Patent Grant
10941502
The present invention belongs to the field of electrochemical process for the surface treatment of metals, in particular of non-ferrous metals.
Anodizing (also spelled anodising, particularly in the UK, India and Australia) is an electrolytic passivation process used to increase the thickness of the natural oxide layer on the surface of metal parts.
The process is called anodizing because the part to be treated forms the anode electrode of an electrical circuit. Anodizing increases resistance to corrosion and wear, and provides better adhesion for paint primers and glues than does a bare metal. Anodic films can also be used for a number of cosmetic effects, either with thick porous coatings that can absorb dyes or with thin transparent coatings that add interference effects to reflected light.
Anodizing is also used to prevent galling of threaded components and to make dielectric films for electrolytic capacitors. Anodic films are most commonly applied to protect aluminum alloys, although processes also exist for titanium, magnesium, niobium, zirconium, hafnium, and tantalum.
Anodizing changes the microscopic texture of the surface and the crystal structure of the metal near the surface. Thick coatings are normally porous, so a sealing process is often needed to achieve corrosion resistance. Anodic films are generally much stronger and more adherent than most types of paint and metal plating, but also more brittle. This makes them less likely to crack and peel from aging and wear, but more susceptible to cracking from thermal stress.
It is not common that one unique treatment can be made suitable for a large range of metals and/or alloys different physically and chemically. There is a need for a multipurpose treatment by the fact that in many finishing shops, different metals are treated and it can be useful, cheaper and efficient to process different non-ferrous metals such as magnesium, aluminum, or titanium using the same layout in the factory.
Magnesium. Magnesium is a metal with physical properties quite similar to aluminum but its chemical properties are quite different. This is the reason why a conversion coating process used for aluminum when applied on magnesium may give bad results on a subsequent painting process. Magnesium is appreciated because it is light and easy to produce and form. It is the lightest metal used for structural applications as being 34% lighter than aluminum. Magnesium and its alloys, especially in cast items, are really sensitive to corrosion and require a surface treatment to ensure aesthetic aspect and functionality of the parts. The most common finishing surface treatment of magnesium and its alloys is painting, but to paint magnesium it is necessary to create a “conversion coating” on which a conventional paint (powder, wet or electrophoretic—e.g. Ecoat) can adhere. Such “conversion coating” can be produced just by dipping or by using an electrolytic process usually named “anodizing” because the coating is formed when the magnesium part acts as a positive pole (anode) of an electrolytic cell.
In the usual procedure, magnesium is treated performing the following steps:
This type of anodizing process, known from the 1940s, presents the following two major problems:
More recent processes known under the acronyms of MAO (Micro Arc Oxidation) or PEO (Plasma Electrolytic Oxidation) have been introduced but even they are not exempt from the following problems. For instance, they produce an evident luminescence all around the parts under treatment due to sparks generated by an arcing phenomenon caused between the cathode and the anode (the magnesium part) by the high electric potential (voltage). Also, the solutions can include toxic compounds like fluorides, borates, and amines or instable salts like silicates or aluminate. Since the conductivity of those solutions is very low, and the applied current density to form the coating can be high reaching even 10-30 A/dm2, the voltage at the end of the process can overcome 600V. In some cases, a combination of positive and negative current is obtained and ΔV can be around 1000 Volt. In practice, these types of processes are really expensive, frequently requiring complex and expensive electrical machines. Sometimes, a frequency variation up to 3000 Hz is obtained. Known anodizing on magnesium processes are expensive.
Anodizing has the advantage to be less sensitive to the alloys and production methods (even casting can give a good result), but the problem caused by the activation dipping can be a real obstacle.
There is thus a need for a new process that would allow:
Aluminum.
Aluminum has its own standardized processes for chemical conversion coatings and anodizing, but those processes frequently give unsuitable results for instance when high silicon containing alloys are treated or a very high hardness is required.
Originally, MAO and PEO have been claimed to achieve very hard coatings (e.g. 2000 HV—hardness in Vickers units) which are not possible with conventional processes using sulfuric acid at low temperature (max 900 HV). When treating high silicon containing alloys in the conventional way, a thick black powdery film remains on the aluminum parts before entering the chemical conversion solution or the anodizing tank. The presence of such coating makes any chemical conversion coating unsuitable to a subsequent painting step and the anodic layer anaesthetic and unsuitable for specific mechanical applications.
There is thus also a need for a new process for anodizing aluminum, allowing:
Anodizing extruded aluminum in acidic medium (bathing H2SO4) is a well-known process, based on the synergy of the oxidizing effect of the acid and the electric current. Indeed, it is the in-depth transformation (from a few microns to tens of microns) of aluminum metal in alpha-aluminum oxide.
Naturally, aluminum, on its surface, presents a very thin layer (angstroms) of very compact oxide which prevents deeper oxidation providing to the aluminum a resistance to corrosion in acid and neutral conditions. Being also much less reactive than magnesium, in general, aluminum can be anodized in neutral or alkaline medium but needs a powerful oxidant, such as a strong acid or H2SO4. The acid is used to bring higher conductivity to the solution, and not for its oxidizing effect. The oxide layer is generated by the current only. The sulfate group (SO42−) is not affected or hydrolyzed by the current. Citric or oxalic acid, and also hydrogen peroxide, bring reactive oxygen to the solution. Monoprotic acids such as nitric and hydrochloric cannot be used because they dissolve the nascent oxide layer. Phosphoric acid forms a very thin layer generally used for gluing.
Magnesium, in the contrary, being much more reactive, will dissolve in acidic conditions.
Apart from a low electrical conductivity, the presence of the silicon surface makes it impossible to develop a continuous oxide layer. Indeed, the layer that could however be obtained, presents discontinuities (deep crevasses representing unprotected attack zones) where silicon is present (the silicon is not anodized) which disqualify the corrosion resistance that the anodizing process is supposed to develop.
To address this aspect, thanks to the thermal effect of the spark anodizing, silicon present at the surface will combine with aluminum oxide to give Mullite (3Al2O3*2SiO2). The Mullite is an aluminosilicate (ceramic) having a mechanical strength and resistance to corrosion near alpha Al2O3. It can be combined in the presence of phosphate with Al2O3 (formed in areas where the silicon is absent) so it is acceptable to think that a hybrid layer of these two elements will present interesting corrosion resistance.
The problem related to this is given by the Mullite formation temperature, or 1450° C., normally achievable by heat treatment in an oven and not in an aqueous solution. It is obvious that at this temperature, the alloy cannot withstand either since its melting temperature is below 600° C. It must be considered that the high temperature (close to the plasma temperature) developed in the electric spark (spark) will have a sufficient thermic effect for synthesizing Mullite in the alloy volume increment located at the workpiece surface.
The present invention overcomes these problems by combining a different electrolytic solution with a specific current density.
Titanium (and its Chemical Group Members: Zirconium, Hafnium and Tantalum).
Titanium and its family members have completely different properties compared to magnesium or aluminum (and their alloys). An electrolytic process can be used to “color” the titanium parts, for instance like a sort of coding for parts for medical applications (like prostheses or dentistry). In that case, the process is performed using essentially a strong acid, such as sulfuric acid. In general, a thick anodic coat is produced in sulfuric acid for generic applications or in phosphates for dentistry and prostheses. For structural or specific medical applications, an alkaline anodizing process may be required (e.g. according to ASM 2488), using for instance chemical treatment containing nitric and/or fluoride based products, similar to what was previously said above concerning magnesium activation.
By using an innovative process as described herein, the toxic dipping mentioned above can be avoided. Since the proposed treatment is alkaline, even the requirements of the above mentioned specification are fulfilled.
European patent application no. EP 1 793 019 A2 discloses an anodization process of non-ferrous metallic parts. However, EP 1 793 019 A2 does not teach the use of an electrolytic solution containing an organic acid and the resulting advantages disclosed herein after.
In conclusion, the drawbacks of the current known processes for treating non-ferrous metals are:
In these conditions, a significant improvement is achieved by the proposed treatment process in that it can avoid any preliminary dipping in toxic solutions, and the subsequent electrolytic process can be performed in a medium alkaline solution, at low current density and, consequently at lower voltage.
The invention is first directed to a process for the electrolytic treatment of non-ferrous metallic parts. The process comprises the step of anodizing the non-ferrous metallic parts by first applying a negative electric current to the non-ferrous metallic parts during a first given period of time and second applying a positive electric current during a second given period of time; while maintaining the metallic parts in an electrolytic cell comprising an alkaline electrolytic solution having a pH from 9 to 12, preferably from 10 to 12, more preferably from 10.5 to 11.5, and comprising at least one organic acid or salt thereof. The process is performed by using a continuous current or a variously shaped pulsating current provided via a rectifier operatively connected to a harmonic filter, the harmonic filter is an Advanced Universal Harmonic Filter (AUHF) providing reduced current distortion on a source side, the AUHF allowing reduced ripple voltage while improving purity of a DC voltage used in the process.
The invention is also directed to an electrolytic solution for use in a process for anodizing non-ferrous metallic parts, the electrolytic solution being an alkaline electrolytic solution having a pH from 9 to 12, preferably from 10 to 12, more preferably from 10.5 to 11.5, and comprising at least one organic acid.
The invention is also directed to an anodized non-ferrous metallic part obtained by the process as defined herein, wherein the anodized non-ferrous metallic part comprises a uniform anodized coating with a thickness up to about 20 μm. Preferably, the uniform anodized coating may comprise metallic salts, such as AgF, the uniform coating being then conductive to electricity.
The anodized non-ferrous metallic parts obtained by the process are preferably for use in the making of transport vehicles, such as, but not limited aircrafts, automobiles or trains.
The invention is also directed to an electrolytic assembly for anodizing non-ferrous metallic parts, comprising:
The subject of the present invention is first a process for the electrolytic treatment of non-ferrous metal materials, such as, in alphabetic order, aluminum, magnesium, hafnium, tantalum, titanium, vanadium, and zirconium, but such a list is just a non-restrictive indication.
Even less common metals like beryllium, scandium, yttrium, molybdenum or tungsten can be treated but they are of limited use.
The present invention allows the production of a surface coating which has both an aesthetic and a protective function. The electrolytic solution of the present invention is free of toxic or harmful elements. The non-ferrous metallic parts will be sent to the electrolytic step without any preliminary chemical treatment, in order to avoid the high toxicity typical of those treatments.
The present invention is a treatment to be applied to non-ferrous metals and their alloys providing the following improvements:
The advantage of using an organic acid in the electrolytic solution is to buffer said solution, leading to a more uniform structure of the layer due to a uniform and constant migration of the elements forming the layer to the surface of the metallic parts.
Other and further objects and advantages of the present invention will be better apparent upon an understanding of the illustrative embodiments about to be described or will be indicated in the appended claims, and various advantages not referred to herein will occur to one skilled in the art upon employment of the invention in practice.
The above and other objects, features and advantages of the invention will become more readily apparent from the following description, reference being made to the accompanying drawings in which:
Although the invention is described in terms of specific illustrative embodiment(s), it is to be understood that the embodiment(s) described herein are by way of example only and that the scope of the invention is not intended to be limited thereby.
The present invention is based on the following main features:
Therefore, the invention is first directed to a process for the electrolytic treatment of non-ferrous metallic parts. As illustrated on
According to a preferred embodiment, the non-ferrous metallic parts comprises aluminum, magnesium, hafnium, tantalum, titanium, vanadium, zirconium, beryllium, scandium, yttrium, molybdenum, tungsten, alloys thereof or combinations thereof.
According to a preferred embodiment, the first given period of time is selected according to the nature of the metal constituting the non-ferrous metallic parts under treatment and its final application. For instance, the negative current may be applied up to 10 minutes, more preferably up to 2 minutes. Also, the current density is selected according to the nature of the metal constituting the non-ferrous metallic parts under treatment and its final application. The negative current may have a current density of 0.5 to 5.0 A/dm2, more preferably a density of 2.0 A/dm2. The positive current may be applied from 30 seconds to 60 minutes, and the positive current may have a current density of 1 to 10 A/dm2, more preferably the positive current has a current density of 2.0 A/dm2.
According to a preferred embodiment, the positive current has a voltage from 200 to 650 Volts.
According to a preferred embodiment, the process according to the present invention may further comprise the step of cooling down the electrolytic solution in a way that the electrolytic solution is maintained at a temperature ranging between 5 and 40° C., more preferably between 15 and 20° C.
According to a preferred embodiment, the at least one organic acid, or its salts, is present in a concentration of from 0.1 g/l up to solubility, more preferably in a concentration of 10 to 20 g/l.
According to a preferred embodiment, the at least one organic acid, or its salts, have a number n of atoms of C from 1 to 20, linear or branched, and comprising from 0 to m hydroxyl groups, where m is a number from 0 to (n−1). For instance, the at least one organic acid can be carbonic acid, formic acid, acetic acid, hydroxyacetic acid, oxalic acid, citric acid, or ascorbic acid, or its salts obtained by the addition of alkali metals hydroxides or ammonium hydroxide in the solution.
According to a preferred embodiment, the pH is obtained by the addition in the solution of at least one alkali metal or ammonium hydroxide NH3OH. Preferably, the said at least one alkali metal is lithium, sodium or potassium.
According to a preferred embodiment, the at least one alkali metal hydroxide is present in a concentration range from 10 to 100 g/l, more preferably in a concentration range from 30-50 g/l.
According to a preferred embodiment, the electrolytic solution further comprises phosphoric acid or its alkali metal salts, in a concentration up to 20 g/l.
According to a preferred embodiment, the electrolytic solution further comprises one or a mixture of tertiary alkanol amines in a concentration up to 75 g/l in the final solution.
According to a preferred embodiment, the electrolytic solution further comprises aluminum hydroxide or an alkaline metal aluminate, in a concentration up to solubility in the final solution.
According to a preferred embodiment, the electrolytic solution may further comprise polyalcohols in a concentration up to 50 g/l in the final solution.
As aforesaid, the present invention also concerns an electrolytic solution for use in a process for anodizing non-ferrous metallic parts, the electrolytic solution being an alkaline electrolytic solution having a pH from 8 to 11 and comprising at least one organic acid. The preferred embodiments regarding the electrolytic solution according to the present invention are as defined here above or in the examples. The non-ferrous metallic parts treated by the solution according to the present invention are, but not limited to, aluminum, magnesium, hafnium, tantalum, titanium, vanadium, zirconium, beryllium, scandium, yttrium, molybdenum, tungsten, alloys thereof or combinations thereof.
As aforesaid, the present invention also concerns anodized non-ferrous metallic parts obtained by the process as defined herein. The non-ferrous metallic parts obtained by the process comprises a uniform anodized coating with a thickness up to about 20 μm. Preferably, those parts once anodized, are particularly for use in the making of transport vehicles, such as but not limited to in the making of an aircraft, an automobile or a train.
As aforesaid, the present invention also concerns an electrolytic assembly for anodizing non-ferrous metallic parts. The set-up of the process tanks in the line is schematized in the flowchart of
As shown on
The electrolytic assembly 1 according to the present invention also comprises at least one counter-electrode 11 located in the cell along the walls thereof. Preferably, the counter-electrodes are preferably placed on long sides of the cell's inner walls. The counter-electrodes may cover at least 75% of an inner surface of the cell's walls. The counter-electrodes 11 can be made of stainless steel, aluminum, titanium or other materials known in the art of electrochemistry for the making of electrodes.
The electrolytic assembly according to the present invention also comprises a hanging system 13 supported by a main support frame 15 located over the electrolytic cell 3. The main frame can be built on the floor of the plant building or can be part of the structure elements of the building.
The hanging system 13 is configured to clamp, hang and fly the non-ferrous metallic parts over the electrolytic cell, and also to dive the metallic parts into the electrolytic cell in a way that the non-ferrous parts are hanged in the cell at a minimum secure distance away from the at least one counter-electrode. The construction and movement of the mechanical elements allowing safely moving and dipping the non-ferrous metallic parts into the electrolytic cell or tank are known in the art of the manufacturing of anodized non-ferrous metallic parts. For instance, according to a preferred embodiment, the hanging system comprises hanging bars 17 spaced apart on a rail 19 and configured to move along the rail. Each hanging bar may comprise at least one jig or clamp 21 for attaching the non-ferrous metallic parts, the hanging bars and jigs being made of a current conductive material. For instance, the current conductive material may be aluminum, titanium or the like. The hanging system is preferably configured to hang the non-ferrous metallic parts in a middle section of the electrolytic cell as it can be seen on the bottom picture of
The electrolytic assembly according to the present invention also comprises an electrical power supply apparatus 23 operatively connected to the counter-electrodes 11, for instance via electric cables 25, and the non-ferrous metallic parts. The electrical power supply apparatus is configured to provide a negative current to the parts for a first period of time and a positive current to the parts for a second given period of time.
According to a preferred embodiment, the electrical power supply apparatus 23 is an electrical rectifier, more preferably a pulse electrical rectifier, such as a 6-pulse rectifier disclosed herein.
According to a preferred embodiment, the electrical power supply can be operatively connected to a harmonic filter, such those known in the art, or in particular a LINEATOR™, AUHF (Mirus International Inc.)
According to a preferred embodiment, the electrical power supply apparatus is controlled by a programmable logic controller (PLC), a host computer or the like.
According to a preferred embodiment, the electrolytic assembly according to the present invention may further comprise a cooling system operatively connected to the electrolytic ell to maintain the electrolytic solution at a temperature ranging from 5 to 40° C.
The terminology used herein is in accordance with definitions set out below.
As used herein % or wt. % means weight % unless otherwise indicated. When used herein % refers to weight % as compared to the total weight percent of the phase or composition that is being discussed.
By “about”, it is meant that the value of weight %, time, or temperature can vary within a certain range depending on the margin of error of the method or device used to evaluate such weight %, time, or temperature. A margin of error of 10% is generally accepted.
By “room temperature”, it is meant the temperature where the compositions have been stored and prepared, or the process is performed. A room temperature of between about 15 and 25° C. is generally accepted.
Electrical Power Supply Apparatus and Type of Current:
The type of machine is available on the market or can be manufactured ad hoc, just reading the simple description detailed below.
As aforesaid, the electrical power supply can be operatively connected to a harmonic filter, such as those known in the art, or in particular a harmonic filter type LINEATOR® AUHF (Mirus International Inc.). It is essentially a passive filter comprising an induction coil combined with a system of small capacitors. It allows for the reduction of all spurious harmonics of the main signal generated by non-linear loads of the system such as inverters or six pulses three phases' rectifiers.
Power System Harmonic Voltage distortion is a function of the Current Distortion of the load (the DC rectifier) and the impedance of the power system. To minimize their effects, high performance filtering of the harmonic currents typically produced by rectifier operation will reduce the non-fundamental current components flowing back through the power system impedance. Reducing Current Distortion on the source side using an Advanced Universal Harmonic Filter (AUHF) to feed the rectifier not only helps meet typical utility harmonic current limits, but reduces voltage ripple as seen on the DC bus as a result of the voltage waveform presented to the rectifier, ensuring greater purity of the DC voltage used in the process.
Using a harmonic filter improves the electrical signal sent to the electrodes and consequently, the resulting coating present a more uniform aspect and quality.
That electrical power supply is preferably managed by a PLC and able to supply a negative current for a given period of time, e.g., up to 10 minutes, preferably from 1 to 5 minutes, more preferably for about 2 min; and subsequently, to supply a positive current for enough time to form a coating layer with a thickness according to the real need. Indicatively, the time is ranging from 2 to 30 minutes, according to the desired coating thickness while depending on the applied current density.
Indeed, the anodization time is directly proportional to the resulting coating thickness, e.g., preferably 5-25 micrometers, more preferably 20 microns; and inversely proportional to the current density, e.g. preferably 1-10 A/dm2, more preferably 2 A/dm2. In practice, a preferable positive current is applied for 15 minutes at 2 A/dm2 to produce a coating of about 20 microns, which is generally considered as the best suggested coating for any subsequent treatment of surface finishing.
As aforesaid, the electrolytic cell or tank for industrial production should be in polypropylene or PVC or simply in steel lined with a nonconductive material like, e.g., polypropylene or PVC, more preferably PVC.
The non-ferrous parts to be treated are placed in the middle of the tank, usually in the length direction, clamped on suitable jigs or racks connected to a main support. The bar with the parts is connected to the positive pole of the electrical supply (made negative, only during the first step of the process). The flying bar and all the jigs and racks are preferably in aluminum.
The counter electrodes (or cathodes when negatives) are placed on the long sides of the tank/cell and are preferably made in stainless steel or aluminum and should preferably cover 75% of the long side walls of the tank/cell.
The length and the depth of the tank will depend on the size and the daily production of the parts. The width should be fixed in order to ensure a distance between parts and counter electrodes ranging preferably from 10 to 50 cm. Too narrow distances could produce an electrical arcing with burning and/or melting of the parts. A too wide distance will need a higher voltage to be applied to ensure the set current density. Stainless steel or aluminum are the preferred metals for the counter electrodes/cathodes.
If we assume to use a suitable power supply/electrical machine managed by a main PLC, or a host computer when the process is included in an industrial plant, a non-limitative indication of the supplied currents can be detailed as in Table 1 below.
It is to be understood that if processed in the same solutions and with the same electrical parameters, the behaviour of the single metals can be different. In practice, with aluminum and some of its cast alloys the yield of the current (or the “coating ratio), i.e. the layer thickness produced by the same current, can be lower if compared with magnesium or titanium. With aluminum part of the current is lost as heat because sparks are necessary to maintain the conductivity of the layer allowing its increase.
Comments on Table 2:
Basic Indicative Data:
Just as an example, when the metal is magnesium or one of its alloys the preferable treatment time can be indicated as 5-15 minutes, according to the thickness of the layer to produce. The current density can range from 0.5 to 25 A/dm2 (preferably 2.0 A/dm2).
Composition of the Solutions:
An indicative solution can be structured as follows:
The electrolytic solution is preferably free of the following harmful compounds because of their toxicity:
Measurements of the Resistance of the Treated Metallic Parts:
Chemical composition of Elektron® 43 alloy (ASTM alloy designation WE43C):
Sample plate measuring approximately (155 mm×55 mm×15 mm) of Elektron® 43 alloy was coated using the following process:
The paint coating system consists of a black polyester type layer of approximately 15-40 μm in thickness on an anodized surface of about 20 μm.
The coating has a low gloss finish and is specified with good adhesion properties; the polyester paint coat requires curing for 7 minutes at 204° C. as outlined in Table 4 below.
The Elektron® 43 alloy plate was subjected to a 20 minute anodizing treatment with the solution approximately at 13-14° C.; to achieve a coating thickness of 0.020-0.025 mm. A three step cleaning method was used following the anodizing treatment where the plate was rinsed in water for 15 seconds at room temperature in stage 1 and 2 followed by rinsing in de-ionised water for 30 seconds in stage 3; the panels were dried using compressed air.
After 2000 hours of salt spray testing there was no apparent damage along the scribe marks (See
Experimental:
The sample was subjected to ASTM B117-11 salt spray test, where a mist of 5% salt solution by mass is atomised in a chamber. The sample was exposed to the spray for intervals of 500, 1000, 1500 and 2000 hours. At each interval the sample was inspected and evaluated for surface condition.
The sample was scribed diagonally across the length with a polycrystalline type diamond tipped scribe. A reference sample of Elektron® 43 alloy was placed alongside the sample coated using the system according to the invention. A 15 mm slice was cut through the scribe marks for analysis on Scanning Electron Microscope (SEM) to observe the coating adherence to magnesium metal surface.
Conclusions:
After 2000 hours of salt spray testing there was no apparent damage or lifting of coating along the scribe marks (See
As shown in
As shown in
Anodization Anod SweetMag™—Alloy 6061-T6
As shown above and on
Indicative Post Treatment to the Proposed Electrolytic Process:
In order to demonstrate the importance of anodizing non-ferrous metallic parts versus non-anodized parts, an experiment has been performed on magnesium cups containing hot liquid (about 55° C. and more).
For the non-treated cup (C1), the spot effect is due to a coating applied to remove the reflectivity of bare magnesium. Accordingly, in the absence of coating (C1), the entire cup would be cold (except for the spot effect). With the coating (C2), the heat transfer would be visible on almost the entire cup (about 45° C.), comparable with the ceramic cup (C3) where the bottom of the cup shows a heat transfer of about 43° C.
In conclusion, the anodization of non-ferrous metallic parts allows a better and uniform heat transfer and heat dissipation, which can be a property of major importance in the making of mechanical components of engines (aircrafts, vehicles or the like) using of these anodized parts.
Some Advantages of Using the Present Invention:
While illustrative and presently preferred embodiment(s) of the invention have been described in detail hereinabove, it is to be understood that the inventive concepts may be otherwise variously embodied and employed and that the appended claims are intended to be construed to include such variations except insofar as limited by the prior art.
The present patent application is a continuation-in-part of international application no. PCT/CA2016/051241 filed on Oct. 27, 2016, and which claims the benefits of priority of commonly assigned U.S. Patent Application No. 62/246,875, filed at the U.S. Trademark and Patent Office on Oct. 27, 2015, both entitled “Electrolytic process and apparatus for the surface treatment of non-ferrous metals” and the content of which being incorporated herein by reference.
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| Number | Date | Country | |
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| Number | Date | Country | |
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| Parent | PCT/CA2016/051241 | Oct 2016 | US |
| Child | 15964450 | US |
