WO2009030011A2

WO2009030011A2 - Method and equipment for extracting the filler used in manufacturing porous materials parts and new porous materials enabled by this new technique

Info

Publication number: WO2009030011A2
Application number: PCT/BR2008/000274
Authority: WO
Inventors: Luis Melchert Faber Schmutzler
Original assignee: Luis Melchert Faber Schmutzler
Priority date: 2007-09-03
Filing date: 2008-09-03
Publication date: 2009-03-12
Also published as: BRPI0706019A2; WO2009030011A3

Abstract

'Method and equipment for extracting the filler used in manufacturing porous materials parts and new materials enabled by this new technique' this invention is a method to remove the polymeric filling material from pieces where it is desired to have communicating empty spaces porosity. This procedure of polymer extraction by dissolution, reduces costs and environmental complications and improves the quality providing the pieces a protective layer already at the end of the filler extraction process. The extracted polymer solution can be sold to other companies and generate cost abatement rather than be burned as in the old porous metals manufacture process. This new invented process will generate a reduction in porous metals production cost, such as aluminum and enable the production of porous metals with lower melting points and with more reactive metals, as an example, the alkali, which previously not survive the burning step of the usual polymer filler removing process. Precisely because this new process do not burn the polymer filler material and rather delicately dissolve this filling material, this process enables the creation of new porous materials with the basis of other polymers, whether thermoplastics, thermo-fixed or elastomers, ceramics, cement and derivatives or even vitreous. Here is presented a batch operation equipment designed to optimize the production and facilitate a large scale production. Here is also presented a marketing and production system for porous metal parts where the company would produce the porous material providing it in some standardized forms like plates and ingots where the porous material providing company would make it available already without the polymeric filler and the final producing company, would cut and press the part to the final form. As the porosity in this material is high, a little loss of it is in time and cost advantageous in comparison to the costs of the mechanical machining required. Cutting and pressing are very quick. Before this process, there was the polystyrene filler burning process which has its limitations. With this new filler material dissolution process, it becomes possible to apply a wide range of polymer-solvent pairs to produce porous parts by the filler extraction by dissolution process being that, the claims are for the process as a whole and the possible combinations, it would be very difficult to achieve list of all possible ones. There are also claims for the new porous materials, with basis of ceramics, polymers, cement and vitreous materials being that, the claims are calling for the porous parts production process, for the production with possible variations of polymer-solvent pairs and by these new types of materials made possible by the new process.

Description

"METHOD AND EQUIPMENT FOR EXTRACTING THE FILLER USED IN MANUFACTURING POROUS MATERIALS PARTS AND NEW POROUS MATERIALS ENABLED BY THIS NEW TECHNIQUE" Patent Presentation.

The present invention deals with a new method to remove the polymeric filler used in porous metals manufacturing and an equipment to perform this process in industrial scale. This new method enables the production of other new porous materials. The manufacturing moulds are filled with polymer grains where a metal is injected, poured or inserted. The removal method already present consists of polymer burning to clear the empty space; the method herein presented addresses the removal through dissolution which is delicate and refined allowing the filler recycling or its other uses.

As the removal of the filler is possible and delicate at low temperature, the creation and production of new porous product becomes possible as well such as ceramics, glasses or polymers which can be thermoplastic, thermo-fixed or elastomers. The equipment herein presented aims at enabling the extraction through dissolving the filler in large scale and the flourishing of the industry and trade of porous materials due to its accessible cost.

Some utilities of metals with communicating pores Porous metal components with communicating pores show interesting characteristics such as: low weight, good energy absortion, high dumping factor, flow permeability and reduced thermal conductivity in relation to the same solid material knowing that in applications where combinations of these properties are needed, the use of these materials provides interesting advantages. Among the main developed applications, we herein present briefly some of them such as improvement and components for the automotive, areospatial, light weight constructions, shipbuilding, railways, chemical, acoustic application and leisure industrys. Among the applications, there are components for a scheduled absorption of mechanical shock, ultra-light panels with good rigidity, noise and vibrations absorption, supports for catalytic converters, filters, battery and fuel cells electrodes, muffler, flame absorpbers, components for acoustic control, gas dispensers and movement absorbers for liquid transportation tanks. There is a considerable list of technological advantages and applications for porous metals of communicating pores; however, the difficulty in eliminating the filler which is used in its manufacturing process and consequently its cost, makes the economical choice an advantage just for few applications.

Description of the technique status referring to order The present technique status in porous metals production can be adequately described in "Handbook of Cellular Metals", a cellular metals manual published by Dr. Hans-Peter Degischer in 2002 and this technique is described as follows: the porous material is manufactured by injecting the cast metal at high speed in a mould previously filled with polymeric material grains, preferrably polysthyrene and pre-syntherized. As the formed metal-polymer block is a joined structure, it goes through a mechanical finishing stage where it is shaped, milled or else till getting the targeted measures and then goes through the polymer removal stage to clear the porous structure of the part. The polymner removal is performed at present by burning at low temperature causing the degradation and decomposition of this filler. This operation is carried out in an oven at controlled temperature and ventilation and it is expensive and polluting.

Presenting the existing problems

At present, the limitation to produce in large scale and the main concern in manufacturing the porous metallic material components is the filler polymer removal, so-called spacer, from inside the injected metal part on the polymer. There is at present a significant technological and market interests on what deals with porous material parts made of aluminum. It melts at a temperature of around 660°C, knowing that the polymeric filler is a hydrocarbon, the polymer burning temperature is normally higher than 1000°C, so it should be controlled as the Aluminum part would melt and would be lost. It is then necessary a delayed controlled burning where there is a material degradation and burning that incurs costs, pollution, and oxidation on all internal and external surfaces of the porous material. Besides that, there would be a geometric distortion of the machining causing a considerable reduction in the manufactured material quality. In all, the present process of the filler polymeric burning requires power and generates greenhouse gas emissions and pollutants resulting from the polymer; due to burning also. The heating up of the part causes a quality loss in the mechanical adjustment and finishing and it oxides the large surface of a porous material. All this increases the cost and reduces quality.

The last obstacle for an in-bulk production for the market eager for porous metal parts is the polymer filler removal from inside the metal-polymer matrix in the manufacturing process. This removal should be performed in a way that generates acceptable economical and environmental costs and it should be able to be implemented in large scale without exposing the material to high temperature so that to avoid melting and compromise the hardening or the machining threshold previously performed or incorporate oxidation to the product. The use of a controlled burning operation even at the lowest possible temperature, it is still considered very high for many materials species; as it can be used at ambient temperature, this filler extraction technique through dissolution, enables the porous materials production as from the matrixes with low fusion point such the one between metals, for example, lithium that casts at 180°C, tin at 232°C or indium at 114°C or materials that oxide in a violent reaction like sodium, lithium, calcium, and potassium. Among almost all polymers melt or start to degrade in the same temperature range of the filler which is also a polymer that would be removed in the controlled burning process used at present. The ceramic component production can also become feasible, mainly with matrixes whose hydration water is sensitive to temperature. The porous parts production in ceramic materials through the traditional technique and using polymeric fillers is not possible by the present process because the polymer dilatation coefficient is higher than the ceramic materials one which means that at the start of the green body burning, the filler dilatation breaks the ceramic part in different points making it useless. This technique allows the polymeric filler extraction from the pressed body with any mechanical stress enabling the part to be taken to the next stage where it undergoes high temperatures to perform its sinterization. So this process invention enables the porous parts manufacturing of ceramic materials and it provides a new technique for porous ceramic materials production.

The porous parts production in polymeric materials through the traditional technique using polymeric fillers burning is not possible, because there would be no way to eliminate selectively one of the polymers without destroying the other using the controlled burning or any other thermal resource, as when the heat is applied in the oven for controlling the filler burning, both polymers are destroyed. This new technique enables the extraction of the polymeric filler from the part produced in a different polymer without compromising the matrix polymer. Thus the invention of the process enables the polymeric porous parts manufacturing using polymeric fillers and a new technique of the porous polymeric materials production. Presenting the general solution.

Here are the objectives of this invention: enabling the manufacturing process of porous metals, the production of other porous materials as ceramics and polymers and providing the commercial production in large scale of metals and other porous materials through an equipment developed for this operation, removing in a delicate way through dissolution or just . washing the polymeric filler that can be recycled or have other applications.

To facilitate the commercial development, a standardization form is presented to facilitate the production of components with pre-manufactured parts. Detailed description of the invention and designs presentation

To simply understand the morphology of a porous material with communicating pores, Figure 1 exposes a geometric description of the process to obtain the porous materials and the manufactured material concept with a filling technique which is removed later on. Item 1 - it is the geometric representation of one mould in a parallelepiped form where the first three layers of the filler grains were designed; they are represented in this design in well arranged spheres for an illustrative effect; actually the disposition is random and the forms can be varied. Item 2 is the design representing the front view of the cut in the layer vertical plan of filler grains arranged in an ideal form. Item 3 represents the same cut after filling the injected material and item 4 is the vertical cut plan of porous material after the filler removal. To get a porous material with connecting or communicating pores, it is important that the filler polymer particles are in contact with each other according to the present process ensuring through a heating that generates a sinterization of polymer grains.

In the new process here presented, the sinterization which was based on heat can be replaced by a bath wash with a polymer solution in a solvent recovered in the extraction process as this solution from the polymer itself promotes an efficient grain sticking and more power savings. The fixation among grains is performed to ensure the contact among removable parts of the manufactured material so that to provide later an external access and to promote the filler removal. For this reason, it is important to have communication among the pores, i.e. among the remaining spaces. The communication among the pores is fundamental to have a filler flow out of the part. A continuous space is formed through grains contact and from which the flow happens and for which the filler is removed, releasing the porosity space by the burning or dissolution process.

Another geometric exemplification is shown in item 5 where there is an upper view of the horizontal plane cut in the first layer of the filler grains of the mould shown in item 1 displaying the filler grains disposition in light gray. In item 6, the upper mould view with the filler polymer, in light gray, and the injected material that should be the porous material manufactured in dark gray. In item 7, the injected material upper view, in dark gray, after the filler removal clearing the empty spaces from porosity and in item 8, the views of the three horizontal cuts of the porous material at the three grains layers heights and their superposition resulting in the emptied and permeable structure of the obtained material,

The biggest problem presented here is basically to remove a filler polymer from inside the compound material aiming at clearing the empty space relative to material porosity that we want to produce. There are two main solutions groups for the problems presented her:

1 -Dissolution of the polymer filler in solvent, knowing that this can be in normal or supercritical state, or the use an emulsifier, adequate for removing the polymer. 2- Reduction of filler polymer viscosity through a plasticizer and removal through an external force, turbulence or centrifugation. In all cases, the heat can be applied in a way to reduce the viscosity and facilitate the work without causing a degradation of the filler material.

The new process herein presented addresses the reduction of the filler viscosity to remove it from inside the manufactured part in a delicate way and which enables such recovering. In all the presented variations, the polymer is not burnt or destroyed, it has the structure of its material temporarily changed and consequently its viscosity is reduced enough, being dissolved, plasticized or melted, to be removed by flow to outside the produced part body. In figure 2, there is in item 1 an image of the material in the polymer-metal matrix form with the measure already adjusted by a mechanical finishing, machining, and in item 2 a part of the same type that underwent the extraction process with a solvent where it is possible to verify the obtained delicate porous structure. As the porous metal parts have a tridimensional structure able to absorb large quantities of power suffering deformation, it is possible to produce sheets and billets of several profiles and thicknesses in a way that the client, who processes the material, can cut in portions or pieces close to final measures and perform the press in a stamp, in a way to get the right measures and forms of the final part. This production procedure avoids the need of mechanical finishing what consumes time and capital. For a solid metal, the expenses with stamping and power for press are much higher that for a porous material. This technique to produce the metal sheets and billets facilitates, accelerates and distributes its cycle of production but the manufacturing company of porous metal undertakes the task to produce the metal-polymer matrix and to extract its filler.

The dissolution is a property that many species of thermoplastic polymers have; it deals with dissolving in specific solvents provided that using this property, the polymeric filler is dissolved and washed from inside the part being manufactured, clearing the internal empty space - its porosity. The solution for the problem should be to remove the filler without increasing the temperature enough to stress the material, without exposing it to oxidant atmospheres or consuming more power or generating an environmental impact. This can be done by dissolving the filler in a way to enable the materials recycling and the trading of the produced polymeric solution; these characteristics are reached through the technique addressed in this work.

According to solubility theory, substances with close numbers of Hildbrand dissolve, however this description is utterly simplified for this case. Aiming at better results, Hansen decomposed Hildebrand number in three components: interactions by Hydrogen Bridges, j _h, Dispersive coming from London forces, j _d, and Polar interactions, j _p, that can be of the type described by Keenman when coming from interactions among polar species or of the type described by Debye, when the interactions among species with dielectric permanent polar moments and induced moments. The unit widely used for j_h, j_d e j_p is the (MPa)¹⁷² (Bueno 1978) and (Hansen 1967).

Hansen developed a way to represent the three components creating a graph in three dimensions, an axle for each component where each solvent occupies a position in the space in relation to others and the polymer, occupies the central position of a sphere where the radius is denominated polymer interaction radius. If the solvent coordinate is contained in the polymer volume, there is a big chance that it dissolves the polymer. However, as a tri-dimensional representation, it is very difficult to put in a text that another representation form was created, where there is a Cartesian graph with axes for units associated to polar interactions and Hydrogen connection, remaining without a dispersive component representation. With the polymer interaction radius, a circumference is designed as from the polar interactions coordinates and hydrogen and that is how solvents closer to the center become the best candidates to dissolve the polymer. The ones close to the edge can be out of the sphere, above or below, but in its shade which does not ensure the sufficient compatibility for the dissolution.

Another form to estimate if there a dissolution is the use of equation (1) where the distance between the solvent and the polymer, D_(Soi_-Poi), is calculated taking into consideration the three components in question, for the solvent and for the polymer as well, knowing that if the distance is smaller than the polymer interaction radius, in this case the new polysthyrene with 12,7 MPa^l/2, there could be a dissolution.

D(soi-Poi) = [ 4.( j _ds- j dp)² +( j _Ps- j pp)² +( j _hs- j hP)² ]^m (1)

Table 1 shows a list of several solvents and the distances calculated through Eq. (1) with Hansen parameters for the candidates to be polysthyrene solvents (Hansen 1971) and (Barton 1983). With these data, a comparison can be carried out to estimate which solvent has a good solubility.

To perform the choice of a solvent for an industrial process, it is not enough to dissolve the polymer, but other factors also are important as they are going to reflect on the facility cost, operation, environment impact, and process safety. Here are the main factors that are listed in Table 1 and discussed below: • The dissolution speed which is the diffusion coefficient function and which in turn is associated to the molecule size and that is going to influence directly the facility size.

• Toxicity and vapor pressure, labor costs and safety measures, IDLH.

• Fire risks, safety costs, facility location and insurance, NFPA.

• Operation pressure and temperature conditions, equipment building costs and expenses with operation and maintenance power.

Table I: some interesting characteristics for selecting the extraction process solvent.

isomer cis, to trans T^evap(°C) = 48. ³ -IDLH - Immediately Dangerous for Life and Health in ppm,. ⁴ -NFPA - National Fire and Protection Association, NL -Not listed. (Cetesb 2007) and (CDC 2007)

Sub-products destination. Taking into consideration the present and future trend to preserve the environment reducing the emissions and environmental impacts, this factor can be the difference between the success and failure of a new production process. Using the technique for dissolving the filler, which is a delicate form to remove a material from inside another one, enables the manufacturing of a wide variety of new materials, not only metallic with low fusion point or reactive to the air like alkaline, but also ceramic materials, glass and polymeric with communicating pores. In one of the main techniques for ceramic components manufacturing, a material powder in which we want a component, is pressed forming the so-called green body which is then sinterized at high temperature. This technique is used in ceramics of molecular types and ionic ones as well since they don't have hydration water or components that get degradation at the sintering temperature. The breaks problems that arise in sintering is due to the fact that ceramic materials have very low dilatation coefficient and the polymeric materials have high coefficients. During the heating there is a break of the weak joints between the grains caused by the difference between thermal dilatations resulting a part highly fragmented component. For this reason, it is not possible to manufacture the porous ceramic part using the polymer fillers. With the use of this dissolution technique, there is a delicate removal by dissolution of the filler remaining the green body cleared from polymeric material before being sinterized and resulting in an entire ceramic part. A ceramic porous component for example: of alumina, silicon carbide or boron carbide can have applications in sensors for hot fluids, ballistic armor or thermal armor. As we do not have to expose the manufactured part to high temperatures to burn the filler, this dissolution technique of filler polymer provides the production of sensitive ceramic materials parts at temperature as they have hydration water or another sensitive component that is to be preserved. An interesting example is the cement or porous concrete parts manufacturing knowing that the part leaves the production area with a protective layer and a polymer finishing. The utility would be in finishing panels for acoustic absorption and impacts absorption and protections shock waves against explosions, bullets or collisions.

It is possible to dissolve a thermoplastic polymer without affecting another polymer since there is a solvent that dissolves only the polymer that is to be eliminated. The material to be eliminated should be a thermoplastic as those can be dissolved. The material in which to produce the porous part should be a thermoplastic, thermo-fixed or elastomer, and it has to be just from another non-soluble species in the same solvent that is to be used to extract the filler. This enables the production of porous polymer parts using other polymers like filler and solvents that do not dissolve any of them, extracting only the filler, preserving the injected or poured material. A possible application would be shock absorbers with several elastic constants able to perform the power absorption in progressive stages for several machines, for example in sportive shoe soles or tennis racket handle.

There is at present a wide variety of polymers and solvents that provide several combinations between these species in a way to use a filler polymer to manufacture the part and a specific solvent to remove the filler from inside the manufactured part, metallic, polymeric, glass, or ceramic. Table II shows some examples:

Until the development of this technique, polysthyrene was used; it has low cost for the filler function so it would be disposed. Nevertheless, this technique provides a way to recover and re-use the filler and then the use of materials with more advanced and premium properties and which are always expensive. An example is the polytetrafluoroethylene, known as Tefion^r or PTFE or Polyetherethercetone, PEEK, which cast at a temperature close to 340°C, or polycarbonate at around 265⁰C, in contrast with the one used at present which is polysthyrene that casts at 100 to 200°C depending on the type. As the solvent intercession is not marked with a polymer, this does not mean that there is no dissolution; just it is not mentioned in the table above.

As we can notice through the explanation above, the use of several solvents or combinations, as well as polymers and combinations is possible to carry out the filling material. The privilege for the filler polymer extraction through dissolution will be asked in the claims section. Once the extraction by dissolution path is found, there could be many possible combinations. Table II: Examples of thermoplastic polymers and solvents common in the market

When the fluids have their temperature and pressure increased above the critical temperature and pressure, they get to a state called supercritical state. In this state, the properties vary continuously between the liquid and the gas ones; there is no boundary of evaporation or condensation knowing that their dissolution and density properties become easily adjustable with small differences of pressure or temperature and the density remain in general close to the liquid one and the viscosity and diffusivity close to the gas one making the operations to be faster and the separation solute-solvent can be carried out with a small change in equilibrium conditions of pressure and temperature conditions. The dissolution capacity becomes tunable knowing that it is possible to carry out separations highly selective as for example by the size of polymerization chain of the same polymer. In order to dissolve Polyesthyrene with pure fluids in supercritical state as carbon dioxide, CO₂, they are needed 2100 atm and 225°C (Rindfleisch. F. 1996), but in supercritical fluids the solvent mixture aiming at more flexible operating conditions is also possible; the mixture CO₂ with ethanol dissolves the polyestherene at 150 atm and 60°C (Tassaing T. 2000).

Despite the difficulties to work with fluids in supercritical state, they can be used in a way where they act as plasticizers reducing drastically the polymer viscosity and allowing a flow from outside with a small external force coming from agitation or centrifugation. As there is a certain heat application, necessary for most fluids to reach the supercritical fluid state, possibly not to have in these cases a clear boundary among dissolution, plasticizing and melting. The extraction of filler material can be performed by a fluid when it is taken to a determined supercritical state; it acts as a specific solvent. This way, adjusting the temperature and the pressure, a fluid for example, liquefied carbon dioxide can be used to dissolve a polymer if the temperature is lower than its fusion one or dissolution and fusion if it is higher than its melting one. Here it is presented a machine to perform the extraction and/or filler material washing in parts batches, this equipment performs a washing with specific solvents knowing that this machine can be used from the laboratory to the industry scale.

For a large scale production, an equipment is needed to produce in bulk and it should have a high performance and put easily in production line. The speed variation of solid dissolution in a solvent depends basically on two controllable variables in the project of an equipment: the diffusion coefficient that can optimized and reproduced with a temperature control and the fluid flow boundary layer thickness, which it can be improved with the increase of forced turbulence by the fluid flow. This information comes from the transport phenomena science applied to unit operations (Cremasco 1998) and (Foust 1983).

In the developed extraction equipment, the temperature is controlled by the use of a heat exchange case with thermal fluid. The fluid turbulence close to parts that are being treated is gotten by the flow of the solvent pumped from the bottom of treatment tank that goes up by the sides between the vase walls and the parts basket and guided by chicanes, overflowing inside the basket which is holding the parts under treatment and then returning to bottom after flowing down the parts and crossing the basket bottom grill as shown in Figure 3, where: 1- main equipment vase, 2- vase lid, 3- motor of the solvent circulation pump, 4- pump impellor disc, 5- solution outlet valve,

6- solvent inlet valve, 7-tube section that compose the basket side of parts to be processed, 9- parts to be treated, 10- side chicanes for basket support and solvent flow direction, 11- case for thermal control fluid, 12- accesses for the thermal control fluid. In case of very big equipment or for processing very delicate parts that cannot be piled, the processing basket can divided into several pieces which avoids damages caused by denting the parts and also it accelerates the loading and unloading process of the machine as shown in Figure 4 where: 1 - receiving of parts coming from the mechanical machining section for dimensions adjustments and their distribution in baskets for the polymer extraction stage, 2- assembly in piling of baskets to put them in extraction machine with a crane when needed, 3- put a basket set with the parts to be processed inside the extraction machine, 4- removal of baskets set with processed parts,

5- baskets sampling, parts removal and delivery to next stage of the production line.

Examples of the invention concretization and comparison with the technique state

Comparative example

There are many advantages of this new process: Recycling and other utilities for polymer solution which is a process by-product:

Through concentration or distillation, the solvent and the polymer can be recovered. The solvent would be easily reused in the extraction process. The polymer would need to be extruded and cut in pellets to be reused as filler for new parts to be cast. Due to degradation observed in the polymer, a part of it should be in the continuous industrial application replaced by a new polymer, knowing that the disposed part still in solution can have other uses.

The Polysthyrene dissolution in ethyl acetate corresponds somehow to the manufacturing process of some types of lacquers, varnish, paints, and glue knowing that in this case and as there is a change of the polymer color to brown, there can be savings in pigments in the formulation of some products. The industrial activity of porous components production can be associated to a manufacturing of some of these products because, the by-product of the aluminum porous parts production, Polyesthyrene solution of in ethyl acetate, is one of the intermediate products of glue and paint industry. In Brazil, some polymer processing companies dissolve their scrap in ethyl acetate and sell them to other companies that produce glues for example.

As it is not necessary to have a burning or thermal degradation of the polymeric filler, the generation of effluent pollutants, power expense and unnecessary gas generation of greenhouse effect are directly avoided, by the burning and indirectly by the consumed power. It favors also permitting the filler polymer recycling and its solvent; if the recycling route is targeted, but it also allows its use in the polymer solution form in solvent in other processes or products such as paints, resins, varnishes, knowing that the removed polymers is dissolved at the end of the extraction from inside the manufactured porous material, producing this way a precursor for other industrial products.

When extracting the filler polymeric material without degrading it to gas, just reducing its viscosity and flowing it outside, a residual layer is allowed to remain adhered on surfaces of the matrix material, supplying an initial protection against oxidation or any action of another agent present in the ambient that is undesired. The residual layer thickness can be regulated by the filler polymer dilution knowing that the more viscous the solution is, the thicker the residual layer is.

The residual layer left after the diluted filler polymer flow, can facilitate the gluing and fixing the porous material structure according to the case of the part use. This layer can be eliminated using a second washing with a solvent adequate for the used polymer. The advantage of not using thermal reactions or expose the part to oxygen, is the preservation of the metallic character of the whole surface that in case of a porous material it is big, if compared to the volume. The oxidation of an uncertain part of the material implies with an unpredictable change of the mechanical properties projected for the manufactured component, though, this technique promotes better superficial characteristics of mechanical properties and of properties dispersion values for the manufactured parts.

As the extraction can occur without high temperatures or thermal gradients, that enables the obtained precision in the mechanical machining of the compound polymer-matrix to be preserved. As the part machining operation in the form of a block of polymer-matrix, it is desired because it is easier to be performed.

The technique herein presented enables the production in bulk to reduce the financial costs and the environmental impact and also for the production capacity possible to be reached by the developed equipment presented here. The equipment herein described allows the large-scale removal of the polymeric material filler, used in the porous metals manufacturing. This equipment also enables the production of other porous materials through the use of the same technique.

The porous material quality is shown in Figure 2 in item 2, where the proof body polymeric material filler was extracted from a previously machined in a mechanical lathe machine as shown in item 1. The extraction operation was performed using the technique presented in this text. Advantages Summary:

The main advantage of this new method, process and equipment is that it enables the production in large scale as it reduces the financial costs and the environmental impact allowing the material recycling and other uses in synergy among companies.

The polymer dissolution is a delicate form to extract the filler used in porous metal parts manufacturing. It preserves details and fine finishings carried out previously in the component. The process of polymer dissolution can, if desired, leave a residual protective layer on the exposed surfaces, internal or external. If the part is fixed with compatible glue with the used polymer in the manufacturing process, the residual layer should help in fixing and distributing the forces through the delicate structure of the porous part.

The polymer solution extracted from the porous material parts can be traded with production units of paints, lacquers, varnishes or glue or even recycled. If the solvent is extracted from the solution through distillation, it can be reused in new extractions and the polymer can be extruded and cut into pellets, so that to act again as a filler in the manufacturing of new porous parts.

The ethyl acetate seems to be the most proper solvent for the process as the solution resulting from the process, can be used in other industrial processes without many difficulties.

The trichloroethylene is an interesting solvent for the process mainly for operations where there is predominantly the materials recycling.

This process minimizes the emissions and the environmental impact of this production phase of porous materials. There is no burning or big power consumption.

There is a possibility to perform the extraction with fluids in a supercritical state, the advantage is that a distillation to recover the polymer and the solvent would not be necessary.

The extraction equipment described in the discussion section is a good form to implement a large scale production line process of polymer filler extraction, as described in this work.

This process allows the synergy among companies that leads to a reduction in costs and environmental impacts.

The description above of the present invention was presented with the objective of illustration and description. In addition, the description does not aim at limiting the invention in the form here revealed, but particularly for eliminating an obstacle, it opens the porous metallurgy area to commercial application. Consequently, variations and modifications compatible with the teachings above and the ability or knowledge of the relevant technique are within the present invention scope. Thus, the modalities described above aim at explaining the modes known for the invention practice and allowing the technicians in the area to use the invention in such modalities or others and with the several modifications necessary for the specific applications or the present invention uses. The intention of the present invention is to include all its modifications and variations within the scope described in the report and attached claims.

Claims

1 - "METHOD AND EQUIPMENT TO EXTRACT POROUS MATERIALS FABRICATION FILLER AND NEW MATERIALS THAT HAD BECOME POSSIBLE BY THIS NEW TECHNIQUE "characterized by the procedure and equipment with which porous materials components with communicating void spaces, manufactured by this process that uses soluble filling material, have this filler removed from its interior by dissolution with a solvent to release the empty space of porosity, with or without the application of heat. In order to finalize the process of manufacture of porous materials with communicating void spaces, allowing if desired to recover the filler material, aimed at recycling, or the use of the produced polymer filler solution in another processes, avoiding the pollution and energy spent in the current process and reducing the cost of the produced component, enabling a financial income increase for the porous material producing industry by the polymer solution sell to another company.

2 - "METHOD AND EQUIPMENT FOR EXTRACTING THE FILLER USED IN MANUFACTURING POROUS MATERIALS PARTS AND NEW MATERIALS ENABLED BY THIS NEW TECHNIQUE " characterized by the procedure and equipment with which porous materials components with communicating void spaces manufactured by process that uses soluble filling material in this case have the polystyrene filler removed from its interior, by dissolution by a solvent that can be ethyl-acetate or trichloroethylene, or toluene, or benzene, or cyclo-hexanone, or triclorotrifluor-ethylene, or other fluid with ability to solve for this polymer, in a liquid or in supercritical state, to release the empty space of porosity, to finalize the process of manufacture of porous material with communicating void spaces, with or without the application of heat.

3 - "METHOD AND EQUIPMENT FOR EXTRACTING THE FILLER USED IN MANUFACTURING POROUS MATERIALS PARTS AND NEW MATERIALS ENABLED BY THIS NEW TECHNIQUE " characterized by the procedure and equipment with which porous materials components with communicating void spaces, manufactured by this process that uses soluble filling material, in any case have this soluble polymer filling removed from its interior, by dissolution by any solvent fit for this task, whether in a liquid state or in supercritical state, to release the empty space of porosity, to finalize the process of manufacture of porous material with communicating pores, with or without the application of heat.

4 - "METHOD AND EQUIPMENT FOR EXTRACTING THE FILLER USED IN MANUFACTURING POROUS MATERIALS PARTS AND NEW

MATERIALS ENABLED BY THIS NEW TECHNIQUE " characterized by the procedure and equipment with which porous materials components with communicating void spaces, manufactured by this process that uses soluble filling material, have this filler removed from its interior by interaction with plasticizer substance and that the plasticized polymer to be removed from the piece by any external force, whether of agitation, vibration or centrifugation, with or without the application of heat.

5 - "METHOD AND EQUIPMENT FOR EXTRACTING THE FILLER USED IN MANUFACTURING POROUS MATERIALS PARTS AND NEW MATERIALS ENABLED BY THIS NEW TECHNIQUE " characterized by the procedure and equipment with which porous materials components with communicating void spaces, manufactured by this process that uses soluble filling material, have this filler grains fixed to each other by a stage of collage performed by exposure to some of the polymer solution from the previously extracted polymer or a solvent bath, to dissolve the surface and get glued after dry, or other glue able to service, with or without the application of heat.

6- "METHOD AND EQUIPMENT FOR EXTRACTING THE FILLER USED IN MANUFACTURING POROUS MATERIALS PARTS AND NEW MATERIALS ENABLED BY THIS NEW TECHNIQUE "characterized by the procedure and equipment with which porous materials components with communicating void spaces, manufactured by this process that uses soluble filling material, have this filler removed from its interior by dissolution in batch cycles, from laboratory to industrial-scale as described in the descriptive report and Figures 3 and 4, where a flow of fluid solvent, which can have a controlled temperature, will be moving in a toroidal path, constantly passing trough the parts in order to provide agitation and accelerate the process of extraction of the filler material.

7- "METHOD AND EQUIPMENT FOR EXTRACTING THE FILLER USED IN MANUFACTURING POROUS MATERIALS PARTS AND NEW MATERIALS ENABLED BY THIS NEW TECHNIQUE characterized by the procedure and equipment that enables the large scale porous aluminum production using a solvent to dissolve and remove the manufacturing filling material.

8- "METHOD AND EQUIPMENT FOR EXTRACTING THE FILLER USED IN MANUFACTURING POROUS MATERIALS PARTS AND NEW MATERIALS ENABLED BY THIS NEW TECHNIQUE " by the procedure and equipment that enable the large scale porous aluminum production using the dissolution of the manufacturing filler material, polystyrene, with the solvent trichloroethylene, or ethyl-acetate. 9 - "METHOD AND EQUIPMENT FOR EXTRACTING THE FILLER

USED IN MANUFACTURING POROUS MATERIALS PARTS AND NEW MATERIALS ENABLED BY THIS NEW TECHNIQUE " characterized by the procedure and equipment that enable the production of porous metals which can be produced in sheets or billets with different thicknesses and profiles to be commercialized and completed by the final-manufacturer.

10- "METHOD AND EQUIPMENT FOR EXTRACTING THE FILLER USED IN MANUFACTURING POROUS MATERIALS PARTS AND NEW MATERIALS ENABLED BY THIS NEW TECHNIQUE " characterized by the procedure and equipment that enable the production of a new material consisting of porous cement or concrete components, to be produced from small to large scale, manufactured by dissolving its polymer filling material. If the process uses any pair of polymer and solvent, citing as an example but not limited only to this, polystyrene and ethyl acetate, and the new porous material based on cement, mortar or concrete.

11 - "METHOD AND EQUIPMENT FOR EXTRACTING THE FILLER USED IN MANUFACTURING POROUS MATERIALS PARTS AND NEW MATERIALS ENABLED BY THIS NEW TECHNIQUE " characterized by the procedure and equipment that enables the new porous material based on cement, mortar or concrete, applicable in absorption of impact, shock waves from explosions, ballistic armor and sound absorbers for acoustic treatment. 12 - "METHOD AND EQUIPMENT FOR EXTRACTING THE

FILLER USED IN MANUFACTURING POROUS MATERIALS PARTS AND NEW MATERIALS ENABLED BY THIS NEW TECHNIQUE " characterized by the procedure and equipment that enable the production of a new material consisting of porous ceramic parts, from small to large scale, manufactured by dissolving its polymer filling material. Using the process any pair of polymer and solvent, citing as an example but not limited only to this, polystyrene and ethyl-acetate, and the new porous material based on ceramics in general.

13 - "METHOD AND EQUIPMENT FOR EXTRACTING THE FILLER USED IN MANUFACTURING POROUS MATERIALS PARTS AND NEW MATERIALS ENABLED BY THIS NEW TECHNIQUE " characterized by the procedure and equipment that enable the production of a new material consisting of porous thermoplastic polymer parts, from small to large scale, manufactured by dissolving its polymer filling material. Using the process, any pair of polymer and solvent, citing as an example but not limited only to this, polystyrene and ethyl-acetate, and the new porous material based on thermoplastic polymers in general.

14 - "METHOD AND EQUIPMENT FOR EXTRACTING THE FILLER USED IN MANUFACTURING POROUS MATERIALS PARTS AND NEW

MATERIALS ENABLED BY THIS NEW TECHNIQUE " characterized by the procedure and equipment that enable the production of a new material consisting of porous thermo-setting polymer parts, from small to large scale, manufactured by dissolving its polymer filling material. Using the process any pair of polymer and solvent, citing as an example but not limited only to this, polystyrene and ethyl-acetate, and the new porous material based on thermo-setting polymers in general.

15 - "METHOD AND EQUIPMENT FOR EXTRACTING THE FILLER USED IN MANUFACTURING POROUS MATERIALS PARTS AND NEW MATERIALS ENABLED BY THIS NEW TECHNIQUE " characterized by the procedure and equipment that enable the production of a new material consisting of porous elastomer polymer parts, from small to large scale, manufactured by dissolving its polymer filling material. Using the process any pair of polymer and solvent, citing as an example but not limited only to this, polystyrene and ethyl-acetate, and the new porous material based on elastomeric polymers in general. 16 - "METHOD AND EQUIPMENT FOR EXTRACTING THE

FILLER USED IN MANUFACTURING POROUS MATERIALS PARTS AND NEW MATERIALS ENABLED BY THIS NEW TECHNIQUE " characterized by the procedure and equipment that enable the production of a new material consisting of porous vitreous polymer parts, from small to large scale, manufactured by dissolving its polymer filling material. Using the process any pair of polymer and solvent, citing as an example but not limited only to this, polystyrene and ethyl-acetate, and the new porous material based on vitreous polymers in general.

17- "METHOD AND EQUIPMENT FOR EXTRACTING THE FILLER USED IN MANUFACTURING POROUS MATERIALS PARTS AND NEW MATERIALS ENABLED BY THIS NEW TECHNIQUE " characterized by the procedure and equipment that enable the production of a new material consisting of two order porosity being, a small size originated from the elimination of load while burning the piece and the larger, originated from the dissolving its polymer filling material. Using the process any pair of polymer and solvent, citing as an example but not limited only to this, polystyrene and ethyl-acetate, and the new porous material based on ceramics in general with tow size of pores. 18- "METHOD AND EQUIPMENT FOR EXTRACTING THE FILLER

USED IN MANUFACTURING POROUS MATERIALS PARTS AND NEW MATERIALS ENABLED BY THIS NEW TECHNIQUE " characterized by the procedure and equipment that enable the production of new porous materials consisting of eliminating by the dissolution of the polymer filler from the produced parts, from small to large scale, consisting the filler of expanded polystyrene, commercially known as Styrofoam, produced or mold-injected in a proper form to fit the part under production and to be removed by dissolution.

19- "METHOD AND EQUIPMENT FOR EXTRACTING THE FILLER USED IN MANUFACTURING POROUS MATERIALS PARTS AND NEW MATERIALS ENABLED BY THIS NEW TECHNIQUE " characterized by the procedure and equipment that enable the production of new porous materials consisting of eliminating by the dissolution of the polymer filler from the produced parts consisting the filler of polystyrene or expanded polystyrene, commercially known as Styrofoam, produced or mold-injected in a proper form to fit the part under production in tri-dimensional planed layers, like shown in Figure 1 but not limited to that design and to be removed by dissolution. 20-"METHOD AND EQUIPMENT FOR EXTRACTING THE FILLER USED IN MANUFACTURING POROUS MATERIALS PARTS AND NEW MATERIALS ENABLED BY THIS NEW TECHNIQUE "characterized by the procedure and equipment that enable the production of new porous materials consisting of eliminating by the dissolution of the polymer filler from the produced parts consisting the filler of polystyrene or expanded polystyrene, commercially known as Styrofoam, produced or mold-injected in a proper form to fit the part under production in tri-dimensional planed layers and to be removed by dissolution for technical or decorative purposes, such as tri-dimensional multi-layers sculptures 21-"METHOD AND EQUIPMENT FOR EXTRACTING THE FILLER

USED IN MANUFACTURING POROUS MATERIALS PARTS AND NEW MATERIALS ENABLED BY THIS NEW TECHNIQUE ""characterized by the procedure and equipment that enable the production of new porous materials consisting of eliminating by the dissolution of the polymer filler from the produced parts, consisting the filler of polystyrene or expanded polystyrene, commercially known as Styrofoam, produced or mold-injected in a proper form to fit the part under production in tri-dimensional planed layers and to be removed by dissolution technique aiming at producing technical parts to form porous structures with tri-dimensional multi-layers for electromagnetic armor, scheduled dispersion of electromagnetic radiation including radar waves.

22-"METHOD AND EQUIPMENT FOR EXTRACTING THE FILLER USED IN MANUFACTURING POROUS MATERIALS PARTS AND NEW MATERIALS ENABLED BY THIS NEW TECHNIQUE " characterized by the procedure and equipment that enable the production of new porous materials consisting of eliminating by the dissolution of the polymer filler from the produced parts, as described earlier as metals, ceramics or polymers, consisting the filler of polystyrene or expanded polystyrene, commercially known as Styrofoam, chopped or crushed originated from recycling sources, giving the possibility to solve the severe ecological problem of Styrofoam used packages destination, using it as filler for porous materials production.

23-"METHOD AND EQUIPMENT FOR EXTRACTING THE FILLER USED IN MANUFACTURING POROUS MATERIALS PARTS AND NEW MATERIALS ENABLED BY THIS NEW TECHNIQUE " characterized by the procedure and equipment that enable the production of new porous materials consisting of eliminating by the dissolution of the polymer filler from the produced parts of porous material based on ceramic and cement material, that can be used to compose the fixing basis of coral organisms so that to form the basis for new coral banks or coral reefs. That helps to prevent the extinction of these species and also facilitates the carbon fixing in oceanic structures.

24-"METHOD AND EQUIPMENT FOR EXTRACTING THE FILLER USED IN MANUFACTURING POROUS MATERIALS PARTS AND NEW MATERIALS ENABLED BY THIS NEW TECHNIQUE "characterized by the procedure and equipment that enable the production of new porous materials consisting of eliminating by the dissolution of the polymer filler from the produced parts of porous material based on any metal in any scale using the dissolution in solvent to remove its manufacturing filling material. 25-"METHOD AND EQUIPMENT FOR EXTRACTING THE FILLER

USED IN MANUFACTURING POROUS MATERIALS PARTS AND NEW MATERIALS ENABLED BY THIS NEW TECHNIQUE " characterized by the procedure and equipment that enable the production of new porous materials consisting of eliminating by the dissolution of the polymer filler from the produced parts of porous material based on any precious metals in any scale using the dissolution in solvent to remove its manufacturing filling material for catalytic objectives or jewellery.