The present disclosure relates to metallic quenching and coating applications. Described techniques include dispersion, carbonated quencher, and ball milling.
Existing processes for producing noble metal particles and noble metal nanoparticles use chemical reactions to release noble metal particles. Noble metals, as used herein, refer to gold and other noble metals, including platinum group metals and silver. Additionally, noble metals are sometimes used to more broadly describe any metallic or semimetallic element that does not react with a weak acid and give off hydrogen gas in the process. This broader set includes, copper, mercury, technetium, rhenium, arsenic, antimony, bismuth and polonium, as well as gold, the six platinum group metals Pt, Ru, Rh, Pd, Os, Ir (platinum, ruthenium, rhodium, palladium, osmium, iridium), and silver.
Suspensions are advanced types of fluids that contain dispersed solid particles. These particles are usually in the range of nanometers (nm) to micrometers (μm) in size. Furthermore, when suspensions are fabricated from particles in the nanoscale they can be referred to as “nanofluids”, whereas the ones made of microns or micrometers (μm) dispersions can be termed as “microfluids”. Such advanced types of fluids are generally targeted towards heat transfer applications; e.g., heat exchangers working fluids, but can also be utilized by the medical sector in the form of medications or inner body diagnostic fluids; e.g., radioactive technetium imaging. Other applications are in the petroleum industry to improve fuel products combustion efficiency or enhance the crude oil recovery at the flooding stage, and as lubricants for mechanical parts.
There are two common approaches to produce these suspensions. The first route is known as the one-step or single-step method, and the second technique is called the two-step method. In the single-step approach, the particles are formed and dispersed within the hosting fluid in a single stage. The advantages of such approach are:
It is noted that this method of production is associated with residuals that are difficult to remove, because of incomplete reactions. The method can only be used to fabricate specific combinations of particles and base fluids (e.g., they cannot be used to produce diamond-water suspensions), and in most cases are very complicated and time consuming.
Known one-step suspension fabrication methods include:
Alternatively, the two-step method uses pre-prepared powders, after which they are added and dispersed in any non-dissolving base fluid through a mixing device, such as ultrasonicator, homogenizer, magnetic stirring, and/or high energy ball (or rod) milling. The advantages of this approach are that any type of suspension can be manufactured, is easy to handle by users with minimum level of experience, the powders are commercially available on a wide scale, and can be used for both small- and large-scale production. Due to the previous advantages, this method of production has been favored by many researchers in the field of advanced fluids. Nevertheless, a downside of this method (i.e., the two-step approach) of suspension production is that the resulting mixture could occasionally have less level of dispersion physical stability than the one-step method; but this can be improved to a certain extent by including surfactants with the mixture at the fabrication stage or by employing surface functionalization to particles.
On the other hand, a quenching process is used to improve the mechanical properties of the as-prepared metallic part. This is done by initially heating the metal to its solution treatment temperature, homogenize the heated alloy through soaking it, and then exposing the metallic part to an appropriate heat transfer media (also known as a quenchant) to cool it down. Furthermore, the common cooling media in a quenching process are water and oil. This because these types of liquids are widely available, easy to handle, and of low cost.
Some disadvantages of using these two types of quenching liquids are:
It has been shown that using carbonated water as a quenchant helps in reducing the geometrical expansion of the final product. This is because the carbon dioxide (CO2) bubbles within the water media reduces the formation of the air pockets on the quenched metal exposed surface, and hence an even heat transfer between the metal and the surrounding liquid can be achieved. Furthermore, when it comes to quenching metals in suspensions, the hot metallic surface will attract the dispersed particles from the host liquid, and thus forming a permanent attached thin film layer. The aforementioned mechanism is similar to the inner pipes foiling formation caused by suspension flowing at elevated temperature conditions.
US Published Patent Application No. 2014/0024026 A1 to Alocilja, et al., describes a method for producing nanoparticles and their dispersions. That reference describes fabrication of gold nanoparticles using a suspension including the gold particles, sodium carbonate, and an acid. The gold/base/acid combination is added to pure water to start a chemical reaction which releases the gold particles. The gold particles disperse within the base fluid, thus forming a gold-carbonated water suspension quencher used for metallic quenching and coating applications.
More generally, it is known to fabricate nanoparticles, functionalize these nanoparticles, and form suspensions of nanaoparticles.
A method for fabricating an effervescent suspension for metallic quenching and coating purposes is implemented by providing water in a container and providing a mixture comprising a solid alkaline, a solid acid, noble metal particles, the noble metal particles being selected from the group consisting of microparticles and nanoparticles. The mixture is added to the water to produce a reaction in the water resulting in the release of CO2 gas, and the CO2 gas disperses the noble metal particles in the water to provide the suspension. A hot material such as a metal or other material to which the noble metal will adhere, is heated to a temperature below its melting point, in the suspension, and is immersed to provide a quenched metal that has a temperature below its melting point in the suspension to provide a quenched metal coated with noble metal particles.
As used herein, noble metals, in addition to gold and platinum, include the other platinum group metals (ruthenium, rhodium, palladium, osmium, iridium), as well as silver. Additionally, the noble metal may include a broader set, including copper, mercury, technetium, rhenium, arsenic, antimony, bismuth and polonium, although in the case of mercury, coating may be impractical.
In non-limiting examples, the noble metal particles may comprise of different percentages of noble metal microparticles or noble metal nanoparticles with other micro or nano metallic particles, e.g., copper, silver, nickel, cobalt, rhodium, aluminium, palladium, and cadmium, depending on the desired coated layer color and carat standard. Thus, in the case of gold, the noble metal particles may comprise of different percentages of gold microparticles or gold nanoparticles with other micro or nano metallic particles, e.g., copper, silver, nickel, cobalt, rhodium, aluminium, palladium, and cadmium, depending on the desired coated layer color and carat standard. The noble metal particles may comprise a single noble metal such as pure gold, or may comprise a noble metal and one or more alloy metals. The solid alkaline may comprises a material selected from the group consisting of sodium bicarbonate (NaHCO2) powder and sodium carbonate (Na2CO3) powder. The solid acid may comprise monosodium phosphate (NaH2PO4) powder.
In further non-limiting examples, the mixture may comprise an effervescent tablet formed by mixing an acid powder and an alkaline powder to form a first mixture component, mixing an acid powder, an alkaline powder, and noble metals powder to form a second mixture component, and providing a tablet press with a die for compressing the powder into an effervescent tablet.
Overview
The present disclosure relates to a technique for producing gold of different carat and apparent color or other noble metal dispersions that depends in its formation using an effervescent tablet or solution. Carbonates and bicarbonates as effervescent agents are used to generate CO2 bubbles. The CO2 bubbles are used as a driving or agitation force for mixing and dispersing the nanoparticles within a host base fluid or liquid to form a suspension within a host base fluid or liquid. The formed suspension can be used for a quenching application and can be used for coating of an external bulk material. This allows coating of bulk materials with precious materials (e.g., gold of different carat and apparent color) that were originally dispersed as particles (e.g., AuNP with other alloys) in a host base fluid (i.e., water) using the effervescent tablet technique, in which the effervescent tablet facilitates forming the suspension. The base fluid and the effervescence tablet content further results in quenching the bulk material or targeted part, which result in the formation of the coating layer on its outer surface and the fixing or adhering of the coating material on the outer surface.
As used herein, noble metals, in addition to gold and platinum, include the other platinum group metals (ruthenium, rhodium, palladium, osmium, iridium), as well as silver. Additionally, the noble metal may include a broader set, including copper, mercury, technetium, rhenium, arsenic, antimony, bismuth and polonium, although in the case of mercury, coating may be impractical. The gold coated layer can be of different carat (e.g., 24, 22, 18 carat . . . etc.) and of different finishing colour (i.e., yellow, white and grey, pink and red, green, black, blue, and purple).
By way of non-limiting example, pre-prepared tablets are used to form a suspension. The carbonates and bicarbonates are used as effervescent agents to generate CO2 bubbles, which are the main driving force for mixing and dispersing the non-dissolving solid particles within the host base fluid or liquid to form the suspension. The technique provides an approach for fabricating gold-based carbonated water suspensions, as a quenchant, for metallic quenching and coating purposes.
This approach, by way of non-limiting example, uses pre-prepared tablets that are made of homogeneously mixed then compressed separate particles of gold and other alloys in the form of particles, decorated carbon nanotubes (CNTs) with gold particles and other alloys in the form of particles, decorated graphene with gold particles and other alloys in the form of particles, or attached particles of gold with other alloy particles via embedded CNTs links along with sodium carbonate powder, and monosodium phosphate powder. The gold particles would be combined with other alloy particles to have a resulting coating layer of different carat and color. The particles can be placed as separate particles within the mixture before being compressed, or via the decoration of CNTs or graphene (i.e., the CNTs or graphene will host the particles), or CNTs can be embedded in the gold and other alloy particles to connect them together. The CNTs embedded method and the CNTs and graphene decoration approach are available in the literature.
Alternatively a single noble metal can be provided, which would result in a coating of the single noble metal.
Furthermore, the manufactured tablet is utilized by adding it to pH-controlled water, pure water, deionized water, or hydrogen peroxide to start a chemical reaction, which then results in generating CO2 bubbles and releasing the gold-based particles. The bubbles then cause the host liquid to carbonate along with the gold and other alloys particles to disperse within the base fluid, and thus forming the gold-based-carbonated water suspension quencher used for metallic quenching and coating applications. This proposed approach is easy to use and reduces the possibility of geometrical expansion to the quenched part while providing a gold-based thin film on the outer surface part. While gold of different carat and colors is given as a non-limiting example, the process can be used for coating with other noble and/or platinum-group metals, and for coating with other metals.
The use of the pre-prepared tablets provides a system and method for forming gold-based-carbonated water suspensions, as a quenchant, for metallic quenching and coating purposes which uses pre-prepared tablets that are made of homogeneously mixed then compressed gold with other alloys particles, sodium carbonate, and monosodium phosphate. The manufactured tablet is utilized by adding it to pure water to start a chemical reaction which then results in generating CO2 bubbles and the releasing of gold with the other alloys particles. The CO2 bubbles then cause the host liquid to carbonate and those causes the gold with the other alloys particles to disperse within the base fluid, and thus form the gold-based-carbonated water suspension quencher used for metallic quenching and coating applications.
The disclosed technology presents an approach for quenching and coating metals using carbonated water gold (Au)-based suspensions. The carbonated water-Au-based suspension quenchant is formed by only adding a pre-prepared solid tablet to a reactive liquid, e.g., water. The selection of Au particles provides advantages in that this noble metal has high resistance to water, acidic, and alkaline environments as well as providing a valuable cost to the quenched part. Furthermore, the proposed method for fabricating the advanced quenchant can be considered as a one-step suspension production approach since no mixing device is required in the process.
A method for fabricating an effervescent suspension for metallic quenching and coating purposes is implemented by providing water in a container and providing a mixture comprising a solid alkaline, a solid acid, and noble and/or platinum-group metal particles. The mixture is added to the water (or a reactive liquid) to produce a reaction in the water resulting in the release of CO2 gas, CO2 gas dispersing the noble and/or platinum-group metal particles in the water to provide the suspension. A hot material, such as a hot metal, that has a temperature below its melting point, in the suspension, is immersed. This provides a quenched metal that has a temperature below its melting point in the suspension to provide a quenched metal coated with noble and/or platinum-group metal particles. The noble and/or platinum-group metal particles can comprise gold microparticles or gold nanoparticles along with other micro or nano metallic particles, e.g., copper, silver, nickel, cobalt, rhodium, aluminum, palladium, and cadmium, depending on the desired coated layer color and carat standard.
In one example of the technique, the solid alkaline comprises a material selected from the group consisting of sodium bicarbonate (NaHCO3) powder and sodium carbonate (Na2CO3) powder. The solid acid comprises monosodium phosphate (NaH2PO4) powder.
In one example of the technique, the mixture comprises a tablet formed by mixing an acid powder and an alkaline powder to form a first mixture component, mixing an acid powder, an alkaline powder, and noble and/or platinum-group metal powders to form a second mixture component, and providing a tablet press with a die for compressing the powder into an effervescent tablet.
In one example of the technique, the tablet comprises a mass ratio of NaH2PO4 to Na2CO3 to gold (Au) with other alloys particles of 20.4:6:1.
Process
The reactions depicted in
In a first stage, the effervescent tablets are fabricated. This is done by adding a solid alkaline, such as sodium bicarbonate (NaHCO3) or sodium carbonate (Na2CO3), with a solid acid and Au with other alloys in the form of standalone particles, decorated particles on the pores of the CNTs or graphene sheets, or interconnected particles via embedded CNTs links in a high energy reactive ball milling vial. The particles of Au and the other alloys can be provided as microparticles or nanoparticles. A non-limiting example of a solid acid used to form the solid acid is solid acid powder in the form of monosodium phosphate (NaH2PO4). The mass ratio of the described solid powders can vary; i.e., based on desired manufacturing processes but as a non-limiting example, the mass ratio of NaH2PO4 to Na2CO3 to Au with other alloys particles is 20.4:6:1, respectively. The aforementioned ratio was selected based on a simulation investigation that was performed in the Aspen Plus™ simulation tool.
The equilibrium composition of the products formed was calculated by minimizing the Gibbs free energy using the Aspen Plus™ RGIBBS reactor model depicted in
Na2CO3+NaH2PO4→NaHCO3+Na2HPO4 (eqn. 1)
NaHCO3+NaH2PO4→CO2+H2O+Na2HPO4 (eqn. 2)
The reactions are such that the balls that are used to mix the solid powders along with the high energy ball milling vial are advantageously made of gold of selected carat and color; i.e., similar to the main metallic powder elements of interest. The reason behind the aforementioned is that, in a high energy ball milling process the centrifugal force causes the ball to not only mix the powder but also to collide into each other and onto the inner vial surface. This collision (or impact) causes the outer surface of the balls and the inner vial surface to erode. Therefore, if the balls or the inner vial surface material are different from the main metal powder of interest, the resulting mixed powder will contain undesired metallic residuals from the cracking of balls and/or vial inner surface. The mixing duration can vary from short durations (e.g., 15 min) and up to days. Accordingly, it depends on the process design choice and how homogeneously the one wants to distribute the solid feedstocks into each other. Once all the solid powders are mixed, they are removed and placed in a tablet press instrument, where the solid powder mixture is mechanically compressed into a tablet.
Referring to
As can be seen from
In the process, a container is provided (step 401) and filled with water (step 402). The mixture of effervescent agents with solid particles are placed in the water (step 404). In the non-limiting example the mixture of effervescent agents with solid particles are provided in the form of a tablet such as described supra. The effervescent agents dissolve in the water and react in the water to release gold with the other alloys particles and release CO2 (step 407), as an effervescent bath.
An object for coating, given in the non-limiting example, as a metallic rod, is heated and placed in the effervescent bath, thereby quenching the rod (steps 411 and 412). This results in coating the portion of the object exposed to the effervescent bath being coated with noble and/or platinum-group materials such as gold with other alloys to coat the rod with gold or with gold and the alloy metals. The coated object can then be removed (step 415). The effervescent bath retains gold with the other alloys particles, which can be extracted and re-used.
While a metallic rod is described, this is given as a non-limiting example. The process is compatible with any suitable material to which the noble and/or platinum-group metals can adhere. This can be a metallic object, an object with a metallic surface, a photoplated object or any other suitable object to which adherence of a noble and/or platinum-group material is possible.
The as-prepared effervescent tablet is dropped in container containing water, of pH 7, to start a chemical reaction between the tablet and the host liquid (i.e., the pH 7 water). The resulting chemical reaction between the as-prepared effervescent tablet and water will cause the tablet to gradually dissolve. As the dissolving process takes place, CO2 gas (in the form of bubbles) will start to generate and the Au with other alloys particles will be released from the tablet. The buoyancy action of the bubbles will then cause the Au with other alloys particles to disperse within the hosting liquid, and thus producing the Au-based-water suspension. Once the tablet is fully dissolved, the high temperature metal is quenched in the suspension to cool it down. At this stage, the CO2 bubbles will provide an even heat transfer mechanism along the quenched part from the coolant media, and thus will highly reduce the possibility of uneven expansion to the final product that is usually experienced by conventional water. Moreover, at the quenching phase, the hot metal will attract the dispersed particles to its surface into forming a thin coated layer of Au with other alloys. The adhesion of the thin layer would be high, which means that the thin film will be highly attached to the surface due to the thermally formed bound between the particles and the hot metallic exposed surface. The previous process will also result in the coated layer having a smooth surface finish (i.e., of low surface roughness), which is the case with most thermal coating approaches.
It is noted that the remaining Au with other alloys particles in the quenchant, after the quenching process is completed, can be easily regained through centrifugation of the used suspension quenchant. At least in theory, no Au with other alloys particles will be lost from the proposed quenching and coating method. The previously explained suspension production and CO2 generation process from the as-prepared tablets, and hot metal quenching step is as depicted in
Several effects are noted, regarding the produced suspension:
The disclosed technology can be used by researchers working on suspensions and for industrial application, such as metallic quenching and coating. Advantages of the proposed technique are:
The disclosed technology provides Au with other alloys-carbonation water suspensions from just adding an as-prepared tablet to water, which can be used at any desired time. As such, it is one of easiest and robust approach to fabricate this type of advanced quenchant (i.e., Au with other alloys-carbonation water suspension) for metallic quenching and Au with other alloys coating purposes compared to all existing methods in the literature.
It is anticipated that the technique can be used for coating using metallic and semimetallic particles other than gold of different carats and colors and other noble and/or platinum-group metals. Therefore, different types of carbonated suspensions can be produced to form coatings of different types. Different parameters (e.g., tablet dimensions and shape, water temperature, and base fluid vial diameter) are expected to be effective in terms of dispersion physical stability and thermophysical properties.
It will be understood that many additional changes in the details, materials, steps and arrangement of parts, which have been herein described and illustrated to explain the nature of the subject matter, may be made by those skilled in the art within the principle and scope of the invention as expressed in the appended claims.
Number | Name | Date | Kind |
---|---|---|---|
10184025 | Ichikawa et al. | Jan 2019 | B2 |
11226335 | Day et al. | Jan 2022 | B2 |
11866610 | Alsayegh | Jan 2024 | B2 |
20020062888 | Stratton | May 2002 | A1 |
20100290043 | White et al. | Nov 2010 | A1 |
20120145554 | Liu | Jun 2012 | A1 |
20120225021 | Qian et al. | Sep 2012 | A1 |
20130189592 | Roumi et al. | Jul 2013 | A1 |
20140024026 | Alocilja et al. | Jan 2014 | A1 |
20140288194 | Niedermeyer | Sep 2014 | A1 |
20150110882 | Ichikawa et al. | Apr 2015 | A1 |
Number | Date | Country |
---|---|---|
106350328 | Jan 2017 | CN |