i.e. for example mercaptan, sulfide, disulphide and polysulfide, sulphamide and thioaldehydes.
If palladium is present in the liquid with colloidal form, use the pH regulator agent as described chemical substance, with fluid and pH regulator agent so that the pH scope is 3 to 12.
In above-mentioned two kinds of situations, all obtain being fit to very much the solution of separate precious metal, be separate palladium at this.
Following advantage is from improvement of the present invention:
A. pre-treatment is very simple.Its liquid that is enough to contain precious metal mixes mutually with the material that requires or with the pH regulator agent respectively.
B. consume other few pharmaceutical chemicals.In order to process, only need 7.5 milliliters the solution that contains 467 grams per liter Sodium dimethyldithiocarbamate 40mins by handling 200 liters of rinse water (palladiums of 7 mg/litre) that the organic palladium complex compound is produced.If desire processing is by handling the rinse water that palladium colloid (organic protective colloid, 25 mg/litre Pd) produces, as long as the NaOH aqueous solution of 0.5 liter 432 grams per liters is just enough.
It is feasible reclaiming precious metal by film filter from scavenging solution and/or working fluid as can be known by main observation of the present invention of product and test.For this reason
A, workpiece is contacted with containing the palladium working fluid,
B, then, with still remove with scavenging solution attached to the working fluid of workpiece surface and
C, at least one filters the ceramic membrane filter device of usefulness by (preferably under pressure) with working fluid and/or scavenging solution, liquid by described at least one ceramic membrane filter device is penetrating fluid, and the liquid by described at least one ceramic membrane filter device is not concentrated solution.
With after containing the palladium liquid treatment, in suitable device by workpiece (preferably being made by non-conducting material) being immersed in the scavenging solution, flooding or preferably scavenging solution is sprayed onto on the described workpiece to keep the scavenging solution volume of trying one's best little with scavenging solution.Then, scavenging solution is passed through the ceramic membrane filter device by pressure pump, described strainer stays the palladium particle and allows scavenging solution pass through.Then, described penetrating fluid is transferred to the wastewater treatment operation.
Before handling with film filter, working fluid and/or scavenging solution can mix mutually with chemical substance (as reductive agent, sulphur compound, selenium compound, tellurium compound or pH regulator agent).
In particularly preferred embodiment of the present invention, only scavenging solution or the preferred scavenging solution that contains the working fluid of 5 volume % are at most handled with film filter (preferably under pressure).Workpiece is contacted with fresh cleaning solution, provide fresh scavenging solution with the predetermined amount in the unit time continuously.More preferably the amount of the penetrating fluid that forms in the unit time can tune to the amount that approximates the scavenging solution that contacts with workpiece in the unit time.As a result, in processing units, reach quiescent conditions: be transported to workpiece fresh cleaning solution amount just in time with by the device effusive penetrating fluid amount identical, thereby obtain stable logistics.Certainly, only can ignore and not have under other the situation of influence factor in the amount of the chemical substance that is added, such state could be realized.In fact, the evaporation of scavenging solution can become an integral part.
Concentrated solution form with the homodisperse liquid of metal or metallic compound exists the palladium that stays of (as with the PdS dispersion liquid) recyclable.The palladium that stays can be for example dissolved, be transformed into Palladous chloride and be used to synthetic new containing the palladium working fluid or be used as other purposes.Containing the palladium concentrated solution also can be concentrated into intimate dry in pressure filter., will import from the concentrated solution of film filter in the container, the palladium slurries that contain that form in the concentration process deposit in described container for this reason, and gained suspension slurries are imported into pressure filter.The palladium filter cake that contains that is obtained by pressure filter can be used as the base-material of making pure palladium and palladium compound.
Come in the equipment of plating workpiece at least a liquid that contains precious metal of usefulness according to the present invention, provide the device that described workpiece is contacted with liquid and the device of the described workpiece of clamping usually.
The device that described workpiece is contacted with liquid for example can be that working fluid or scavenging solution are sprayed, spray, flood or be released into shower nozzle on the workpiece surface.For example requiring liquid to reach described surface or when the amount of required liquid need minimize, often need such setting with high flow rate.In another embodiment of the present invention, used contact device is the processing vessel that fills working fluid, and workpiece is immersed wherein.
The device of holding workpiece is various ways also: for example workpiece can come clamping with clamp, screw clamp, fire tongs or screw fixed traditional way.In addition, workpiece also can be simply on roller, wheel or cylinder or be clipped in therebetween, with level attitude clamping, conveying and processing.
Except aforementioned feature, described equipment also comprises the facility of separating at least one precious metal from liquid.This facility comprises that at least one evacuation aperture size surpasses 10,000 daltonian ceramic membranes.This facility also comprises at least one pump that described liquid is delivered to described at least one ceramic membrane and the fluid conduits that described liquid is guided to described at least one ceramic membrane by the device that described workpiece is contacted with liquid.Described pump also can be anyly not use the pump of motor or only by the pump of gravity feed of fluid.
According to the explanation that provides above, the facility of separate precious metal also provides the mixing facility from liquid.Mix in the facility at this, can mix with chemical substance with the liquid of workpiece contact device from liquid.For this reason, can utilize any known conventional hybrid facility in the chemical reaction technology, as stirring the mixing zone in facility and the fluid reactor.
In addition, the facility of separate precious metal also provides heterogeneous separating unit from liquid, and in this unit, the slurries that produce in the sepn process and isolate the facility of described at least a precious metal in described liquid can carry out sedimentation.This type of heterogeneous separating unit is for example formed by settling bowl, does not wherein have liquid convection to take place basically.Described suspension slurries can be imported pressure filter then with significantly purifying and the dry slurries that mainly contain precious metal.
The invention will be further described below in conjunction with accompanying drawing.More specifically,
Fig. 1: be the perspective diagram of ceramic membrane filter device;
Fig. 2: be the synoptic diagram of workpiece plater according to the present invention.
Fig. 1 describes the purpose ceramic-film filter of pipe 1 form. The stay pipe 3 that described pipe uses highly porous ceramic material to make is aluminium oxide as used herein. Provide another oxide ceramic layer as film filter layer 2 in the inboard of stay pipe 3. Described film filter layer 2 is not made up of two layers (clearly showing) successively, namely by α-Al2O
3The first microfiltration layer of making and by ZrO2And TiO2That makes second surpasses filtering layer, TiO2Hole dimension very little, for for example 20,000 daltonian evacuation aperture sizes, filter still feasible like this. The evacuation aperture size of film filter layer 2 is about 20,000 dalton. Therefore, average cell size is about 20nm.
The internal diameter of pipe is about 6 millimeters. Pipe range is about 1000 millimeters. Fluid flows along the direction of mark 4 under the pressure. Differential pressure range between the entrance of pipe and outlet is 1.5 to 3 bar.
In order to collect the penetrating fluid by inside pipe wall, earthenware places another concentric pipe.
Fig. 2 Lower Half comprises two filters shown in Figure 11, and filter 1 is the earthenware part with boring of several forms shown in Figure 1. For this reason, get out for example 19 axle borings in the earthenware that is made up of highly porous ceramic material, this axle boring is for parallel.
In the first half of Fig. 2, partly shown the processing district of printed circuit board (PCB) processing unit (plant). Printed circuit board (PCB) transmits by different processing districts continuously along machine direction R. The representative instance of this method is described in WO 93/17153 A1 especially.
After through the preliminary treatment step, the printed circuit board (PCB) (not shown) is dipped in the activating bath that contains pallamine at region of activation A-pd. For this reason, in the dipping bath cabinet, fill described liquid.
Then, printed circuit board (PCB) is transmitted by three continuous cleaning area S1、S
2And S3 Here, being attached to the lip-deep activating solution of printed circuit board (PCB) is fallen by continuous wash. For this reason at different cleaning area S1、S
2And S3All provide shower nozzle. Cleaning area S1、S
2And S3Be configured to the container of upper shed, arrange to have shower nozzle on the wall on its long limit. In order to wash the activating solution that adheres to, in that being sunk to and/or rise, printed circuit board (PCB) leaves cleaning area S1、S
2And S3The time, cleaning fluid is sprayed on the circuit board surface. Cleaning fluid is respectively at cleaning area S1、S
2And S3Container bottom collect. Fresh cleaning solution is dispensed to cleaning area S with 200 l/hs mean flow rate3, guide to arrangement cleaning area S at its upstream with the direction opposite with printed circuit board (PCB) machine direction R thus2, cause again thus cleaning area S1, flow velocity is kept identical. Each cleaning area S1、S
2And S3Also dispose a collecting pit (not shown), wherein collect respectively cleaning fluid. The cleaning fluid of collecting with 200 l/hs flow rate by cleaning area S1Collecting pit get rid of further processing.
By cleaning except after the activating solution of attachment removal, it is carried out post processing on the printed circuit board (PCB) surface. Such working fluid is sulfinic acid solution for example. In post processing zone B, printed circuit board (PCB) immersed in the solution of containing in the container handling process.
Afterwards, the aftertreatment fluid that adheres to is again at cleaning area S4、S
5And S6In be cleaned. Similarly, cleaning fluid is by being located at cleaning area S4、S
5And S6In shower nozzle be sprayed onto on the surface of printed circuit board (PCB). The cleaning fluid of collecting is concentrated to the collecting pit (not shown), introduces continuously the cleaning area S that is located at its upstream along the direction opposite with printed circuit board (PCB) machine direction R thus5And S4 Cleaning fluid is by cleaning area S4Get rid of, immerse wastewater treatment operation subsequently.
Then, printed circuit board (PCB) is immersed in the etching solution in the container of etching region C-Pd. Here, absorb to the palladium on copper surface and remove by etching copper surfaces is activated a little. In this case the same, printed circuit board (PCB) is dipped in the etching solution.
The working fluid that will adhere to afterwards, washes from the printed circuit board (PCB) surface again. For this reason, printed circuit board (PCB) is sent to cleaning area S7、S
8And S9 The etching solution that is attached to the printed circuit board (PCB) surface removes by be sprayed at the lip-deep cleaning fluid of printed circuit board (PCB) from shower nozzle. For this reason, fresh cleaning solution is introduced cleaning area S with 200 l/hs flow velocity9, the cleaning fluid of collecting at this cleaning area is collected in the collecting pit (not shown). Similarly, the cleaning fluid of collection along the direction opposite with printed circuit board (PCB) machine direction R by cleaning area S9Introduce cleaning area S8, and enter thus cleaning area S7 By cleaning area S7, the cleaning fluid that is rich in palladium is introduced regenerating unit with 200 l/hs flow velocity.
The mode of aforementioned processing printed circuit board (PCB) is a kind of possible selection. Printed circuit board (PCB) also can be processed in so-called horizontal device. The circuit board along continuous straight runs is carried and to be oriented horizontally or vertically by each treatment region thus. In different treatment regions, liquid is delivered to the printed circuit board (PCB) surface by shower nozzle.
By cleaning area S4The cleaning fluid that produces is substantially free of noble metal and can be dispensed to traditional waste water system of processing. With it contrast is by cleaning area S1And S7The cleaning fluid that produces contains palladium, and these cleaning fluids are regenerated in mode of the present invention:
At first, various rinse water is collected in respectively in dashpot 11.1 and 11.2. Cleaning fluid is got rid of with 200 l/hs flow velocity by dashpot 11.1 and 11.2, guides to conduit 13.1 and 13.2 by pump 12.1 and 12.2 respectively then, and is delivered to common conduit 13.3. In order to adjust pH, cleaning fluid (if needs) and the pH adjusting agent (being NaOH herein) that merge are mixed. For this reason, NaOH solution is added the cleaning fluid that merges by accumulator tank 14. Control the dosage of NaOH solution with automatically controlled path (not shown). Described control access comprises that pH probe 15 (for example pH measurement electrode) is with the constant displacement pump of control NaOH solution. The pH of cleaning fluid near 7 situation under, pH does not need to adjust to 7 exact value.
If utilize ion or ionization palladium solution to replace palladium colloidal solution, use the solution of other suitable chemical substances to replace pH adjusting agent, it is added in the liquid stream in order to filter containing palladium liquid.
Then, the cleaning fluid of pH adjusted to about 7 imported collecting pits 16 by another pump 12.3 by conduit 13.4.
In collecting pit 16, provide low level sensor 17.1 and high level sensor 17.2. If liquid level is higher than high level sensor 17.2, liquid is imported into pump 18 by conduit 13.5 by container 16. And if the liquid level of collecting pit 16 is lower than level sensor 17.1, cleaning fluid is no longer pumped by collecting pit 16.
By pump 18, liquid is conducted through the membrane filter tube 1 of two series windings under the pressure of 1.5-3 bar. Permeation liquid by Guan Bi is removed to wastewater treatment A. Stay ring duct 13.6 circulations of concentrate by sealing in the screen pipe, thereby the palladium in the liquid is carried out continual concentrating. By branch conduit 13.7, the partial concentration cleaning fluid is back in the collecting pit 16 continuously, by pump 18 it is directed at film filter thus, so palladium content progressively increases in the described fluid.
In collecting pit 16, deposit in the multi-phase separation district by concentrating the palladium slurries that contain that produce. Described suspension slurries can be got rid of to another container 19.
Directly also can directly emit regeneration and be directed at the hyperfiltration operation from the fluid of region of activation A-Pd. For this reason, described liquid can pass through the path manual transfer of numbering M to collecting pit 20, or by pump 12.4 it is guided to dashpot 11.1 on a small quantity. Then, can will remove and manual transfer to the liquid of collecting pit 20 is dispensed to collecting pit 16 by for example another pump 12.5.
The 16 inner suspension liquid slurries of container in the multi-phase separation unit are imported filter press 21 further separate palladium. Filter press 21 is presented among Fig. 2 with dotted line. It contains hole dimension is about 50 microns filter material. Pressure in the filter press is about 4 bar. The liquid that leaches can loop back collecting pit 16 or be dispensed to wastewater treatment district A by other conduit 22.
Following example is used to explain the present invention:
Embodiment 1:
For testing, use in printed circuit board is contained the acidic activated liquid of colloidal state of the pallamine of 400 mg/litre, the protective colloid of polymer form and the reductive agent of sodium hypophosphite form and handle.Average footpath of palladium colloidal solid is about 4nm.
After cleaning, the aftertreatment fluid that use in printed circuit board is contained organic-sulfinic acid is handled, and then cleans and handle in containing the Sodium Persulfate etching solution of 300 grams per liters at last.The palladium that removes from the copper surface is assigned to the etching solution thus, and enters subsequently scavenging solution with the etching solution attached to printed circuit board surface.
Under the condition of mentioning in front at cleaning area S
1To S
3And S
7To S
9The scavenging solution that obtains in the (see figure 2) is distributed to described regenerating unit with 200 liters/hour flow velocity respectively.Use pottery to make (α-Al
2O
3As propping material, be covered with two-layer filtering layer: the ZrO of surpassing on it
2And TiO
2, TiO
2Have superfine hole dimension, and finish filtering evacuation aperture size and be about 20,000 dalton; TiO
2With sol-gel method coating) film filter filter described liquid.The pH of the concentration of palladium and these liquid is listed in (test 1 and 2) in the table 1 in the scavenging solution.
By cleaning area S
1To S
3And S
5To S
7The pH of the liquid that produces does not use the pH regulator agent to regulate.
When ultra-filtration, concentrated solution is handled by the ceramic membrane filter device with 2,800 liters/hour flow velocity.The seepage velocity that is reached is 40 to 45 liters/hour.
Undergo ultrafiltration and obtain penetrating fluid and concentrated solution.Also be listed in the table 1 according to the penetrating fluid of test 1 and 2 and the concentration of the palladium in the concentrated solution.
Embodiment 2:
In another test, will be with 1: 1 volume ratio from the colloidal state activation solution with from the cleaning liquid-phase mixing of etching solution (test 3).Use the ceramic membrane filter device identical with embodiment 1.The initial palladium concentration in the mixing scavenging solution and the pH of mixture list in the table 1.For the pH that will mix scavenging solution is adjusted to 7, in scavenging solution, add NaOH solution.
Palladium concentration＜0.5 mg/litre at the penetrating fluid that carries out obtaining after the ultra-filtration.Palladium concentration in the concentrated solution＞1 grams per liter (seeing Table 1).
Embodiment 3:
In another test 4, use identical ceramic membrane filter device with embodiment 1.The colloidal state activation solution adds in the scavenging solution mixed solution that obtains according to embodiment 2 with 1: 100 volume ratio.Palladium concentration equals 15.0 mg/litre in this liquid.Use NaOH solution that the pH of described liquid is adjusted to 7.Palladium concentration after carrying out ultra-filtration in penetrating fluid and the concentrated solution is listed in the table 1.
Embodiment 4:
In another test 5, use identical ceramic membrane filter device with embodiment 1.Use the inorganic activation agent solution to replace the colloidal state activation solution in this test.Described activator contains organic palladium complex compound (Neoganth Activator, Atotech Deutschland GmbH, Germany), and palladium concentration is 250 mg/litre in this solution.
With this solution activatory printed circuit board (PCB), and then by three cleaning area S
1, S
2And S
3Carry out clean, the flow of washing water direction is with shown in Figure 2 consistent.Cleaning area S
1Palladium concentration is about 1.5 mg/litre in the rinse water that produces.For adjusting the ultra-filtration ability of rinse water, in rinse water, add the aqueous solution of the Sodium dimethyldithiocarbamate 40min of 467 grams per liters.Penetrating fluid and the palladium concentration in the concentrated solution that described solution ultra-filtration is produced are listed in table 1 (test 5).
Embodiment 5:
In another test 6, use identical ceramic membrane filter device with embodiment 1.In this test, the rinse water that obtains according to embodiment 4 is mixed with activating bath solution with 100: 1 volume ratio.The sodium sulfide solution that in mixture, adds 10 grams per liters.Initial palladium concentration is 8.0 mg/litre.Palladium concentration in ultra-filtration rear filtrate and concentrated solution is listed in the table 1.
Above-described test has produced the concentrated solution that contains a large amount of slurries.After the slurries sedimentation, concentrated solution is assigned to pressure filter.The palladium concentration that is rich in the concentrated solution of palladium is 2 to 5 grams per liters.Palladium concentration in the filter cake that obtains after compression is 2 to 15 weight %.
Embodiment 6:
In another test 7, use identical ceramic membrane filter device with embodiment 1.To add the cleaning liquid mixture that obtains according to embodiment 2 according to the mixture of embodiment 5 with 2: 1 volume ratios.
Palladium concentration in the described liquid is 4.2 mg/litre.Use NaOH solution that PH is adjusted to 7.In addition, the Sodium dimethyldithiocarbamate 40min aqueous solution that in described liquid, adds 467 grams per liters.Penetrating fluid that obtains after the ultra-filtration and the palladium concentration in the concentrated solution are listed in the table 1.
Be understood that, embodiment described here and embodiment are only described purpose, those skilled in the art can easily expect according to the combining of the application's various improvement and feature described in variation and the application, and these all should comprise within the spirit and scope of the present invention and by incidental claim and covering.Incorporate this paper by reference in this all publications, patent and patent application of quoting.
Table 1:
| Test number | Mixture of products | Initial Pd concentration [mg/l] | pH | Pd concentration [mg/l] in the penetrating fluid | Pd concentration [mg/l] in the concentrated solution | Add pharmaceutical chemicals |
| 1 | Scavenging solution colloidal state activator | ?5.5 | ?5 | ＜0.5 | ＞1,000 | Do not add |
| 2 | The scavenging solution etching solution | ?2.5 | ?3 | ＜0.5 | ＞1,000 | Do not add |
| 3 | Scavenging solution colloidal state activator+etching solution: 1: 1 | ?4.0 | ?7 | ＜0.5 | ＞1,000 | NaOH |
| 4 | Scavenging solution colloidal state activator+etching solution: 1: 1+1 volume % colloidal state activator | ?15.0 | ?7 | ＜0.5 | ＞1,000 | NaOH |
| 5 | Scavenging solution ionization activator | ?1.5 | ?8 | ＜0.5 | ＞1,000 | Sodium dimethyldithiocarbamate 40min |
| 6 | Scavenging solution ionization activator+1 volume % ionization activator | ?8.0 | ?8 | ＜0.5 | ＞1,000 | Na 2S |
| 7 | (cleaning fluid ionization activator+1 volume % ionization activator)+cleaning fluid colloidal state activator+cleaning fluid etching solution: 1: 1: 1 | ?4.2 | ?7 | ＜0.5 | ＞1,000 | NaOH, Sodium dimethyldithiocarbamate 40min |
Claims (20)
1, a kind of method with liquid plating workpiece, described liquid contains at least a precious metal, described method comprises with described liquid and contacts described workpiece, behind the described workpiece of plating, filter described liquid so that from this liquid, isolate described at least a precious metal by at least one ceramic membrane filter device, the evacuation aperture size of wherein said ceramic membrane filter device surpasses 10,000 dalton.
2, method as claimed in claim 1, the evacuation aperture size range of wherein said at least a ceramic membrane filter device are about 15,000 dalton 25,000 dalton extremely.
3, method as claimed in claim 2, the evacuation aperture of wherein said at least one ceramic membrane filter device are of a size of about 20,000 dalton.
4, a method as claimed in any preceding claim, wherein said at least one ceramic membrane filter device is made by aluminum oxide/titanium dioxide/zirconia ceramic material.
5, a method as claimed in any preceding claim, wherein said workpiece are fit to make circuit carrier.
6, a method as claimed in any preceding claim, wherein said precious metal are palladium.
7, method as claimed in claim 6, wherein behind the described workpiece of plating and before filtering described liquid by at least one ceramic membrane filter device, described liquid is mixed with suitable chemical substance changing described at least a precious metal, thereby this precious metal is stayed when filtering basically fully.
8, method as claimed in claim 7, wherein palladium exists with ion and/or ionized form, and described liquid mixes mutually with the chemical substance that is selected from reductive agent, sulphur compound, selenium compound and tellurium compound.
9, method as claimed in claim 8, wherein said chemical substance are selected from hydroborons, amine borine, hypophosphite, inorganic sulphide and organic sulfide.
10, method as claimed in claim 9, wherein palladium exists with colloidal form, and wherein said chemical substance is the pH regulator agent, and it is 3 to 12 that itself and described liquid mixing make the pH scope of solution.
11, the method arbitrary as claim 7-10, it comprises following method steps:
A. described workpiece is contacted with containing the palladium working fluid,
B. then, will attached to the working fluid of described workpiece surface remove with scavenging solution and
C. by described at least one ceramic membrane filter device described working fluid and/or described scavenging solution are filtered, the liquid by described at least one ceramic membrane filter device is penetrating fluid, and the liquid by described at least one ceramic membrane filter device is not concentrated solution.
12, as the method for claim 11, wherein before handling, described working fluid and/or described scavenging solution are mixed with described chemical substance by described at least one ceramic membrane filter device.
13,, wherein the highest scavenging solution that contains the described working fluid of 5 volume % is handled by described at least one ceramic membrane filter device as method arbitrary in claim 11 and 12.
14, as the method for claim 13, wherein in the unit time, described workpiece is contacted with the fresh cleaning solution of predetermined amount, and the amount of the described penetrating fluid that wherein forms in the unit time approximates the amount of the scavenging solution that contacts with described workpiece in the unit time.
15, at least a liquid that contains precious metal of a kind of usefulness comes the equipment of plating workpiece, described equipment comprises the device that described workpiece is contacted with liquid and the device of the described workpiece of clamping, this equipment also comprises the facility of isolating described at least a precious metal from described liquid, this facility comprises at least one ceramic membrane, at least one is delivered to described liquid the pump of described at least one ceramic membrane and the fluid conduits that described liquid is guided to described at least one ceramic membrane by the device that described workpiece is contacted with liquid, the evacuation aperture size of wherein said at least one ceramic membrane surpasses 10,000 dalton.
16, as the device of claim 15, the evacuation aperture size range of wherein said at least one ceramic membrane is that about 15,000 dalton are to about 25,000 dalton.
17, as the device of claim 15 or 16, the evacuation aperture of wherein said at least one ceramic membrane is of a size of about 20,000 dalton.
18, as device arbitrary among the claim 15-17, the facility of wherein isolating described at least a precious metal from described liquid also provides the liquid and chemical substance blended mixing facility that makes from the device that described workpiece is contacted with described liquid.
19, as device arbitrary among the claim 15-18, a heterogeneous separating unit wherein is provided, in this unit, the slurries that produce in the sepn process and isolate the facility of described at least a precious metal in described liquid can carry out sedimentation.
20, as device arbitrary among the claim 15-19, wherein said at least a ceramic membrane is made by aluminum oxide/titanium dioxide/zirconia ceramic material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10148632.4 | 2001-09-26 | ||
| DE10148632A DE10148632C1 (en) | 2001-09-26 | 2001-09-26 | Method and device for the galvanotechnical treatment of workpieces with a liquid containing precious metals |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1633521A true CN1633521A (en) | 2005-06-29 |
Family
ID=7701145
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA028188861A Pending CN1633521A (en) | 2001-09-26 | 2002-08-15 | Precious metal recovery |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US20040237717A1 (en) |
| EP (1) | EP1430163B1 (en) |
| JP (1) | JP2005504178A (en) |
| KR (1) | KR20040043168A (en) |
| CN (1) | CN1633521A (en) |
| AT (1) | ATE380264T1 (en) |
| AU (1) | AU2002333428A1 (en) |
| BR (1) | BR0212823A (en) |
| CA (1) | CA2460015A1 (en) |
| DE (2) | DE10148632C1 (en) |
| ES (1) | ES2297045T3 (en) |
| MX (1) | MXPA04002772A (en) |
| MY (1) | MY147747A (en) |
| TW (1) | TWI293999B (en) |
| WO (1) | WO2003029518A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103945654A (en) * | 2013-01-18 | 2014-07-23 | 北大方正集团有限公司 | Method for leaving palladium ions in non-metallized holes of passivation circuit board and circuit board manufactured through same |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1884278A1 (en) * | 2006-07-24 | 2008-02-06 | ATOTECH Deutschland GmbH | Apparatus and method for rinsing of liquid from work pieces |
| KR101211740B1 (en) * | 2007-03-30 | 2012-12-12 | 미쯔이 죠센 가부시키가이샤 | Method of membrane treatment for ballast water |
| JP6234070B2 (en) * | 2013-06-03 | 2017-11-22 | 木田精工株式会社 | Method and apparatus for regenerating surface treatment wastewater |
| PL3168326T5 (en) * | 2014-07-10 | 2024-02-05 | Okuno Chemical Industries Co., Ltd. | Resin plating method |
| JP6340302B2 (en) * | 2014-10-24 | 2018-06-06 | 田中貴金属工業株式会社 | Waste liquid treatment method, waste liquid treatment device, and waste liquid reuse method |
| EP3133175A1 (en) * | 2015-08-19 | 2017-02-22 | Enthone, Inc. | System and process for recovering catalytic precious metal from aqueous galvanic processing solution |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4078918A (en) * | 1976-11-26 | 1978-03-14 | Perman Craig A | Method for precious metal recovery |
| US4435258A (en) * | 1982-09-28 | 1984-03-06 | Western Electric Co., Inc. | Method and apparatus for the recovery of palladium from spent electroless catalytic baths |
| US4895739A (en) * | 1988-02-08 | 1990-01-23 | Shipley Company Inc. | Pretreatment for electroplating process |
| US5205937A (en) * | 1992-04-30 | 1993-04-27 | U.S. Filter Membralox | Recovery and reuse of water-based cleaners |
| DE10024239C1 (en) * | 2000-05-15 | 2001-09-20 | Atotech Deutschland Gmbh | Process for galvanically treating workpieces used e.g. in the production of circuit boards comprises contacting the workpieces with a palladium colloidal solution, and recovering the solution after use |
| KR20020061530A (en) * | 2001-01-18 | 2002-07-24 | 쉬플리 캄파니, 엘.엘.씨. | A method for recovering catalytic metals |
-
2001
- 2001-09-26 DE DE10148632A patent/DE10148632C1/en not_active Expired - Fee Related
-
2002
- 2002-08-15 JP JP2003532726A patent/JP2005504178A/en not_active Withdrawn
- 2002-08-15 ES ES02800002T patent/ES2297045T3/en not_active Expired - Lifetime
- 2002-08-15 AU AU2002333428A patent/AU2002333428A1/en not_active Abandoned
- 2002-08-15 KR KR10-2004-7001290A patent/KR20040043168A/en not_active Application Discontinuation
- 2002-08-15 US US10/490,004 patent/US20040237717A1/en not_active Abandoned
- 2002-08-15 BR BR0212823-3A patent/BR0212823A/en not_active Application Discontinuation
- 2002-08-15 WO PCT/EP2002/009125 patent/WO2003029518A2/en active IP Right Grant
- 2002-08-15 DE DE60223934T patent/DE60223934T2/en not_active Expired - Lifetime
- 2002-08-15 EP EP02800002A patent/EP1430163B1/en not_active Expired - Lifetime
- 2002-08-15 CA CA002460015A patent/CA2460015A1/en not_active Abandoned
- 2002-08-15 MX MXPA04002772A patent/MXPA04002772A/en unknown
- 2002-08-15 AT AT02800002T patent/ATE380264T1/en not_active IP Right Cessation
- 2002-08-15 CN CNA028188861A patent/CN1633521A/en active Pending
- 2002-08-22 MY MYPI20023105A patent/MY147747A/en unknown
- 2002-08-23 TW TW091119189A patent/TWI293999B/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103945654A (en) * | 2013-01-18 | 2014-07-23 | 北大方正集团有限公司 | Method for leaving palladium ions in non-metallized holes of passivation circuit board and circuit board manufactured through same |
Also Published As
| Publication number | Publication date |
|---|---|
| US20040237717A1 (en) | 2004-12-02 |
| EP1430163A2 (en) | 2004-06-23 |
| WO2003029518A3 (en) | 2004-03-25 |
| BR0212823A (en) | 2004-10-13 |
| ES2297045T3 (en) | 2008-05-01 |
| ATE380264T1 (en) | 2007-12-15 |
| TWI293999B (en) | 2008-03-01 |
| DE60223934D1 (en) | 2008-01-17 |
| JP2005504178A (en) | 2005-02-10 |
| MXPA04002772A (en) | 2004-06-29 |
| KR20040043168A (en) | 2004-05-22 |
| DE10148632C1 (en) | 2003-06-05 |
| AU2002333428A1 (en) | 2003-04-14 |
| WO2003029518A2 (en) | 2003-04-10 |
| DE60223934T2 (en) | 2008-12-04 |
| MY147747A (en) | 2013-01-15 |
| EP1430163B1 (en) | 2007-12-05 |
| CA2460015A1 (en) | 2003-04-10 |
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