Article of manufacture and process for producing the same

Abstract

The present disclosure provides an article of manufacture and a process for obtaining an article of manufacture. The disclosed article of manufacture comprises a solid body including a core region, a surface layer, the surface layer being at a periphery segment of said core region, and optionally a topcoat over said surface layer; the core region comprises an essentially homogenous blend of (i) inorganic particulate matter comprising rock particles and unfired clay particles, (ii) fibrous material and (iii) a polymerized first drying oil; the surface layer comprises a polymerized second drying oil which may be the same or different from said polymerized first drying oil; the topcoat layer, if present, comprises a polymerized third drying oil and a resin; wherein said inorganic particulate matter have a particle size within a range of about 0.1 micron and about 20mm; and wherein at least one of the following is fulfilled: said polymerized first drying oil and said polymerized second drying oil are from different raw drying oils; and said polymerized second drying oil is present, in a volume unit, at a concentration, that is greater than concentration of said polymerized first drying oil in a same volume unit of said core region.

Description

[0001] ARTICLE OF MANUFACTURE AND PROCESS FOR PRODUCING THE SAME

[0002] TECHNOLOGICAL FIELD

[0003] The invention is in the field of environmentally friendly articles of manufacture and methods of manufacturing the same.

[0004] BACKGROUND ART

[0005] References considered to be relevant as background to the presently disclosed subject matter are listed below:

[0006] International patent application publication No. WO2015173819

[0007] Great Britain patent application publication No. GB464864

[0008] - United States patent application publication No. US20220251387

[0009] Japanese patent application publication No. JPH0383842

[0010] - United States patent application publication No. US20240059821

[0011] - United States patent No. US6358305

[0012] Oxidation of drying oils containing non-conjugated and conjugated double bonds catalyzed by a cobalt catalyst, Z.O. Oyman, W. Ming, R. van der Linde, Progress in Organic Coatings Volume 54, Issue 3, 1 November 2005, Pages 198-204. https: / / www.youtube.com / watch?v=brpLJcBr7-k

[0013] Acknowledgement of the above references herein is not to be inferred as meaning that these are in any way relevant to the patentability of the presently disclosed subject matter.

[0014] BACKGROUND

[0015] The use of earth-based mixtures for producing new products has been described by WO2015173819. GB464864 describes road surfaces and articles such as tiles and slabs for building purposes made by mixing together a drying or semi-drying oil, a drier and a hard, mineral or rock-like, water-insoluble filler of a granular form readily separable into individual particles and retained on a 150-mesh sieve and substantially free from powdery or absorbent materials, and heating the mixture. The oil may be linseed or tung or sunflower, soya or foots, and may be present as oil varnishes and oil lacquers.

[0016] US20220251387 describes compositions and methods of making and using asphalt roofing materials. The asphalt roofing materials include sterols. The sterols improve various rheological and aging properties of the asphalt roofing materials.

[0017] JPH0383842 describes a process comprising mixing pulverized natural stone, an inorganic pigment and a silane coupling agent with water glass or linseed oil and then treating with a silane to produce colored stone powder, which is subsequently mixed with a filler composed of magnesium hydroxide powder, glass powder or calcium aluminate powder and an unsaturated polyester resin to produce a base layer. A transparent gel coat surface layer composed of an unsaturated polyester resin is then formed on the surface of the obtained base layer to produce grained artificial stone.

[0018] US20240059821 describes a process for the manufacture of articles made of conglomerate material, e.g. in the form of slabs or blocks, starting from a mixture comprising an optionally expanded granulate of stone material or lithoid material, and a binder based on a resin obtained from acrylate vegetal oils. Also describes are articles thus obtained.

[0019] US6358305 describes a composition and a process of producing a top layer for roof shingles. This layer is based on the addition of a small amount of mixed binder, including drying oils. The mixture is based on particulate mixture, without small particles below 0.5mm. The drying oils are not pre-treated / pre-heated.

[0020] Z.O. Oyman et. al. describe a theory of cobalt-based acceleration of the oxidation process, how the double bonds in the oil molecule break, the mechanism of free radicals, and the overall oxidation process. GENERAL DESCRIPTION

[0021] The present disclosure provides, in accordance with a first of its aspects, a process for producing an article of manufacture, the process comprising: providing a liquid blend of (i) a liquid oxidized first drying oil (ii) water, (iii) inorganic particulate matter comprising rock particles, unfired clay particles and (iv) fibrous material; molding within a mold the liquid blend under conditions to cause the blend to solidify into a shaped core region of a solid body; applying, at least once, over the solidified shaped core region of the solid body, a liquid oxidized second drying oil, which can be the same or different from said liquid oxidized first drying oil, to form a surface layer of the solid body, the surface layer being peripheral to said solidified core region of the solid body; and optionally, applying a topcoat composition over said surface layer to form a topcoat layer, said topcoat composition comprises a resin and a liquid oxidized third drying oil.

[0022] The present disclosure provides in accordance with a second of its aspects, an article of manufacture comprising a solid body including a core region, a surface layer, the surface layer being at a periphery segment of said core region, and optionally a topcoat over said surface layer; the core region comprises an essentially homogenous blend of (i) inorganic particulate matter comprising rock particles and unfired clay particles, (ii) fibrous material and (iii) a polymerized first drying oil; the surface layer comprises a polymerized second drying oil which may be the same or different from said polymerized first drying oil; the topcoat layer, if present, comprises a polymerized third drying oil and a resin; wherein said inorganic particulate matter have a particle size within a range of about 0.1 micron and about 20mm; and wherein at least one of the following is fulfilled: said polymerized first drying oil and said polymerized second drying oil are from different raw drying oils; and said polymerized second drying oil is present, in a volume unit of said surface layer, at a concentration, that is greater than a concentration of said polymerized first drying oil in a same volume unit of said core region.

[0023] BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to better understand the subject matter that is disclosed herein and to exemplify how it may be carried out in practice, embodiments will now be described, by way of non-limiting example only, with reference to the accompanying drawings, in which:

[0025] Figure 1 is a schematic illustration of an article of manufacture according to some examples of the presently disclosed subject matter.

[0026] Figure l is a schematic illustration of another article of manufacture according to some examples of the presently disclosed subject matter.

[0027] Figure 3 is a schematic illustration of yet another article of manufacture according to some examples of the presently disclosed subject matter.

[0028] Figure 4 provides a scatter plot representing cumulative particle size distribution with an optimal shape parameter, illustrated by the dashed line.

[0029] Figure 5 provides a scatter plot representing cumulative particle size distribution in an insoluble particulate material mixture with an optimal shape parameter based on fitting to the optimal distribution curve, with a target shape factor range of 0.24-0.33 being represented by the solid lines, and the optimal distribution being illustrated a dashed line, and particle size distribution of the experimental mixture being represented by a doubled line.

[0030] Figure 6A-6C are viscosity temperature response curves of raw Tung oil having viscosity of between lOOcP and 300cP at 30°C (Figure 6A), liquid oxidized Tung oil having viscosity of between 2,500 cP and 80,000cP at 30°C (Figure 6B), and liquid oxidized Tung oil having viscosity of between 300 cP and 10,000cP at 30°C (Figure 6C). Two logarithmic equations are shown, corresponding to the boundary curves, offering a tool for calculating viscosity at intermediate temperatures if desired.

[0031] DETAILED DESCRIPTION

[0032] The presently disclosed subject matter is based on the development of articles of manufacture comprising engineered-stones having improved water / humidity resistance and / or stability. Specifically, a unique feature of the presently disclosed articles of manufacture is that they have a flexural strength at water-soaked conditions (referred to herein by the term ‘wet flexural strength’) of at least 3MPa, preferably, at least 3.5MPa and even at least 4MPa, as a result of the unique combination of oxidized / polymerized oils. Such flexural strength is measured on wet conditions and is determined by three points bending according to the demands of EN 15286 and by the practice and requirements of EN 14617-2.

[0033] As will be further elaborated herein below, a flexural strength of at least 3MPa, or even at least 3.5MP, or even at least 4MPa (under wet conditions, as described herein) is a non-obvious improvement over prior art articles of manufacture (showing a lower flexural strength under same test conditions), as exemplified herein, in the nonlimiting comparative examples.

[0034] In the context of the presently disclosed subject matter, it is critical to emphasize the importance of durability and strength in the disclosed articles of manufacture, which may be used as bricks and tiles, where there is frequent exposure to environmental and mechanical stresses. Such articles are routinely brought into contact with water, from sources such as rain and routine cleaning activities, and are also subjected to constant pressure, such as of foot traffic. Consequently, it is essential that such articles not only possess high flexural strength in dry conditions but maintain their strength. In addition, such may be subjected to sawing and drilling, thus exposing the bulk of the articles and make them more sensitive to water absorption.

[0035] In the context of the presently disclosed subject matter, when referring to an "article of manufacture" it is to be understood to encompass any tangible, man-made object or product, having a concrete physical form. An article of manufacture typically refers to an item produced through manufacturing processes and is distinguishable from raw materials or products of nature. According to a first aspect of the presently disclosed subject matter there is provided a process for producing an article of manufacture, the process comprising: providing a liquid blend (mixture) of (i) a liquid oxidized first drying oil (ii) water, (iii) inorganic particulate matter comprising rock particles, unfired clay particles, and (iv) fibrous material; molding, within a mold, the liquid blend under conditions that cause the liquid blend to solidify into a shaped core region of a solid body; applying, at least once, over the shaped core region of the solid body, a liquid oxidized second drying oil, which can be the same or different from the liquid oxidized first drying oil, to form a surface layer of the solid body, the surface layer being peripheral to the core region of the solid body; and optionally, applying a topcoat composition over the surface layer to form a topcoat layer, the topcoat composition comprises a resin and a liquid oxidized third drying oil.

[0036] The present disclosure also provides, in accordance with its second aspect, an article of manufacture comprising a solid body including a core region, a surface layer, the surface layer being at a periphery segment of said core region, and optionally a topcoat over said surface layer; the core region comprises an essentially homogenous blend of (i) inorganic particulate matter comprising rock particles and unfired clay particles, (ii) fibrous material and (iii) a polymerized first drying oil; the surface layer comprises a polymerized second drying oil which may be the same or different from said polymerized first drying oil; the topcoat, if present, comprising a polymerized third drying oil and resin; wherein the inorganic particulate matter have a particle size within a range of about 0.1 micron and about 20mm; and wherein at least one of the following is fulfilled: the polymerized first drying oil and the polymerized second drying oil are from different raw drying oils; and the polymerized second drying oil is present in a volume unit of said surface layer, at a concentration, that is greater than concentration of the polymerized first drying oil in a same volume unit of said core region.

[0037] In the context of the presently disclosed subject matter, when referring to a blend it is to be understood to mean a mixture that is preferably essentially homogenous, meaning that the components are distributed with respect to one another in a substantially uniform manner, without apparent formation of phases.

[0038] As used herein, the terms "essentially" and "substantially" are intended to mean that the specified feature, parameter, or characteristic is present to a degree that is sufficient to achieve the intended purpose or result, while allowing for the presence of minor deviations or variations. The term "minor" refers to an amount or deviation that does not exceed about 10% or even about 5% by weight, volume, or proportion, unless otherwise specified, provided such deviations do not materially affect the performance, function, or desired outcome of the subject matter described.

[0039] For simplicity and clarity, components that are common to both the blend (as used in the context of the presently disclosed process) and the solid core (as used in the context of the article of manufacture) are defined identically, unless explicitly stated otherwise. In other words, unless expressly indicated to the contrary, any component that appears in both the blend (used in the context of the process) and the solid core (used in the context of the article of manufacture) shall be understood to have the same definition in both contexts.

[0040] In the context of the presently disclosed subject matter, the term "liquid oxidized drying oil", whether referring to the liquid oxidized first drying oil, liquid oxidized second drying oil or liquid oxidized third drying oil, is understood to encompass a drying oil that has undergone polymerization to an intermediate state in which it remains in liquid state but exhibits a viscosity that is above the viscosity of the raw (natural) drying oil from which it is derived (referred to herein by the term "corresponding raw" or "corresponding natural" drying oil). As used herein, "corresponding raw" or "corresponding natural" drying oil refers to the unmodified, non-oxidized form of the drying oil prior to undergoing polymerization or oxidation. Further, in the context of the presently disclosed subject matter, the term "liquid oxidized drying oil" generally refers to a drying oil having a viscosity at least above 300cP and not more than 80,000cP, as measured at 30°C, using standard testing methods, such as, and at times, preferably, ASTM D7867.

[0041] Within the context of the term "liquid oxidized drying oil" and in accordance with certain examples of the presently disclosed subject matter, the liquid oxidized first drying oil is a liquid oxidized drying oil having a viscosity of between about 2,500 cP and about 80,000 cP as determined at a temperature of 30°C. At times, the liquid oxidized first drying oil is a liquid oxidized drying oil having a viscosity of between about 400 cP and about 10,000 cP as determined at a temperature of 30°C.

[0042] Within the context of the term liquid oxidized drying oil and in accordance with some further, or alternative examples of the presently disclosed subject matter, the liquid oxidized first drying oil is a liquid oxidized drying oil having a viscosity of between about 100 cP and about 4,000 cP as determined at a temperature of 90°C.

[0043] Within the context of the term liquid oxidized drying oil and in accordance with certain examples of the presently disclosed subject matter, the liquid oxidized second drying oil is a liquid oxidized drying oil having a viscosity of between about 300 cP and about 10,000 cP as determined at a temperature of 30°C. At times, the liquid oxidized second drying oil is a liquid oxidized drying oil having a viscosity of between about 400 cP and about 10,000 cP as determined at a temperature of 30°C.

[0044] Within the context of the term liquid oxidized drying oil and in accordance with certain examples, or alternative examples of the presently disclosed subject matter, the liquid oxidized second drying oil is a liquid oxidized drying oil having a viscosity of between about 15 cP and about 500 cP determined at a temperature of 90°C.

[0045] Within the context of the term liquid oxidized drying oil and in accordance with certain examples of the presently disclosed subject matter, the liquid oxidized third drying oil is a liquid oxidized drying oil having a viscosity of between about 300 cP and about 40,000cP as determined at a temperature of 30°C.

[0046] At times, the liquid oxidized third drying oil is a liquid oxidized drying oil having a viscosity of between about 400 cP and about 40,000 cP as determined at a temperature of 30°C. Within the context of the term liquid oxidized drying oil and in accordance with certain examples, or alternative examples of the presently disclosed subject matter, the liquid oxidized third drying oil is a liquid oxidized drying oil having a viscosity of between about 15 cP and about 500 cP determined at a temperature of 90°C.

[0047] Further, in the context of the presently disclosed subject matter, the term "polymerized drying oil" is to be understood to refer a drying oil that has undergone polymerization and curing and as a result can be quantitatively distinguished from the corresponding raw drying oil and from the corresponding liquid oxidized drying oil in at least one measurable property, such as or even preferably, viscosity or hardness (determined as described herein).

[0048] In some examples of the presently disclosed subject matter, the polymerized drying oil is a drying oil that has a degree of polymerization such that if measured separate from the article of manufacture would exhibit a viscosity that is above 80,000cP when measured at 30°C, using standard testing methods, such as ASTM D7864.

[0049] In certain examples, the polymerization is such that it is not possible to determine viscosity of the drying oil, due to its high viscosity and lack of pourability, even at a temperature of between about 100°C -200°C, e.g. 150°C.

[0050] In certain examples, the degree of polymerization is determined to confirm that the drying oil is polymerized to the extent that it is no longer liquid or even semi liquid at a temperature between about 100°C -200°C, e.g. 150°C. Those versed in the art would readily appreciate that a degree of polymerization can be analytically determined, even if part of a composite material, such as in the presently disclosed article of manufacture, by any one of Fourier Transform Infrared Spectroscopy (FTIR), Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA), Rheological Measurements (e.g. on isolated polymerized drying oil), gel permeation chromatography (GPC), size exclusion chromatography (SEC), and Microscopy Techniques, such as scanning electron microscopy (SEM) or transmission electron microscopy (TEM).

[0051] In some examples of the presently disclosed subject matter, the polymerized drying oil is one that is in solid, cured state. The liquid oxidized drying oil and the polymerized drying oil are both derived from a raw drying oil. In the context of the presently disclosed subject matter, the term "raw drying oil" also referred to as "natural drying oil" refers to a drying oil in its form as obtained directly from a natural source, e.g. plant source and fish source, without undergoing chemical modification, polymerization, or oxidation intended to alter its natural properties. As such, it is to be understood that a raw drying oil is one that essentially retains its original triglyceride structure and is typically obtained through mechanical extraction methods including cold pressing or expeller pressing. Such raw drying oils are characterized by a high content of polyunsaturated fatty acids such as linoleic acid and alpha-linolenic acid, which are prone / susceptible to natural drying when exposed to air.

[0052] In some examples of the presently disclosed subject matter, a raw drying oil is characterized by an iodine value higher than 110g / 100 g; at times, from 110g to 200g / 100g, as measured according to Standard GB / T5532-2008.

[0053] In some examples of the presently disclosed subject matter, a raw drying oil is characterized by a saponification value of from 175 to 210 mg KOH / g.

[0054] Further, in the context of the presently disclosed subject matter, when referring to an oxidized drying oil or polymerized drying oil with reference to a "corresponding raw drying oil" it is to be understood to define that the oxidized drying oil or the polymerized drying oil and the raw drying oil are derived from the same source. For example, a corresponding raw drying oil of liquid oxidized tung oil or polymerized tung oil would be tung oil in its native / natural chemical composition and structure.

[0055] The oxidized drying oil, polymerized drying oil and raw drying oil are typically plant-derived, or fish- derived, the derivation being by mechanical extraction methods known in the art.

[0056] As used herein, the term "oxidized drying oil" refers to a drying oil that has undergone partial oxidation and polymerization such that it remains in a liquid state with increased viscosity, suitable for further processing or application. In contrast, the term "polymerized drying oil" refers to a drying oil that has undergone further polymerization and curing, resulting in a solid or semi-solid material that is part of the final article of manufacture. The oxidized and polymerized drying oils are both derived from the same corresponding raw drying oil but represent distinct stages in the transformation process.

[0057] In some examples of the presently disclosed subject matter, the process comprises the liquid oxidized first drying oil and a liquid oxidized second drying oil from a same source. The corresponding article of manufacture comprises a polymerized first drying oil and a polymerized second drying oil derived from the same source.

[0058] In some examples of the presently disclosed subject matter, the process comprises the liquid oxidized first drying oil and a liquid oxidized second drying oil from different sources. The corresponding article comprises a polymerized first drying oil and a polymerized second drying oil derived from different sources.

[0059] In some examples of the presently disclosed subject matter, the comprises the liquid oxidized second drying oil and a liquid oxidized third drying oil from a same source. The corresponding article, when a topcoat is present, comprises a polymerized second drying oil and a polymerized third drying oil derived from the same source.

[0060] In some examples of the presently disclosed subject matter, the process comprises the liquid oxidized second drying oil and a liquid oxidized third drying oil from different sources. The corresponding article, when a topcoat is present, comprises a polymerized second drying oil and a polymerized third drying oil derived from different sources.

[0061] In some examples of the presently disclosed subject matter, the process comprises the liquid oxidized first drying oil and a liquid oxidized third drying oil from a same source. The corresponding article comprises a polymerized first drying oil and a polymerized third drying oil derived from the same source.

[0062] In some examples of the presently disclosed subject matter, the process comprises the liquid oxidized first drying oil and a liquid oxidized third drying oil from different sources. The corresponding article comprises a polymerized first drying oil and a polymerized third drying oil derived from different sources.

[0063] In some examples of the presently disclosed subject matter, the comprises the liquid oxidized first drying oil, liquid oxidized second drying oil and liquid oxidized third drying oil are derived from a same source (e.g. from the same plant or fish source). The corresponding article comprises the polymerized first, second, and third drying oils derived from the same source.

[0064] A non-limiting list of plant-derived drying oil includes tung oil, hemp oil, biofene or trans- beta-farnesene, linseed oil, poppy oil, walnut oil, palm oil, sunflower oil, cottonseed oil, corn oil, soybean oil, safflower oil, perilla oil, oiticica oil, rapeseed oil, tobacco oil, rubber seed oil, Manihot glaziovii oil, grape oil, sesame oil, colza oil, camelina oil and argemone oil.

[0065] A non-limiting list of fish-derived drying oils includes sardine oil, cod liver oil and herring oil.

[0066] Accordingly, in some examples of the presently disclosed subject matter, when referring to any one of the liquid oxidized first drying oil, liquid oxidized second drying oil, liquid oxidized third drying oil, polymerized first drying oil, polymerized second drying oil, polymerized third drying oil, it is to be understood that such oils may be derived from plant-based drying oils (such as those exemplified above), fish-based drying oils (such as those exemplified above), or any combination of same.

[0067] In some examples, at least one of the liquid oxidized first drying oil, liquid oxidized second drying oil, liquid oxidized third drying oil, polymerized first drying oil, polymerized second drying oil, or polymerized third drying oil is derived from tung oil.

[0068] The liquid oxidized drying oil - whether the first, second or third - used in the context of the presently disclosed process, may be obtained by various techniques.

[0069] In some examples of the presently disclosed process, the first oxidized drying oil, the second oxidized drying oil and the third oxidized drying oil are, independently obtained by subjecting each of the raw first, second or third drying oil to thermal treatment. In the absence of active bubbling, and to promote enrichment with oxygen, the thermal heating is conducted with high surface exposure to the surrounding air, e.g. by using a large surface area, and / or by vigorous mixing.

[0070] In some examples of the presently disclosed process, the liquid oxidized first drying oil, the liquid oxidized second drying oil and the liquid oxidized third drying oil are, independently obtained by introducing into a gas containing oxygen into a raw drying oil to produce, respectively, an oxygen-enriched first, second or third drying oil and subj ecting the oxy gen-enriched first, second or third drying oil to thermal treatment.

[0071] As used herein, the term "oxygen enriched" refers to a drying oil having a concentration of dissolved oxygen that is above the oxygen concentration present under natural or ambient conditions.

[0072] In some examples of the presently disclosed subject matter, the gas containing oxygen - used to obtain the liquid oxidized first drying oil, liquid oxidized second drying oil or liquid oxidized third drying oil - may be the same or different for each and is selected from oxygen and air.

[0073] In some examples of the presently disclosed subject matter, the gas containing oxygen - used to obtain the liquid oxidized first drying oil, liquid oxidized second drying oil or liquid oxidized third drying oil- is air.

[0074] In some examples of the presently disclosed subject matter, the introducing of gas containing oxygen is by bubbling, preferably of micro bubbles.

[0075] Following the introduction of oxygen containing gas, the resulting oxygen enriched drying oil - whether the first, second and / or third - is subjected to thermal treatment, namely, heating, while maintaining the fluidity of the drying oil, and preferably until it reaches a viscosity within the ranges defined hereinabove for the respective liquid oxidized first, liquid oxidized second and / or liquid oxidized third drying oils.

[0076] In some examples of the presently disclosed subject matter, and as noted hereinabove, the liquid oxidized first drying oil, liquid oxidized second drying oil and / or liquid oxidized third drying oil may each, independently, be obtained by subjecting the corresponding raw drying oil to thermal treatment, even without the enrichment with oxygen.

[0077] In the context of the presently disclosed subject matter, it is to be understood that thermal treatment of raw drying oil involves at least heating to a temperature above 100°C, for a time sufficient that facilitate / is sufficient to increase in viscosity of the drying oil, preferably to a viscosity level suitable for the intended functionality of the drying oil, i.e. being the liquid oxidized first drying oil, the liquid oxidized second drying oil or the liquid oxidized third drying oil. In some examples of the presently disclosed subject matter, the liquid oxidized first drying oil, liquid oxidized second drying oil and / or liquid oxidized third drying oil are obtained, independently, by exposing a raw drying oil to irradiation such as ultraviolet (UV) irradiation, (e.g. irradiation within a wavelength range from 100 to 400 nanometers), or infrared (IR) irradiation, (e.g. irradiation within a wavelength range from 780nanometer to Imilimetter).

[0078] In the presently disclosed process, the liquid blend comprises the liquid oxidized first drying oil in an amount constituting at least 0.5wt% out of the total weight of the blend, prior to adding the water.

[0079] In some examples of the presently disclosed subject matter, the liquid oxidized first drying oil is present in the blend in an amount constituting at least 0.5wt%; at times, at least 0.6wt%; at times, at least 0.7wt%; at times, at least 0.8wt%; at times, at least 0.9wt%; at times, at least 0.95wt%; at times, at least 0.97wt%; at times, at least 0.99wt%, at times, at least 1.0wt%, out of the total weight of the blend, prior to adding the water.

[0080] In some examples of the presently disclosed subject matter, the liquid oxidized first drying oil is present in the blend in an amount constituting between 0.5wt% and 5wt%. In certain examples, the liquid oxidized first drying oil is in an amount of between 0.8wt% and 3wt%; at times, between 0.97wt% and about 4wt%; at times, between lwt% and about 3wt%; at times, between 1.2wt% and about 4wt%; at times, between 1.1 wt% and 3wt%, prior to adding the water.

[0081] In certain examples of the presently disclosed subject matter, a preferred range for the liquid oxidized first drying oil is between 0.5% and 2wt%.

[0082] As described above, the liquid blend of the presently disclosed process also comprises inorganic particulate matter.

[0083] In the context of the presently disclosed subject matter, the inorganic particulate matter is of natural source and comprises at least rock particles and unfired clay particles.

[0084] In some examples of the presently disclosed subject matter, the inorganic particulate matter of the blend forming the solid core comprises water-insoluble inorganic particles. In some examples of the presently disclosed subject matter, the inorganic particulate matter of the blend forming the solid core comprise natural inorganic materials having a Mohs hardness of at least 3.

[0085] In some examples of the presently disclosed subject matter, the water insoluble inorganic material comprises inorganic material consists essentially of earth derived inorganic matter.

[0086] In some examples of the presently disclosed subject matter, the rock particles of the inorganic particulate matter are selected from the group consisting of igneous rocks, sedimentary rocks and metamorphic rock and any combination of same.

[0087] For the purposes of the present disclosure, when referring to "sedimentary rock material" it is to be understood to include any one or combination of the three major categories of sedimentary rocks, being (1) terrigenous clastic sedimentary rocks, (2) carbonates (e.g. limestone and dolomite) and (3) metamorphic, e.g. marble and quartzite.

[0088] When referring to "terrigenous clastic sedimentary rocks" it is to be understood to refer to sedimentary rocks composed of the detrital fragments of preexisting rocks and minerals and are conventionally considered to be equivalent to clastic sedimentary rocks in general. Because most of the clasts are rich in silica, they are also referred to as siliciclastic sedimentary rocks. Thus, in some examples of the presently disclosed subject matter, the water insoluble inorganic material comprises at least siliciclastics. These siliciclastics can be identified or further classified on the basis of clast diameter as conglomerate and breccia, sandstone, siltstone, and finer-than-silt-sized mudrock (shale, claystone, and mudstone), all of which constitute part of the "water insoluble inorganic material" of the presently disclosed subject matter.

[0089] When referring to "carbonates" in the context of sedimentary rocks, it is to be understood to encompass one or both of limestones and dolomites, which, in turn, known to consist essentially of the minerals aragonite, calcite, and dolomite.

[0090] In some examples of the presently disclosed subject matter, the water insoluble rock particles comprise at least terrigenous clastic sedimentary rock.

[0091] In some examples of the presently disclosed subject matter, the water insoluble rock particles comprise at least limestone and / or dolomite. In some examples of the presently disclosed subject matter, the water insoluble inorganic rock particles comprise a combination of terrigenous clastic sedimentary rock and limestone and / or dolomite.

[0092] In some examples of the presently disclosed subject matter, the sedimentary rock comprises any one or combination of limestone, chalk, sandstone, shale.

[0093] In some examples of the presently disclosed subject matter, the water insoluble inorganic rock particles comprise igneous rock. Igneous rocks are known as a type of rock that is formed when molten rock (rock liquefied by intense heat and pressure) cools to a solid state. A non-limiting list of igneous rock includes basalt, quartz, pumice, obsidian, rhyolite, scoria, dacite, granite, gabbro, diabase, diorite, pegmatite, and peridotite.

[0094] In some examples of the presently disclosed subject matter, the water insoluble inorganic rock particles comprise at least one igneous rock.

[0095] In some examples of the presently disclosed subject matter, the water insoluble inorganic particles comprise at least basalt.

[0096] In some examples of the presently disclosed subject matter, the water insoluble inorganic particles comprise at least quartz.

[0097] In some examples of the presently disclosed subject matter, the water insoluble inorganic rock particles comprise at least metamorphic rock, e.g. marble, quartzite etc.

[0098] In some examples of the presently disclosed subject matter, a non-limiting list of water insoluble inorganic particulate matter includes quartz, limestone, dolomite, chalk, sandstone, shale, pumice, obsidian, rhyolite, scoria, dacite, granite, gabbro, diabase, diorite, pegmatite, peridotite, basalt, marble, quarzite and any combination of same.

[0099] In the context of the present disclosure, it is to be understood that the term "water insoluble inorganic particulate matter" is to be understood to refer to materials other than the unfired clay material described herein. This distinction applies notwithstanding any overlap that may exist between the clay material and the water insoluble particulate matter (e.g. inorganic rock particles) in terms of their natural composition (e.g., the presence of common clay minerals). The "water insoluble inorganic particles" in the context of the present disclosure are to include any particulate matter composed of inorganic substances that do not dissolve in water under standard conditions (room temperature and pressure), even when exposed to prolonged contact or agitation. For clarity, materials are considered "insoluble" if their solubility in water is less than 0.1 g / 100 mL at 25°C.

[0100] In some examples, the term "unfired clay" should be understood to have its commonly accepted meaning, namely, granular or powdered forms of clay that have not been subjected to heat treatment processes such as firing or sintering. These particles retain the chemical and physical properties characteristic of raw, natural clay, including plasticity when mixed with water and the ability to harden when dried in air, but remain soluble or disintegrable when re-submerged in water. Within this context, it is thus to be understood that the solid core according to the presently disclosed process and article of manufacture excludes any clay material that has undergone thermal processing altering its intrinsic binder properties and structural integrity.

[0101] In some examples of the presently disclosed subject matter, the unfired clay material comprises fine-grained natural rock or soil material that includes one or more clay minerals, at times, with variable amounts of iron, magnesium, alkali metals, alkaline earths, and other cations, and at times trace amounts of metal oxides.

[0102] In some examples of the presently disclosed subject matter, the unfired clay particles comprise at least one oxide selected from the group consisting of silica, alumina, magnesia, and combinations of same.

[0103] In some examples of the presently disclosed subject matter, the unfired clay particles comprise at least aluminum phyllosilicate.

[0104] The unfired clay particles can be characterized by plasticity of one or more of the clay minerals therein. The plasticity can be determined by standard test methods for liquid limit, plastic limit, and plasticity index of soils.

[0105] In some examples of the presently disclosed subject matter, the unfired clay particles have a plasticity that is defined by the combination of its plasticity index and its liquid limit. In the context of the present disclosure, the term "plasticity index" is used to define the range of the water content within which the unfired clay particles achieve their plastic state.

[0106] The PI is determined by the liquid limit and the plastic limit of the unfired clay particles according to the following accepted equation: lp= Wt- Wp

[0107] Where:

[0108] Wi = liquid limit

[0109] Wp= plastic limit

[0110] Ip= plasticity index

[0111] The term "liquid limit" is to be understood as the water / moisture content (in weight percentage, wt%) at which the behavior of a material changes from a plastic state to a liquid state.

[0112] The term "plastic limit" is to be understood as the water / moisture content at which a thread of material with a diameter of 3.2mm begins to crumble.

[0113] In some examples, the PI and liquid limit are determined according to ASTM D 4318 and / or according to Israeli Standard 253, paragraphs 103.3.2, 103.4, 103.8-103.10, 206.1, 206.1.2, 206.2.2.

[0114] In some examples of the presently disclosed subject matter, the unfired clay particles comprise a combination of clay minerals, each defined by its PI and liquid limit, the liquid limit being greater than the PI.

[0115] In some examples of the presently disclosed subject matter, the unfired clay particles comprise at least one clay mineral having a PI above about 20% and a liquid limit above about 40%.

[0116] In some examples of the presently disclosed subject matter, the unfired clay particles comprise at least one clay mineral having a PI above about 35%.

[0117] In some examples of the presently disclosed subject matter, the unfired clay particles comprise at least one clay mineral having a liquid limit above about 55%. In some examples of the presently disclosed subject matter, the unfired clay particles comprise at least one clay mineral having a PI above about 35% and a liquid limit above about 55%.

[0118] In some examples of the presently disclosed subject matter, the unfired clay particles comprise at least one clay mineral having a liquid limit above about 400%.

[0119] In some examples of the presently disclosed subject matter, the unfired clay particles comprise at least one clay mineral having a liquid limit above about 450%.

[0120] In some examples of the presently disclosed subject matter, the unfired clay particles comprise at least one clay mineral having a liquid limit above about 500%.

[0121] In some examples of the presently disclosed subject matter, the unfired clay particles comprise at least the mineral ball clay.

[0122] In some examples of the presently disclosed subject matter, the unfired clay particles comprise at least ball clay having a PI above about 20%, at times above about 35%, and liquid limit above about 40%, at times above 55%.

[0123] In some examples of the presently disclosed subject matter, the unfired clay particles comprise at least bentonite.

[0124] In some examples of the presently disclosed subject matter, the unfired clay particles comprise at least bentonite having a liquid limit above about 400%, at times above 450%, at times, above 500%.

[0125] In some examples of the presently disclosed subject matter, the unfired clay particles comprise at least a combination of said bentonite and said ball clay.

[0126] In some examples of the presently disclosed subject matter, the unfired clay particles comprise a combination of bentonite and ball clay at a weight ratio of between about 1 : 11 and about 1.2:1.

[0127] In some examples of the presently disclosed subject matter, the unfired clay particles comprise a combination of bentonite and ball clay at a weight ratio between about 1 :2 and about 1 :5.

[0128] In some examples of the presently disclosed subject matter, the unfired clay particles comprise a combination of bentonite and ball clay at a weight ratio of between about 1 :2.1 and about 1 :3; at times between about 1 :2.1 and about 1 :2.6; at times, between about 1 :2.1 and 1 :2.5; at times between about 1 :2.1 and about 1 :2.4.

[0129] In some examples of the presently disclosed subject matter, the unfired clay particles are a clay material recognized as an industrial clay.

[0130] In some examples of the presently disclosed subject matter, the water-insoluble inorganic material comprises inorganic material that consists essentially of earth- derived inorganic matter.

[0131] In some other examples of the presently disclosed subject matter, the waterinsoluble inorganic material comprises recycled matter comprising water insoluble inorganic material.

[0132] The term "recycled matter comprising water insoluble inorganic material" is to be understood to encompass material that comprises processed earth-derived material and, as such, may also include synthetic material, such as inorganic binders.

[0133] In some examples of the presently disclosed subject matter, the recycled matter comprises recycled construction and demolition waste, such as concrete.

[0134] In some examples of the presently disclosed subject matter, the recycled matter comprising water-insoluble inorganic material comprises at least 50wt%, at times at least 60wt%, at times, at least 70wt%; at times, at least 80wt%; at times, at least 90wt%, or even, at times 100wt% of said water insoluble inorganic material.

[0135] In some examples of the presently disclosed subject matter, the recycled matter comprises water insoluble inorganic material comprises or is recycled concrete.

[0136] The inorganic particulate matter has a wide range of particle sizes. A unique feature of the presently disclosed process and article of manufacture is that the inorganic particulate matter is also present in a powder form. In other words, there is no need to remove powdery inorganic material prior to blending.

[0137] In some examples of the presently disclosed subject matter, the inorganic particulate matter in the blend or in the solid core has a particle size distribution ranging from 0.1 micron to 20 mm. In some examples of the presently disclosed subject matter, the inorganic particulate matter in the blend or in the solid core has at least 10wt% particles equal to or below 10 micron.

[0138] In accordance with some examples of the presently disclosed subject matter, the water insoluble inorganic material is selected to provide a cumulative particle size distribution that behaves within an upper and lower limit, derived from the mathematical equation Andreasen and Andersen particle size distribution model of:

[0139] Wherein

[0140] P(D) is the cumulative percentage of particles with size <D,

[0141] D is the particle diameter,

[0142] Dmax is the maximum particle size in the specific mixture and q is the shape parameter (also called the distribution modulus, typically between 0.2 and 1.0).

[0143] The selection of particles is carried out to achieve the desired value of the shape parameter "q".

[0144] To achieve a desired shape parameter, insoluble inorganic materials with various particle sizes are mixed together to achieve a particle size distribution fitting a curve corresponding to desired shape parameter, i.e. that fits the curve of Figure 4. The dry mixture is then wet with the liquid.

[0145] The blend forming part of the presently disclosed process, and the solid core of the presently disclosed article of manufacture, also comprise fibrous material.

[0146] In some examples of the presently disclosed subject matter, the fibrous material is a natural fibrous material, i.e. derived from natural substances.

[0147] In some examples of the presently disclosed subject matter, the fibrous material is derived from plant material.

[0148] In some examples of the presently disclosed subject matter, the fibrous material comprises at least one of cellulose, hemicellulose, and lignocellulose fibers. In some examples of the presently disclosed subject matter, the fibrous material comprises at least one of cellulose.

[0149] In some examples of the presently disclosed subject matter, the fibrous material comprises fibers selected from the group consisting of flax, sisal, hemp, jute, cotton, abaca, bamboo, ramie, banana, and kenaf, and combinations of same.

[0150] In some examples of the presently disclosed subject matter, the fibrous material comprises at least flax fibers.

[0151] In some examples of the presently disclosed subject matter, the fibrous material comprises basalt fibers.

[0152] In some examples of the presently disclosed subject matter, the fibrous material comprises synthetic fibers.

[0153] In some examples, synthetic fibers comprise any one of glass fibers, polyester fibers, basalt fibers, carbon fibers.

[0154] In some examples of the presently disclosed subject matter, the fibrous material comprises fibers have a filamentous or thread shape, with a length (longitudinal dimension) of at least 2mm; at times of at least 3mm; at times, of at least 4mm; at times, of at least 5mm.

[0155] In some examples of the presently disclosed subject matter, the fibrous material has a length within a range of between about 2mm and about 30mm; at times, between about 2mm and about 20mm; at times, between about 2mm and about 15mm; at times, between about 4mm and about 18mm; at times, between about 7mm and about 12mm; at times, between about 5mm and about 16mm; at times between about 15mm and about 20mm.

[0156] It is to be appreciated that such longitudinal dimensions of the fibrous material can be determined by observation with the naked eye or by light microscopy.

[0157] The amount of the fibrous material within the article can be determined. In some examples, the amount of fibrous material is determined by one of polarizing microscopy, density gradient separation or Thermal Gravimetry Analysis (TGA) and Microscopy Techniques, such as scanning electron microscopy (SEM). In some examples of the presently disclosed subject matter, the fibrous material in the blend (as described with respect to the disclosed process) or in the resulting solid core constitutes at least lvol% out of a total volume of the blend (before adding water) or of the solid core.

[0158] In some examples, the fibrous material in the blend or resulting solid core constitutes between about 1% and about 20% out of a total volume of the presently disclosed article; at times, between about 1% and about 12%; at times, between about 1% and about 6%; at times, between about 5% and about 10%; at times, between about 8% and about 16%.

[0159] In some examples of the presently disclosed subject matter, the fibrous material is characterized, prior to introduction into the blend, by a tensile strength of at least 400 MPa. In this context, it is to be understood that when referring to tensile strength of the fibrous material, it means the tensile strength of the elementary fibrous material, i.e. the smallest diameter fibre that can be separated by physical separation. In some examples of the presently disclosed subject matter, the fibrous material is characterized by tensile strength of at least 450 MPa; at times, of at least 500 MPa.

[0160] The blend of the presently disclosed process also comprises water (which may be de-ionized, but not necessarily) and an inorganic cation.

[0161] When referring to "inorganic cation" it is to be understood to encompass any one or combination of potassium, ammonium, sodium, calcium, magnesium, lithium, and aluminum.

[0162] In some examples, the inorganic cation is a monovalent cation.

[0163] In some examples, the inorganic cation is potassium.

[0164] In some other examples, the inorganic cation is ammonium.

[0165] The inorganic cation is present in an amount that is greater than its combined amount in clay material and rock derived water-insoluble inorganic material from which the article is made, when they are in their natural state (i.e., in nature). The amounts present in clay material and the rock-derived water insoluble inorganic material are known in the art for each. The greater amount is a result of externally added cations during the method of manufacturing, as will be further described below. The amount of water (preferably already containing the inorganic salt) in the blend constitutes at most 50wt% out of the total weight of the wet, liquid blend.

[0166] In some examples of the presently disclosed subject matter, the amount of water (with or without the inorganic salt) added is such to constitute between about 5 wt% and about 50 wt% out of a total weight of the resulting wet blend; at times between about 8 wt% and about 40 wt%; at times between about 11 wt% and about 30 wt%; at times between about 14 wt% and about 20 wt%.

[0167] In some examples of the presently disclosed subject matter, the amount of water added is to provide a wet mixture where the liquid constitutes between about 12 wt% and about 20 wt% out of the total weight of the wet mixture.

[0168] The water is preferably prepared by dissolving the salt (namely a salt comprising the inorganic cation, as described hereinabove), in deionized water prior to mixing into the solid inorganic particles.

[0169] In some examples, the amount of salt dissolved in the water (preferably deionized) is up to about 0.1 wt%; at times, up to about 0.09 wt%; at times, up to about 0.08 wt%; at times, up to about 0.07 wt%; at times, up to about 0.06 wt%; at times, up to about 0.05 wt%; at times, about up to 0.04 wt%; at times, about up to 0.03 wt%; at times, up to about 0.02 wt%; at times, up to about 0.01 wt%; at times, up to about 0.0099 wt%; at times, up to about 0.0098 wt%; at times, up to about 0.0095 wt%; at times, about up to 0.009 wt% out of the total weight of the wet mixture, prior to adding the oil.

[0170] In some examples of the presently disclosed subject matter, the liquid blend is obtained by mixing the inorganic particles with water (preferably containing the inorganic cation) prior to introducing the liquid oxidized first drying oil.

[0171] In some examples of the presently disclosed subject matter, the liquid blend is obtained by mixing the inorganic particles with at least 50 wt% of the water (preferably containing the inorganic cation) prior to introducing the liquid oxidized first drying oil, the rest of the water being introduced with the liquid oxidized first drying oil, e.g. as an emulsion.

[0172] In the context of the presently disclosed subject matter, it is preferable that the inorganic particles are brought into contact with enough water to occupy the voids in the inorganic particles (e.g. the clay) before contacting the inorganic particles with the oil.

[0173] The molding is under conditions that cause the liquid blend to solidify into the shaped core region of the solid body.

[0174] In some examples of the presently disclosed subject matter, the conditions causing solidification of the blend in the mold comprise thermal treatment.

[0175] In some examples of the presently disclosed subject matter, the thermal treatment comprises heating the mold to a temperature of at least about 30 °C.

[0176] In some examples of the presently disclosed method, the mold per se is heated to a temperature of between about 30°C and about 140°C; at times, between about 60°C and about 90°C; at times, between about 85°C and about 105°C; at times, between about 100°C and about 120°C; at times, between about 115°C and about 135°C; at times, between about 130°C and about 140°C. The heating of the mold per se causes heating of the blend held by the mold.

[0177] In some examples of the presently disclosed subject matter, the conditions causing solidification of the blend in the mold comprise compression.

[0178] In some examples of the presently disclosed method, the compression of the blend comprises applying a pressure, preferably a constant pressure, of at least about lOBar.

[0179] In some examples of the presently disclosed method, the compression is controlled to be at range of between about lOBar and about 300Bar; at times, between about 40Bar and about 80Bar; at times, between about 70Bar and about 120Bar; at times, between about lOOBar and about 140Bar; at times, between about 130Bar and about 170Bar; at times, between about 160Bar and about 200Bar.

[0180] In some examples of the presently disclosed subject matter, the conditions causing solidification of the blend in the mold comprise a combination of the abovedescribed compression and the above-described thermal treatment.

[0181] In some examples of the presently disclosed subject matter, the conditions causing the solidification result in water removal. In some examples of the presently disclosed subject matter, the water removal is further facilitated by applying negative air pressure (i.e. vacuum) within a mold cavity, during at least portions of the molding duration. When referring to negative pressure it means negative gauge pressure within the mold structure.

[0182] In some examples of the presently disclosed subject matter, the water removal is obtained by using a mold including a porous plate such that the water is extracted via the pores of the porous plate. In some cases, the extraction of the water via the pores is aided by applying the negative air pressure.

[0183] In some examples of the presently disclosed subject matter, the water removal is obtained using a moisture wicking fabric. Moisture-wicking fabrics are fabrics with the ability to pull moisture away (in this case, from the wet particulate mass) using tiny, built-in capillaries. Moisture is drawn into the fabric, which makes it easier to be translocated from the mold. A non-limiting list of possible moisture wicking fabrics includes wool, polyamide, polyester, polypropylene, Gore-Tex, Nylon, bamboo, Modal, acrylic, Rayon and Spandex. In some examples of the presently disclosed method, the moisture wicking fabric is placed within the mold, and the wet mixture is introduced at least onto the moisture wicking fabric. Moisture wicking fabrics are known in the art and typically are fabrics with the ability to pull moisture away via capillary action.

[0184] Following the molding stage, the shaped core region of the solid body is removed from the mold (cast) and further dried.

[0185] In some examples of the presently disclosed subject matter, the drying of the extracted core region of the solid body is to a moisture content that is between about 0.1 wt% and about 1 wt% out of the total weight of the extracted core region of the solid body; at times, between about 0.1 wt% and about 0.4 wt%; at times, between about 0.3 wt% and about 0.6 wt%; at times, between about 0.5 wt% and about 0.8 wt%; at times, between about 0.7 wt% and about 1 wt%.

[0186] In accordance with some examples of the presently disclosed process, the drying of the extracted core region of the solid body comprises any one or combination of air drying, oven drying, controlled humidity oven and dry air blowing. In some examples of the presently disclosed subject matter, the drying of the extracted core region of the solid body is carried out in a drying chamber with low humidity of, for example, 20 % relative humidity (RH) and temperature of 40°C-70°C until the moisture content is of less than 1 wt% (determined, for example, based on the weight difference of the article before pressing and after being placed in the drying chamber).

[0187] In some examples, the water content can be determined by the Pfefferkorn plasticity test. Without being limited thereto, it has been found that for tiles formation an advantageous physical property, as disclosed herein, are obtained if the wet mixture before compression had Pfefferkorn value of 8 to 1.15. In this connection, it is to be understood that a Pfefferkorn value of 1 means that the mixture has zero plasticity.

[0188] The dried extracted shaped core region of the solid body is then subjected to further processing, by applying at least once, over the shaped core region of the solid body, the liquid oxidized second drying oil.

[0189] As noted above, the liquid oxidized second drying oil can be derived from the same raw drying oil as the liquid oxidized first drying oil, yet with a different degree of viscosity, or it can be derived from a different raw drying oil.

[0190] In some examples of the presently disclosed subject matter, the liquid oxidized second drying oil is applied by dipping or immersing the shaped core region of the solid body into the liquid oxidized second drying oil.

[0191] In some examples of the presently disclosed subject matter, the liquid oxidized second drying oil is applied by dipping or immersing the shaped core region of the solid body into the liquid oxidized second drying oil and subjecting the dipped / immersed shaped core region to ultrasonic vibrations (e.g. using UD600SH-28L by KWUN WAH INTERNATIONAL LIMITED, marketed under the Eumax brand, device volume of 28 liters, an ultrasonic power output of 600 W, and operates at a frequency of 40 kHz) thereby generating ultrasonic waves within the liquid oxidized second drying oil.

[0192] In some examples of the presently disclosed subject matter, the liquid oxidized second drying oil is applied by spraying the liquid oxidized second drying oil over the shaped core region. In some examples of the presently disclosed subject matter, the liquid oxidized second drying oil is applied by spreading the liquid oxidized second drying oil over the shaped core region.

[0193] The application of the liquid oxidized second drying oil can be performed using the liquid in either cold or hot form. The liquid oxidized second drying oil has a viscosity that permits the liquid to penetrate or diffuse into the shaped core region of the solid body. As a result, a surface layer of the solid body is formed. In some cases, to facilitate such penetration, the liquid oxidized second drying oil is applied in hot form.

[0194] As such, the resulting solid body comprises a core region enveloped by the surface layer.

[0195] In some examples of the presently disclosed subject matter, the surface layer comprises a surface penetration depth of the liquid oxidized second drying oil into the shaped core region of the solid body, as further described and illustrated with respect to the presently disclosed article of manufacture.

[0196] In some examples of the presently disclosed subject matter, the process comprises applying a liquid oxidized second drying oil more than once.

[0197] It is appreciated that the additional applications of the liquid oxidized second drying oil can involve a different second drying oil, e.g. different raw drying oil, different viscosity etc.

[0198] It is further to be appreciated that the additional applications of the liquid oxidized second drying oil need not to fully envelop the shaped core.

[0199] In some examples of the presently disclosed subject matter, the liquid oxidized second drying oil is dissolved in a natural solvent prior to being applied onto the shaped core region.

[0200] Without being limited thereto, the solvent may be selected from the group consisting of natural solvents: wood turpentine and / or citric acid, or from a group of synthetic solvents such as mineral spirit, xylene and naphtha.

[0201] In some examples of the presently disclosed subject matter, the applying of the liquid oxidized second drying oil is in a total concentration in a volume unit of the surface layer that is greater than the concentration of the liquid oxidized first drying oil in a same volume unit, in the core region. For example, if a volume unit is defined as a square cube sample of 1mm* 1mm, the concentration is determined with respect to a cubic lmm*mm sample of the surface layer vs. a cubic lmm*mm sample of the core region.

[0202] Either after each application of the liquid oxidized second drying oil, or after completing the application of the liquid oxidized second drying oil, the resulting solid body comprising the core region and the surface layer thereof is subjected to thermal treatment, to facilitate polymerization of the liquid oxidized second drying oil. In some examples, this polymerization is promoted by the application of heat and / or ultrasonic vibrations, which accelerate the oxidative curing of the drying oil and thereby harden the surface layer.

[0203] In some examples of the presently disclosed process, the solid body comprising the core region and the surface layer is subjected to a further stage comprising application of a topcoat composition.

[0204] In some examples of the presently disclosed subject matter, the topcoat composition comprises a liquid oxidized third drying oil (which may be the same as or different from the first and second drying oils), topcoat inorganic particles, and a topcoat resin, preferably a meltable natural resin.

[0205] The liquid oxidized third drying oil, while generally as defined hereinabove with respect to oxidized drying oils, is selected or prepared so as to be suitable for incorporation into a topcoat composition. In this context, the third drying oil is typically characterized by a viscosity, in the range of about 300 cP to about 10,000 cP at 30°C, or, at times, 400cP to 10,000cP, to allow for improved flowability, uniform spreading, and effective mixing with the topcoat resin and inorganic particles. This viscosity profile also supports applications by brushing, spraying, dipping, or varnishing techniques.

[0206] The liquid oxidized third drying oil is formulated to participate in polymerization and curing upon application, either by co-curing with the topcoat resin or by undergoing independent oxidative polymerization, depending on the specific resin type and curing protocol employed. The oil may thus contribute directly to the mechanical integrity, barrier properties, and surface durability of the final topcoat layer.

[0207] The liquid oxidized third drying oil may be derived from the same or different raw drying oil as the first or second drying oils but may be subjected to distinct oxidation or thermal treatment conditions — for example, shorter oxidation times or lower temperatures — to tailor its viscosity and reactivity for surface-layer application, without compromising compatibility with the resin or inorganic components.

[0208] Accordingly, the third drying oil is functionally adapted to serve as a surfacefinishing component, promoting formation of a durable, cohesive, and protective outer layer over the surface layer of the solid body.

[0209] In some examples of the presently disclosed subject matter, the inorganic particles of the topcoat composition have a Mohs hardness above 3, according to the Mohs hardness scale.

[0210] In some examples of the presently disclosed subject matter, the inorganic particles of the topcoat composition have a particle size ranging from about 10 nm to about 1000 nm.

[0211] In some examples of the presently disclosed subject matter, the inorganic particles of the topcoat composition have a particle size ranging from about 10 nm to about 300 nm.

[0212] In some examples of the presently disclosed subject matter, the inorganic particles of the topcoat composition are selected from the group consisting of ceramic, alumina, silica, diatomaceous earth, wollastonite, zirconia, titanium oxide, zinc oxide, calcium carbonate, magnesium carbonate, and any combination of same.

[0213] In some examples, the topcoat resin comprises a meltable natural resin. Meltable natural resins may be plant-extracted resins, such as resins secreted in response to injury. Meltable natural resins include, without being limited thereto, damar, copal, amber, balm, balsam, sandarac, gums, mastics, and rosin.

[0214] In some examples of the presently disclosed subject matter, the topcoat composition comprises a natural solvent. In some examples of the presently disclosed subject matter the natural solvent is selected from the group consisting of wood turpentine, citric acid, and / or synthetic solvents such as, mineral spirit, xylene and naphtha. Notably, the solvent used for the liquid oxidized second drying oil, if used, and the solvent used for the topcoat composition may be the same or different.

[0215] In some examples of the presently disclosed subject matter, the topcoat composition is applied in the form of a varnish, and accordingly, varnishing the surface layer of the solid body.

[0216] A unique feature of the presently disclosed process, and as such, of the presently disclosed article of manufacture is that the eventual article of manufacture comprises a metal content of less than 200 ppm, when the metal is selected from the group consisting of lead, manganese, vanadium, titanium, zinc, and cobalt.

[0217] In some examples of the presently disclosed subject matter, the eventual article of manufacture comprises a heavy metal content of less than 200 ppm, the heavy metal being defined as one having a density of 5g / cm3or more.

[0218] In some examples of the presently disclosed subject matter, the eventual solid core of the article of manufacture comprises a heavy metal or a metal selected from the group consisting of lead, manganese, vanadium, titanium, zinc, and cobalt content of less than 200 ppm, at times, less than 150 ppm, at times, less than 100 ppm, at times less than 80 ppm, at times less than 60 ppm, at times less than 25 ppm.

[0219] In the context of the present disclosure, when referring to content of a heavy metal or to a metal selected from the group consisting of lead, manganese, vanadium, titanium, zinc, and cobalt, it is to be understood that if the blend or the solid core of the article of manufacture comprises more than one such metal, the content of each of the metals is not more than the recited limit.

[0220] A unique feature of the presently disclosed process is that it is free from the use of metal as a catalyst, such as heavy metal containing catalyst.

[0221] A further or alternative unique feature of the presently disclosed process - and as such, of the presently disclosed article of manufacture - is that the liquid blend, and the eventual article of manufacture is essentially free of a binding active amount of sterol, acrylate, asphalt, and / or polyester. In the context of the presently disclosed subject matter, when referring to "essentially free" it is to be understood to include no detectable (undetectable) amount or, if detected, an amount that has no binding or curing effect on the oxidized drying oil (be it the first, second or third).

[0222] Similarly, in the context of the presently disclosed subject matter, when referring to an amount of "up to" a specified limit, it is to be understood to also encompass the absence of the specified material, including no detectable amount of the specified material. For example, a reference to a blend comprising up to 200 ppm of a metal it is to be understood to encompass also a blend that comprises either no metal or no detectable amount of the metal.

[0223] In connection with the above, it is to be understood that the determination of the presence (or absence / no detectable amount) of the metal is carried out by techniques known in the art, such as inductively coupled plasma mass spectrometry (ICP-MS), atomic absorption spectroscopy (AAS), or X-ray fluorescence (XRF).

[0224] A further or alternative unique feature of the presently disclosed process, and as such, of the presently disclosed article of manufacture is that the solid core is essentially free of synthetic binders.

[0225] A further or alternative unique feature of the presently disclosed process, and as such, of the presently disclosed article of manufacture is that the topcoat, if present, is essentially free of synthetic resins.

[0226] The present disclosure also provides an article of manufacture. According to the presently disclosed subject matter, the article of manufacture comprises a solid body that has a core region, a surface layer and optionally a topcoat layer.

[0227] The core region of the article of manufacture comprises a mixture of (i) inorganic particulate matter comprising rock particles and unfired clay particles, as defined hereinabove, (ii) fibrous material, as defined hereinabove and (iii) a polymerized first drying oil, the term "polymerized drying oil" being as defined hereinabove.

[0228] The surface layer of the article of manufacture comprises a polymerized second drying oil which may be the same or different from the polymerized first drying oil. The topcoat layer, if present, comprises a polymerized third drying oil and a topcoat resin, preferably, meltable natural resin, the meltable natural resin being as defined hereinabove.

[0229] In the context of the presently disclosed subject matter, it is to be understood that the surface layer is characterized by a total layer width and a penetration depth. The layer width refers to the overall extent of the surface layer formed from the polymerized second drying oil, measured in a direction perpendicular to the surface of the core region, and including both the portion extending above the core region and the portion that penetrates the solid core. The penetration depth defines the portion of the surface layer that extends into and diffuses within / infiltrated into the core region of the solid body.

[0230] In some examples of the presently disclosed subject matter, the surface layer width and the penetration depth are essentially equal.

[0231] In some examples of the presently disclosed subject matter, the surface layer width is greater than the penetration depth. When the surface layer width is greater than the penetration depth, it means that at least a portion of said shaped core region is free of said polymerized second drying oil.

[0232] In some examples of the presently disclosed subject matter, the polymerized first drying oil and said polymerized second drying oil are derived from different raw drying oils, and at least a portion of the surface layer comprises the polymerized first drying oil and the polymerized second drying oil. The presence of both the polymerized first drying oil and the polymerized second drying oil in the surface layer is a result from penetration of the polymerized second drying oil into the shaped and solid blend (resulting in the formation of the solid core).

[0233] In some examples of the presently disclosed subject matter, the shaped core region and the surface layer have a common polymerized drying oil (i.e. of the same raw drying oil), and at least a portion of the shaped core region has a concentration, in a volume unit, of the common polymerized drying oil that is different from the concentration of the common polymerized drying oil at the periphery of the solid body. In other words, when the core region and the surface layer have the same polymerized drying oil, the core region and the surface layer may be distinguished from one another by the concentration of the polymerized drying oil in a segment (volume unit) of the core region and the concentration of the polymerized drying oil in a same volume of a segment of the surface layer.

[0234] In this context, it is to be understood that when referring to a "volume unit of the core region" it means a volume that contains only the core region and when referring to a volume unit of the surface layer, it refers to a volume that contains only the surface layer. Thus, for example, if a volume unit is defined as a square cube sample of 1mm* 1mm, the concentration is determined with respect to a cubic lmm*mm sample of the surface layer vs. a cubic lmm*mm sample of the core region.

[0235] In some examples of the presently disclosed article of manufacture, the polymerized first drying oil, is at a concentration, in a volume unit of the core region, of at least 0.5wt% out of a total dry weight of the solid core. In some examples of the presently disclosed article of manufacture, the polymerized first drying oil, is at a concentration, in a volume unit of the core region, of at least 0.6 wt%; at times, of at least 0.7wt%; at times, at least 0.8 wt%; at times, at least 0.9 wt%, at times, at least 0.97 wt%; at times, at least 0.98wt%; at times, at least 0.99wt%; at times, at least 1.0wt%, out of a total dry weight of said solid core.

[0236] In some examples of the presently disclosed article of manufacture, the polymerized first drying oil, is present at a concentration, in a volume unit of the core region, of between 0.5wt% and about 5wt%.

[0237] In some examples of the presently disclosed article of manufacture, the polymerized first drying oil, is present at a concentration, in a volume unit of the core region, of between 0.8wt% and 3wt%; at times, between 0.97wt% and about 4wt%; at times, between lwt% and about 3wt%; at times, between 1.2wt% and about 4wt%; at times, between 1.1 wt% and 3wt%, at times, of between 0.97wt% and about 4wt%; at times, between lwt% and about 3wt%; at times, between 1.5wt% and about 4wt%; at times, between 1.5wt% and 3wt%.

[0238] In certain examples of the presently disclosed subject matter, a preferred range for the polymerized first drying oil in a volume unit is between 0.5% and 2wt% out of a total weight of the solid core. In some examples of the presently disclosed article of manufacture, the resulting solid core is characterized by its inorganic content.

[0239] In some examples of the presently disclosed subject, the solid core has an inorganic cation that is equal or above 0.00034wt%.

[0240] In some examples of the presently disclosed subject, the solid core of the article of manufacture has an inorganic cation content of at least 0.00034wt%; at times, of at least 0.0007wt%; at times, of at least 0.001wt%; at times, of at least 0.003wt%; at times, of at least 0.004wt%; at times, of at least 0.005wt%; at times, of at least 0.006wt%; at times, of at least 0.007wt%; at times, of at least 0.008wt%; at times, of at least 0.009wt%; at times, of at least 0.01wt%; at times, of at least 0.01 lwt%; at times, of at least 0.0115wt%; at times, of at least 0.012wt%; at times, of at least 0.0125wt%; at times, of at least 0.013wt%.

[0241] In some examples of the presently disclosed subject, the solid core of the article disclosed herein has an inorganic cation content of at most 0.5wt%.

[0242] Generally, the amount of inorganic cation can be determined by any one of methods known to those versed in the art of analytical chemistry. Analysis can be made by any one of atomic emission spectroscopy (AES) and in particular Inductively Coupled Plasma AES (ICP-AES), Inductively Coupled Plasma Mass Spectrometry (ICP-MS) or Ion Chromatography (IC).

[0243] The final article of manufacture has a moisture content of less than lwt%.

[0244] A unique feature of the presently disclosed article of manufacture resides in the enveloping of the core region with the polymerized second drying oil. In some preferred examples, the surface layer formed by the polymerized second drying oil is present along the entire periphery of the solid core region. It has been found that the surface layer, preferably a continuous surface layer, surrounding the entire solid core, contributes to the improved flexural strength of the resulting article of manufacture, being at least 3MPa, at times, at least 3.5MPa, and preferably at least 4MPa.

[0245] A further unique feature of the presently disclosed article of manufacture resides in the fact that there is no need to treat or coat the inorganic particulate matter of the core region prior to mixing the same with the oxidized first drying oil. In other words, the polymerized first drying oil in the article of manufacture is in direct contact with the inorganic particulate matter.

[0246] As noted above, the solid body comprising the solid core region and the surface layer can comprise also a topcoat layer, over at least a segment of the surface layer. The topcoat layer needs not to be over the entire surface layer.

[0247] It has been surprisingly found that the presently disclosed process and / or the composition of the presently disclosed article of manufacture, including the surface layer over the solid core, provides the article of manufacture with an improved flexural strength of at least 3MPa, at times, at least 3.5MPa, and preferably at least 4MPa, when measured on surface-dry article, without the topcoat layer and after said article has been immersed in water at room temperature for 24 hours. The flexural strength according to the presently disclosed subject matter is measured according to EN 14617-2.

[0248] Generally, flexural strength defines the ability of the material to withstand bending forces applied perpendicular to its longitudinal axis. The higher the value, means the article is more resilient to the bending forces applied.

[0249] Reference now is made to Figures 1-3, providing schematic illustrations of different articles of manufacture according to some examples of the presently disclosed subject matter.

[0250] Specifically, Figure 1 schematically illustrates a cross-sectional view of a tile 100 comprising a solid body 102. The solid body includes a core region 104 that comprises a polymerized first drying oil according to the presently disclosed subject matter (depicted schematically as black particles) and a surface layer 106 comprising a polymerized second drying oil according to the presently disclosed subject matter (depicted as amorphous structures).

[0251] Solid body 102 has a perimeter 108, which coincides with the perimeter of surface layer 106.

[0252] Core region 104 includes two zones: an interfacial zone 104A, into which the polymerized second drying oil has penetrated, and which thus includes both the polymerized first drying oil and the polymerized second drying oil, and an internal zone 104B, bounded by perimeter 110, which remains free of the polymerized second drying oil.

[0253] Surface layer 106, located at the periphery of solid surface 102 and has a surface layer width 106A and in this example is shown to be fully embedded within core region 104

[0254] Reference is now made to Figure 2, which schematically illustrates a further example of an article of manufacture according to the presently disclosed subject matter.

[0255] For simplicity, reference numerals used in Figure 1 are incremented by 100 in Figure 2 to denote components having similar structure or function. For example, core region 204 in Figure 2 corresponds functionally to core region 104 in Figure 1.

[0256] Figure 2 schematically illustrates a cross-sectional view of another example of a tile, denoted as tile 200, comprising a solid body 202. The solid body includes a core region 204 analogues to the structure described in Figure 1, and comprising the polymerized first drying oil according to the presently disclosed subject matter (depicted as black particles) and a surface layer 206 comprising the polymerized second drying oil according to the presently disclosed subject matter (depicted as amorphous structures).

[0257] The outer perimeter 208 of solid body 202, is shared with the outer boundary of surface layer 206, which is located along the periphery of solid surface 202.

[0258] Core region 204 is further subdivided into three distinct zones: an interfacial zone 204A into which the polymerized second drying oil has partially penetrated, resulting in the presence of both the polymerized first drying oil and the polymerized second drying oil, an internal / central zone 204B, enclosed by perimeter 210, which is free of the polymerized second drying oil, and a peripheral transition zone 204C, which comprises only the polymerized second drying oil, i.e. is free of the polymerized first drying oil.

[0259] Surface layer 206 is characterized by a surface layer width 206A and a penetration depth 206B. In this example, surface layer width 206A is greater than the penetration depth 206B indicating that the polymerized second drying oil has only partially penetrated into / infiltrated the core region 204.

[0260] Reference is now made to Figure 3, which schematically illustrates yet another example of an article of manufacture according to the presently disclosed subject matter.

[0261] For simplicity, reference numerals used in Figure 1, are incremented by 200 to denote components having a similar structure or function. For example, core region 304 in Figure 3 corresponds functionally to core region 104 in Figure 1.

[0262] Specifically, Figure 3 schematically illustrates a cross-sectional view of a tile 300 comprising a solid body 302. The solid body 302 includes a core region 304 and a surface layer 306, arranged similarly to the configuration shown in Figure 1. In this example, however, an additional topcoat layer 312 is applied over at least a portion of surface layer 306.

[0263] As in the previous examples, the core region 304 comprises a polymerized first drying oil, while the surface layer 306 comprises a polymerized second drying oil. The topcoat layer 312 may include a polymerized third drying oil and a topcoat resin, such as a meltable natural resin, as described elsewhere herein.

[0264] The application of the topcoat layer provides an additional barrier or protective function and may further influence the aesthetic, mechanical, or environmental resistance properties of the final article.

[0265] All definitions, as defined and used herein, should be understood to take precedence over dictionary definitions, definitions in documents incorporated by reference, and / or ordinary meanings of the defined terms.

[0266] As used herein, the term “about” refers to a deviation from a stated value that may extend up to ±1%, ±5%, ±10%, ±15%, and in some embodiments up to ±20%, including both integer and non-integer values, unless otherwise specified. In some embodiments, “about” refers to ±10% of the stated value.

[0267] The indefinite articles “a” and “an”, as used in the description and claims, unless clearly indicated otherwise, should be understood to mean “at least one”. Similarly, the singular forms “a,” “an,” and “the” are intended to include the plural unless the context clearly dictates otherwise.

[0268] The phrase “and / or” should be understood to mean “either or both” of the elements it joins. Multiple elements joined by “and / or” should be construed similarly, meaning “one or more” of the elements may be present, optionally along with others not explicitly listed.

[0269] The term “or”, as used herein, should also be interpreted as “and / or” unless the context clearly dictates otherwise. Only terms such as “only one of’, “exactly one of’, or closed transitional phrases like “consisting of’ shall imply exclusivity.

[0270] The phrase “at least one of’ followed by a list of elements should be interpreted as including any one or more of the elements listed, optionally including combinations, and optionally including other elements not listed.

[0271] Unless otherwise explicitly required, steps recited in methods are not restricted to any particular sequence. Steps may be performed in any logical order, or concurrently, as suited to the specific embodiment.

[0272] All transitional phrases such as “comprising,” “including,” “carrying,” “having,” “containing,” and “involving” are to be construed as open-ended, meaning “including but not limited to.” Only “consisting of’ and “consisting essentially of’ shall be considered closed or semi-closed language, in accordance with their conventional meanings.

[0273] Where numerical ranges are provided, they are to be understood as disclosing all sub-ranges and individual values within the stated range. For example, a range from 1 to 6 includes 1, 2, 3-5, and 6, and all appropriate sub-ranges, such as 2-5 or 3-6. This applies regardless of the breadth or increment of the range.

[0274] The phrases “ranging between,” “ranges from... to...,” and equivalents are used interchangeably and are inclusive of the endpoints and all intermediate values (including fractional or decimal values).

[0275] The term “process,” unless indicated otherwise, refers to manners, means, methods, and procedures for accomplishing a task, including but not limited to those used in material formulation, curing, molding, polymerization, drying, and finishing — and includes any such techniques known to or developable by those skilled in the chemical, materials, or manufacturing arts.

[0276] Further, in the context of the present disclosure:

[0277] The terms “blend”, “solid core”, and “core region” refer to substantially the same combination of components, differentiated by their physical state and processing stage (e.g., liquid vs. solidified), unless expressly stated otherwise.

[0278] The term “drying oil” refers broadly to raw, oxidized, or polymerized forms as separately defined, and any references to first, second, or third drying oils apply analogously to their respective stages in the process or position in the article.

[0279] The term “polymerized drying oil” denotes a drying oil that has undergone sufficient polymerization and / or curing such that its physical and chemical properties are measurably distinct from its raw or oxidized form, including (but not limited to) increased hardness, thermal stability, or decreased solubility.

[0280] The term “liquid oxidized drying oil” denotes a drying oil that has undergone partial oxidation or polymerization, resulting in increased viscosity while retaining fluidity. Specific viscosity ranges for each oil (first, second, third) are detailed in the respective sections.

[0281] Certain features of the presently disclosed subject matter, while described in connection with specific embodiments, may be provided separately or in various sub- combinations, unless the embodiment would be inoperative without them. Conversely, features described separately may be provided in combination.

[0282] Any examples or experimental data provided herein are illustrative and not limiting. Those skilled in the art may apply the disclosed principles using variations in process steps, material selection, or formulation without departing from the scope of the invention as claimed.

[0283] LIST OF PARAGRAPHS

[0284] The following statements / paragraphs disclose features of the present disclosure: 1. A process for producing an article of manufacture, the process comprising: providing a liquid blend of (i) a liquid oxidized first drying oil (ii) water, (iii) inorganic particulate matter comprising rock particles, unfired clay particles and (iv) fibrous material; molding within a mold the liquid blend under conditions to cause the blend to solidify into a shaped core region of a solid body; applying, at least once, over the solidified shaped core region of the solid body, a liquid oxidized second drying oil, which can be the same or different from said liquid oxidized first drying oil, to form a surface layer of the solid body, the surface layer being peripheral to said solidified core region of the solid body; and optionally, applying a topcoat composition over said surface layer to form a topcoat layer, said topcoat composition comprises a resin and a liquid oxidized third drying oil.

[0285] 2. The process of paragraph 1, wherein said liquid oxidized first drying oil has a viscosity of between about 2,500 cP and about 80,000 cP as determined at a temperature of 30°C.

[0286] 3. The process of paragraph 1 or 2, wherein said liquid oxidized second drying oil has a viscosity of between about 300 cP and about 10,000 cP as determined at a temperature of 30°C.

[0287] 4. The process of any one of paragraphs 1 to 3 or any combinations of paragraphs 1 to 3, wherein said liquid oxidized third drying oil, if present, has a viscosity of between about 300 cP and about 10,000 cP as determined at a temperature of 30°C.

[0288] 5. The process of any one of paragraphs 1 to 4 or any combinations of paragraphs 1 to 4, wherein said liquid oxidized first drying oil has a viscosity in a range of about 100 cP and about 4,000 cP, as determined at a temperature of 90°C.

[0289] 6. The process of any one of paragraphs 1 to 5 or any combinations of paragraphs 1 to 5, wherein said liquid oxidized second drying oil has a viscosity in a range of 15 cP and 500 cP determined at a temperature of 90°C. 7. The process of any one of paragraphs 1 to 6, or any combinations of paragraphs 1 to 6, wherein said liquid oxidized third drying oil has a viscosity in a range of 15 cP and 500 cP determined at a temperature of 90°C.

[0290] 8. The process of any one of paragraphs 1 to 7, or any combinations of paragraphs 1 to 7, wherein said conditions comprises reduction in water content to below 10wt%.

[0291] 9. The process of any one of paragraphs 1 to 8, or any combinations of paragraphs 1 to 8, wherein said liquid oxidized first drying oil, said liquid oxidized second drying oil and said liquid oxidized third drying oil, if present, may be subjected, independently, by introducing into the raw drying oil gas containing oxygen to form respectively, an oxygen enriched first, second or third drying oil and subjecting the oxygen enriched first, second or third drying oil to thermal treatment.

[0292] 10. The process of paragraph 9, wherein said gas containing oxygen, which may be the same or different for obtaining the liquid oxidized first drying oil, liquid oxidized second drying oil and liquid oxidized third drying oil, is selected from oxygen and air.

[0293] 11. The process of paragraph 9 or 10, wherein said introducing gas containing oxygen is by bubbling.

[0294] 12. The process of any one of paragraphs 1 to 8, or any combinations of paragraphs 1 to 8, wherein said liquid oxidized first drying oil, said liquid oxidized second drying oil and said liquid oxidized third drying oil, if present, are obtained, independently, by subjecting raw drying oil to thermal treatment.

[0295] 13. The process of any one of paragraphs 1 to 12, or any combinations of paragraphs 1 to 12, wherein said liquid oxidized first drying oil, said liquid oxidized second drying oil and said liquid oxidized third drying oil are obtained, independently, by exposing a raw drying oil to irradiation.

[0296] 14. The process of any one of paragraphs 1 to 13, or any combinations of paragraphs 1 to 13, comprising sequentially applying more than once the liquid oxidized second drying oil over said solid core or over previously applied liquid oxidized second drying oil, the two or more applications may comprise the same or different liquid oxidized second drying oil. 15. The process any one of paragraphs 1 to 14, or any combinations of paragraphs 1 to 14, wherein said liquid blend comprises said liquid oxidized first drying oil content of at least 0.5wt% out of the total weight of said blend, without said water.

[0297] 16. The process any one of paragraphs 1 to 15, or any combinations of paragraphs 1 to 15, wherein said liquid blend comprises said liquid oxidized first drying oil content of between 0.5wt% and about 5wt%.

[0298] 17. The process of any one of paragraphs 1 to 16, or any combinations of paragraphs 1 to 16, wherein said liquid oxidized first drying oil and liquid oxidized second drying oil and said liquid oxidized third drying oil are obtained from a same raw drying oil.

[0299] 18. The process of any one of paragraphs 1 to 17, or any combinations of paragraphs 1 to 17, wherein said liquid oxidized first drying oil, liquid oxidized second drying oil and liquid oxidized third drying oil, are each, independently, obtained from a plant derived drying oil or fish derived drying oil.

[0300] 19. The process of paragraph 18, wherein the plant derived drying oil is selected from the group consisting of tung oil, hemp oil, biofene or trans- beta- farnesene, linseed oil, poppy oil, walnut oil, palm oil, sunflower oil, cottonseed oil, corn oil, soybean oil, safflower oil, perilla oil, oiticica oil, rapeseed oil, tobacco oil, rubber seed oil, Manihot glaziovii oil, grape oil, sesame oil, colza oil, camelina oil, argemone oil, and combinations thereof.

[0301] 20. The process of paragraph 18, wherein said fish derived drying oil is selected from the group consisting of fish-derived, such as, sardine oil, cod liver oil, herring oil, and combination of same.

[0302] 21. The process of any one of paragraphs 1 to 20, or any combinations of paragraphs 1 to 20, wherein said inorganic particulate matter of said solid core comprises water insoluble inorganic particles.

[0303] 22. The process of any one of paragraphs 1 to 21, or any combinations of paragraphs 1 to 21, wherein said inorganic particulate matter are natural inorganic materials having a Mohs hardness of at least 3. 23. The process of any one of paragraphs 1 to 22, or any combinations of paragraphs 1 to 22, wherein said rock particles are selected from the group consisting of igneous rocks, sedimentary rocks and metamorphic rock and any combination of same.

[0304] 24. The process of paragraph 23, wherein said rock particles are selected from the group consisting of Pumice, Obsidian, Rhyolite, Scoria, Dacite Granite, Gabbro, Diabase, Diorite, Pegmatite, Peridotite, Basalt, quarts (igneous rocks); limestone, sandstone, shale, dolomite, chalk (sedimentary rocks), and marble, quartzite (metamorphic rocks) and combinations of same.

[0305] 25. The process of any one of paragraphs 1 to 24, or any combinations of paragraphs 1 to 24, wherein said unfired clay particles comprise at least one oxide selected from the group consisting of silica, alumina, magnesia, and combination of same.

[0306] 26. The process of any one of paragraphs 1 to 25, or any combinations of paragraphs 1 to 25, wherein said unfired clay particles comprise at least aluminum phyllosilicate.

[0307] 27. The process of any one of paragraphs 1 to 26, or any combinations of paragraphs 1 to 26, wherein said unfired clay particles comprise at least one clay mineral having a plasticity index above 20% and liquid limit above 40% as determined according to ASTM4318.

[0308] 28. The process of any one of paragraphs 1 to 27, or any combinations of paragraphs 1 to 27, wherein said inorganic particulate matter in the blend have particle size distribution ranging from 0. Imicron to 20mm.

[0309] 29. The process of any one of paragraphs 1 to 28, or any combinations of paragraphs 1 to 27, wherein said fibrous material is a natural fibrous material.

[0310] 30. The process of any one of paragraphs 1 to 29, or any combinations of paragraphs 1 to 29, wherein said fibrous material comprises plant derived fibrous material. 31. The process of any one of paragraphs 1 to 30, or any combinations of paragraphs 1 to 30, wherein said fibrous material comprises at least one of cellulose, hemicellulose, and lignocellulose fibers.

[0311] 32. The process of any one of paragraphs 1 to 31, or any combinations of paragraphs 1 to 31, wherein said fibrous material comprises fibers selected from the group consisting of flax, sisal, hemp, jute, cotton, abaca, bamboo, ramie, banana, and kenaf and combinations of same.

[0312] 33. The process of any one of paragraphs 1 to 32, or any combinations of paragraphs 1 to 32, wherein said fibrous material comprises basalt fibers.

[0313] 34. The process of any one of paragraphs 1 to 33, or any combinations of paragraphs 1 to 33, wherein said fibrous material has a longitudinal dimension of between 2mm and 30mm.

[0314] 35. The process of any one of paragraphs 1 to 34, or any combinations of paragraphs 1 to 34, wherein said fibrous material is in an amount of at least 1% out of a total volume of the blend.

[0315] 36. The process of any one of paragraphs 1 to 35, or any combinations of paragraphs 1 to 35, wherein said fibrous material is in an amount of between about 1% and 20% out of a total volume of the blend.

[0316] 37. The process of any one of paragraphs 1 to 36, or any combinations of paragraphs 1 to 36, comprising applying said topcoat composition over said surface layer.

[0317] 38. The process of any one of paragraphs 1 to 37, or any combinations of paragraphs 1 to 37, wherein said topcoat composition comprises topcoat inorganic particles.

[0318] 39. The process of paragraph 38, wherein said inorganic particles of the topcoat composition have a Mohs hardness above 3, according to the Mohs hardness scale.

[0319] 40. The process of paragraph 38 or 39, wherein said inorganic particles of the topcoat composition have a particle size ranging from about lOnm to about l,000nm. 41. The process of any one of paragraphs 38 to 40, or any combinations of paragraphs 38 to 40, wherein said topcoat inorganic particles of the topcoat composition are selected from the group consisting of ceramic, Alumina, Silica, Diatomic earth, Wollastonite, Zirconia, Titanium oxide, Zinc oxide, Calcium carbonate, Magnesium carbonate, and any combination of same.

[0320] 42. The process of any one of paragraphs 1 to 41, or any combinations of paragraphs 1 to 41, wherein said topcoat composition comprises a natural solvent and / or synthetic solvent.

[0321] 43. The process of paragraph 42, wherein said natural solvent is selected from the group consisting of wood turpentine or and / or citric acid, or a synthetic solvent selected from the group consisting of mineral spirit, xylene and naphtha.

[0322] 44. The process of any one of paragraphs 1 to 43, or any combinations of paragraphs 1 to 43, wherein conditions causing the blend to solidify in said mold comprises a combination of thermal treatment and compression of the liquid blend.

[0323] 45. The process of paragraph 44, wherein said thermal treatment of the liquid blend in said mold comprises heating to a temperature of at least 30°C.

[0324] 46. The process of paragraph 45, wherein said thermal treatment of the liquid blend in said mold comprises heating to a temperature of between about 30°C and about 140°C.

[0325] 47. The process of any one of paragraphs 44 to 46, or any combinations of paragraphs 44 to 46, wherein said compression comprises a pressure of at least 10 Bar.

[0326] 48. The process of any one of paragraphs 44 to 47, or any combinations of paragraphs 44 to 47, comprising applying negative air pressure during at least portions of the compression duration.

[0327] 49. The process of any one of paragraphs 1 to 48, or any combinations of paragraphs 1 to 48, comprising extracting the shaped core region from said mold and drying the shaped core region to a moisture content of between 0.1% and 1%.

[0328] 50. The process of any one of paragraphs 1 to 49, or any combinations of paragraphs 1 to 49, wherein said applying, at least once, of the second drying oil is by any one or combination of steps comprising immersing the shaped core region within the liquid oxidized second drying oil,; spraying the liquid oxidized second drying oil over the shaped core region; spreading the liquid oxidized second drying oil over the shaped core region.

[0329] 51. The process of paragraph 50, wherein said immersing of the shaped core region within the liquid oxidized second drying oil is performed with ultrasonic treatment.

[0330] 52. The process of any one of paragraphs 1 to 51, or any combinations of paragraphs 1 to 51, wherein said applying of the liquid oxidized second drying oil form a surface layer of the solid body, the surface layer comprising surface penetration depth of the liquid oxidized second drying oil into the shaped core region of the solid body.

[0331] 53. The process of any one of paragraphs 1 to 52, or any combinations of paragraphs 1 to 52, wherein said oxidized second drying oil is dissolved in a natural solvent prior to being applied onto the shaped core region.

[0332] 54. The process of paragraph 53, wherein said solvent is selected from the group consisting of wood turpentine or and / or citric acid, or a synthetic solvent selected from the group consisting of mineral spirit, xylene and naphtha.

[0333] 55. The process of any one of paragraphs 1 to 54, or any combinations of paragraphs 1 to 54, comprising applying said liquid oxidized second drying oil in a total concentration in a volume unit that is greater than the concentration of the liquid oxidized first drying oil in a same volume unit, in the core region.

[0334] 56. The process of any one of paragraphs 1 to 55, or any combinations of paragraphs 1 to 55, wherein said liquid oxidized first drying oil and liquid oxidized second drying are of a same raw drying oil.

[0335] 57. The process of any one of paragraphs 1 to 56, or any combinations of paragraphs 1 to 56, when dependent on paragraph 37, comprising varnishing said topcoat composition.

[0336] 58. The process of any one of paragraphs 1 to 57, or any combinations of paragraphs 1 to 57, comprising applying thermal treatment onto the solid body after formation of said surface layer and / or prior to applying the topcoat composition, the thermal treatment comprises heating the solid body to a temperature of between 30°C and about 300°C.

[0337] 59. The process of any one of paragraphs 1 to 58, or any combinations of paragraphs 1 to 58, comprising irradiating the solid body, after formation of said surface layer and / or prior to applying the topcoat composition, the irradiation selected from the group consisting of UV irradiation and IR irradiation.

[0338] 60. The process of any one of paragraphs 1 to 59, or any combinations of paragraphs 1 to 59, wherein said liquid blend comprises a heavy metal content or a content of a metal selected from the group consisting of lead, manganese, vanadium, titanium, zinc and cobalt, of less than 200ppm.

[0339] 61. The process of any one of paragraphs 1 to 60, or any combinations of paragraphs 1 to 60, being essentially free of a binding active amount of sterol, acrylate, asphalt or polyester.

[0340] 62. The process of any one of paragraphs 1 to 61, or any combinations of paragraphs 1 to 61, wherein said blend is essentially free of synthetic binders and / or said topcoat, if present, is essentially free of synthetic resins.

[0341] 63. An article of manufacture comprising a solid body including a core region, a surface layer, the surface layer being at a periphery segment of said core region, and optionally a topcoat over said surface layer; the core region comprises an essentially homogenous blend of (i) inorganic particulate matter comprising rock particles and unfired clay particles, (ii) fibrous material and (iii) a polymerized first drying oil; the surface layer comprises a polymerized second drying oil which may be the same or different from said polymerized first drying oil; the topcoat layer, if present, comprises a polymerized third drying oil and a resin; wherein said inorganic particulate matter have a particle size within a range of about 0.1 micron and about 20mm; and wherein at least one of the following is fulfilled: said polymerized first drying oil and said polymerized second drying oil are from different raw drying oils; and said polymerized second drying oil is present, in a volume unit of the surface layer, at a concentration, that is greater than concentration of said polymerized first drying oil in a same volume unit of said core region.

[0342] 64. The article of manufacture of paragraph 63, wherein said polymerized first drying oil and said polymerized second drying oil are of different raw drying oils, and at least a portion of said surface layer comprises the polymerized first drying oil and the polymerized second drying oil.

[0343] 65. The article of manufacture of paragraph 63 or 64, wherein said polymerized first drying oil is in direct contact with said inorganic particulate matter.

[0344] 66. The article of manufacture of any one of paragraphs 63 to 65, or any combinations of paragraphs 63 to 65, wherein said surface layer has a layer width and a penetration depth into said core region, the penetration depth being the same or smaller than the layer width.

[0345] 67. The article of manufacture of any one of paragraphs 63 to 66, or any combinations of paragraphs 63 to 66, wherein at least a portion of said shaped core region is free of said polymerized second drying oil.

[0346] 68. The article of manufacture of any one of paragraphs 63 to 67, or any combinations of paragraphs 63 to 67, wherein shaped core region and said surface layer have a common polymerized drying oil, and at least a portion of said shaped core region has a concentration, in a volume unit, of the common polymerized drying oil that is different from the concentration of the common polymerized drying oil at the periphery of the solid body.

[0347] 69. The article of manufacture of any one of paragraphs 63 to 68, or any combinations of paragraphs 63 to 68, wherein said surface layer is present along the entire periphery of said solid core region.

[0348] 70. The article of manufacture of any one of paragraphs 63 to 69, or any combinations of paragraphs 63 to 69, comprising a topcoat over at least a segment of said surface layer. 71. The article of manufacture of any one of paragraphs 63 to 70, or any combinations of paragraphs 63 to 70, comprising said polymerized first drying oil, at a concentration, in a volume unit of said core region, of at least 0.5wt% out of a total dry weight of said solid core.

[0349] 72. The article of manufacture of any one of paragraphs 63 to 71, or any combinations of paragraphs 63 to 71, comprising said polymerized first drying oil, at a concentration, in a volume unit of said core region, of between 0.5wt% and about 5wt%.

[0350] 73. The article of manufacture of any one of paragraphs 63 to 72, or any combinations of paragraphs 63 to 72, having has a flexural strength of at least 3MPa, when measured on surface-dry article, without said topcoat layer, after said article has been immersed in water at room temperature for 24 hours.

[0351] 74. The article of manufacture of any one of paragraphs 63 to 73, or any combinations of paragraphs 63 to 73, wherein said inorganic particulate matter have a particle size within a range of about 0.1 micron and about 20mm.

[0352] 75. The article of manufacture of any one of paragraphs 63 to 74, or any combinations of paragraphs 63 to 74, having a moisture content of less than lwt%.

[0353] 76. The article of manufacture of any one of paragraphs 63 to 75, or any combinations of paragraphs 63 to 75, wherein said polymerized first drying oil, said polymerized second drying oil and said polymerized third drying oil, if said topcoat is present, are independently from a same or different raw drying oil.

[0354] 77. The article of manufacture of any one of paragraphs 63 to 76, or any combinations of paragraphs 63 to 76, wherein said polymerized first drying oil, said polymerized second drying oil and said polymerized third drying oil, if said topcoat is present, are independently from a plant derived raw drying oil and fish derived raw drying oil.

[0355] 78. The article of manufacture of paragraph 77, wherein said plant derived raw drying oil is selected from the group consisting of tung oil, hemp oil, biofene or trans- beta-farnesene, linseed oil, poppy oil, walnut oil, palm oil, sunflower oil, cottonseed oil, corn oil, soybean oil, safflower oil, perilla oil, oiticica oil, rapeseed oil, tobacco oil, rubber seed oil, Manihot glaziovii oil, grape oil, sesame oil, colza oil, camelina oil, argemone oil, and combinations thereof 79. The article of manufacture of any one of paragraphs 63 to 78, or any combinations of paragraphs 63 to 78, being free of an active amount of sterol, acrylate, asphalt and polyester.

[0356] 80. The article of manufacture of any one of paragraphs 63 to 79, or any combinations of paragraphs 63 to 79, wherein said solid core is essentially free of a detectable amount of synthetic binder and / or said topcoat, if present, is essentially free of detectable amounts of synthetic resins.

[0357] 81. The article of manufacture of any one of paragraphs 63 to 80, or any combinations of paragraphs 63 to 80, wherein said first drying oil and second drying oil are each, independently, selected from a plant derived drying oil, or animal derived drying oil.

[0358] 82. The article of manufacture of paragraph 81, wherein said plant derived drying oil is selected from the group consisting of tung oil, hemp oil, biofene or trans- beta-farnesene, linseed oil, poppy oil, walnut oil, palm oil, sunflower oil, cottonseed oil, corn oil, soybean oil, safflower oil, perilla oil, oiticica oil, rapeseed oil, tobacco oil, rubber seed oil, Manihot glaziovii oil, grape oil, sesame oil, colza oil, camelina oil, argemone oil, and combinations thereof.

[0359] 83. The article of manufacture of paragraph 81, wherein said fish derived raw drying oil is selected from the group consisting of sardine oil, cod liver oil, herring oil and combination of same.

[0360] 84. The article of manufacture of any one of paragraphs 63 to 83, or any combinations of paragraphs 63 to 83, wherein said inorganic particulate matter comprise water insoluble inorganic particles.

[0361] 85. The article of manufacture of any one of paragraphs 63 to 84, or any combinations of paragraphs 63 to 84, wherein said inorganic particulate matter are natural inorganic materials having a Mohs hardness of at least 3.

[0362] 86. The article of manufacture of any one of paragraphs 63 to 85, or any combinations of paragraphs 63 to 85, wherein said rock particles are selected from the group consisting of igneous rocks, sedimentary rocks and metamorphic rock and any combination of same. 87. The article of manufacture of paragraph 85, wherein said rock particles are selected from the group consisting of Pumice, Obsidian, Rhyolite, Scoria, Dacite Granite, Gabbro, Diabase, Diorite, Pegmatite, Peridotite, Basalt, quarts, limestone, sandstone, shale, dolomite, chalk, and marble, quartzite, and combinations of same.

[0363] 88. The article of manufacture of any one of paragraphs 63 to 87, or any combinations of paragraphs 63 to 87, wherein said unfired clay particles comprise at least one oxide selected from the group consisting of silica, alumina, magnesia, and combination of same.

[0364] 89. The article of manufacture of any one of paragraphs 63 to 88, or any combinations of paragraphs 63 to 88, wherein said unfired clay particles comprise at least aluminum phyllosilicate.

[0365] 90. The article of manufacture of any one of paragraphs 63 to 89, or any combinations of paragraphs 63 to 89, wherein said unfired clay particles comprise at least one clay mineral having a plasticity index above 20% and liquid limit above 40% as determined according to ASTM4318.

[0366] 91. The article of manufacture of any one of paragraphs 63 to 90, or any combinations of paragraphs 63 to 90, wherein said fibrous material is a natural fibrous material.

[0367] 92. The article of manufacture of any one of paragraphs 63 to 91, or any combinations of paragraphs 63 to91, wherein said fibrous material comprises plant derived fibrous material.

[0368] 93. The article of manufacture of any one of paragraphs 63 to 92, or any combinations of paragraphs 63 to 92, wherein said fibrous material comprises at least one of cellulose, hemicellulose, and lignocellulose fibers.

[0369] 94. The article of manufacture of any one of paragraphs 63 to 93, or any combinations of paragraphs 63 to 93, wherein said fibrous material comprises fibers selected from the group consisting of flax, sisal, hemp, jute, cotton, abaca, bamboo, ramie, banana, and kenaf and combinations of same.

[0370] 95. The article of manufacture of any one of paragraphs 63 to 91, wherein said fibrous material comprises basalt fibers. 96. The article of manufacture of any one of paragraphs 63 to 95, or any combinations of paragraphs 63 to 95, wherein said fibrous material has a longitudinal dimension of between about 2mm and about 30mm.

[0371] 97. The article of manufacture of any one of paragraphs 63 to 96, or any combinations of paragraphs 63 to 96, wherein said fibrous material is present in a volume unit of said core region, at a concentration of at least 1%.

[0372] 98. The article of manufacture of any one of paragraphs 63 to 97, or any combinations of paragraphs 63 to 97, wherein said fibrous material is present, in a volume unit of said core region, at a concentration of between about 1% and 20%.

[0373] 99. The article of manufacture of any one of paragraphs 63 to 98, or any combinations of paragraphs 63 to 98, wherein said topcoat comprises topcoat inorganic particles.

[0374] 100. The article of manufacture of paragraph 99, wherein said topcoat inorganic particles have a Mohs hardness above 3, according to the Mohs hardness scale.

[0375] 101. The article of manufacture of paragraph 99 or 100, wherein said topcoat inorganic particles have a particle size ranging from about 10 to about l,000nm.

[0376] 102. The article of manufacture of any one of paragraphs 99 to 101, or any combinations of paragraphs 99 to 101, wherein said inorganic particles of the topcoat composition are selected from the group consisting of ceramic, Alumina, Silica, Diatomic earth, Wollastonite, Zirconia, Titanium oxide, Zinc oxide, Calcium carbonate, Magnesium carbonate and any combination of same.

[0377] 103. The article of manufacture of any one of paragraphs 63 to 102, or any combinations of paragraphs 63 to 102, comprising a metal content of less than 200ppm, the metal being a heavy metal or a metal selected from lead, manganese, vanadium, titanium, zinc and cobalt.

[0378] 104. The article of manufacture of any one of paragraphs 63 to 103, or any combinations of paragraphs 63 to 103, wherein said solid core is free of a binding active amount of sterol, acrylate, asphalt and polyester. 105. The article of manufacture of any one of paragraphs 63 to 104, or any combinations of paragraphs 63 to 104, wherein said solid core is essentially free of a detectable amount of synthetic binders and / or said topcoat, if present, is essentially free of synthetic resins.

[0379] 106. The article of manufacture of any one of paragraphs 63 to 105, or any combinations of paragraphs 63 to 105, wherein said core region is a compressed region.

[0380] The invention will now be described by non-limiting examples.

[0381] DESCRIPTION OF NON-LIMITING EXAMPLES

[0382] Methods

[0383] Determining oil gas enrichment - To determine its value, in this example Polarographic Dissolved Oxygen Sensors were used. However, several other methods exist and are suitable such as Optical Dissolved Oxygen Sensors, Electrochemical Dissolved Oxygen Sensors, Galvanic Dissolved Oxygen Sensors, Measuring Dissolved Oxygen by the Colorimetric Method.

[0384] Determining degree of polymerization - Higher polymerization results in larger molecules of the oil, i.e. higher molecular weight, thus it can be tested and characterized by any method sensitive to molecule size, the main technique used in the following examples is viscosity testing, however Size Exclusion Chromatography (SEC) was also used to verify the correlation and transformation of the small molecules into large molecules.

[0385] Viscosity -A rotary viscometer was used to determine the oil viscosity. The treated oil was first cooled to room temperature after the treatment in order to stop the polymerization reaction. To avoid extensive heating during the viscosity test, a sample of the oil was re-heated to 150°C while being placed under the viscometer probe, then the heating was stopped and allowed to cool down slowly while measuring the viscosity every 5°C. Viscosity at temperatures 90°C and 30°C are the most important during the quality control process that has been done. % Absorption - Water absorption tests were performed according to the demands of EN 15286 and by the practice of EN 14617-1. In all of the following examples the values presented are the values of 24-hour immersion in water.

[0386] Flexural strength - WA determined by three points bending test according to the demands of EN 15286 and by the practice of EN 14617-2.

[0387] In the following non-limiting examples,

[0388] - when referring to FOO3.6 it is to be understood to refer to oxidized first drying oil with a viscosity value at 30°C of 2,300 cP.

[0389] - when referring to FOO42.5 it is to be understood to refer to oxidized first drying oil with a viscosity value at 30°C of 42,500 cP..

[0390] Example 1: Preparing particulate mixture

[0391] Clay material - Clay material was prepared from mixing bentonite and ball clay at a ratio of 1 :2.4. The bentonite and ball clay were obtained from a commercial supplier.

[0392] The bentonite and ball clay were each dried and downsized by milling until reaching D50<7 microns. Both clay materials (bentonite and ball clay) are considered non-organic high plasticity clays (according to Israeli Standard 253, paragraphs 103.3.2, 103.4, 103.8-103.10, 206.1, 206.1.2, 206.2.2 and Table 6 therein, and plasticity test according to ASTM D 4318). The ball clay was selected to have a minimum index plasticity above 30% and liquid limit above 50%, The Bentonite was selected to have liquid limit above 400%.

[0393] Water insoluble inorganic material - water insoluble inorganic material included any one of

[0394] Inorganic material I: limestone powder

[0395] Inorganic material 2 limestone and basalt mixture at a weight ratio of about 2.2: 1.

[0396] Inorganic material 3: limestone and quarts mixture at a weight ratio of about

[0397] 0.75: 1. The insoluble inorganic material was downsized by milling and separated by sieving to different fractions distinguished by their D50 according to Table 1 :

[0398] Table 1: Inorganic material composition

[0399] The clay material, each of the water insoluble inorganic material and Flax fibers (fibrous material, fiber length of 14mm) were then combined into different dry compositions (1 to 3), with the ratio of the different components as provided in Table 2. The amounts of the clay material and water insoluble inorganic material were selected to provide one cumulative distribution that behaves within an upper and lower limit (derived from the mathematical equation of , in order to reach a desired shape parameter (q) within the range of 0.24 and 0.33.

[0400] Figure 4 provides a scatter plot representing cumulative particle size distribution with an optimal shape parameter, with a target shape factor range of 0.24- 0.33 being presented by the solid lines, and the optimal distribution being illustrated by the dashed line.

[0401] Figure 5 provides a scatter plot representing cumulative particle size distribution in an insoluble particulate material mixture (based on Table 2) with an optimal shape parameter based on fitting to the optimal distribution curve, with a target shape factor range of 0.24-0.33 being represented by the solid lines, and the optimal distribution being illustrated a dashed line, and particle size distribution of the experimental mixture being represented by a doubled line. Table 2: Dry Compositions (weight %)

[0402] Example 2: powder particles content necessity

[0403] The properties of the mixture are highly dependent on the existence of small particles, creating higher packing density which results in higher strength. Mixture 1 (Mix 1) is an example of a mixture with small inorganic particles below 40 microns (except for the clay particles). Mixture 2 (Mix 2) is an example of a mixture without small inorganic particles below 40 microns (except for the clay particles). Both mixtures were constructed with the same principle of particle size distribution. Both mixtures were coated with the second liquid oxidized oil only. The comparison shows significant difference when there was a use of powder particles in the mixture, making them essential for the discussed mixtures.

[0404] Table 3: Dry Compositions (weight %)

[0405] Example 3: Preparing of liquid oxidized drying oils

[0406] For the preparation of the blend, raw Tung oil, cold pressed, free of additives, was used. To obtain the liquid oxidized tung oil, the Tung oil was bubbled with air pump and “air stone”, having air pumping rate of 35 liter / min. 10 Liters of the oil was aerated for 4 hours to achieve air enriched Tung oil. At this stage, the oil viscosity or the air enriched Tung oil is similar to the raw oil, the only difference is the presence of dissolved oxygen in the oil which allows faster oxidation / polymerization reaction, upon thermal treatment.

[0407] Treated Tung oil / liquid oxidized Tung oil - was obtained by applying thermal treatment to polymerize the oil until reaching the desired viscosity. During the heating of the oil, the air enriched oil was stirred to allow homogeneity to heat uptake.

[0408] Two types of liquid oxidized first oil were prepared and tested in the following examples.

[0409] One liquid oxidized first drying oil (referred to herein by the abbreviation FOO3.6), the heat of the oil was measured using a thermocouple, which controlled the heating elements thermostat, the temperature set for this treatment was 200°C, for 8 hours. The resulted partial polymerized oil (FOO) had viscosity of 164 cp @ 90°C and viscosity of 3,615 cp @ 30°C.

[0410] Second liquid oxidized first drying oil (referred to herein by the abbreviation FOO42.5), the heat of the oil was measured using a thermocouple, which controlled the heating elements thermostat, the temperature set for this treatment was 200°C, for 9.5 hours. The resulted partial polymerized oil (FOO) had viscosity of 1,895 cp @ 90°C and viscosity of 42,545 cp @ 30°C.

[0411] For the liquid oxidized second drying oil (referred to herein by the abbreviation SOO), the heat of the oil was measured using a thermocouple, which controlled the heating elements thermostat, the temperature set for this treatment was 200°C, for 6.5 hours. The resulted partial polymerized oil (SOO) had viscosity of 101 cp @ 90°C and viscosity of 2,272 cp @ 30°C.

[0412] For the liquid oxidized third drying oil (referred to herein by the abbreviation TOO), the heat of the oil was measured using a thermocouple, which controlled the heating elements thermostat, the temperature set for this treatment was 200°C, for 6.5 hours. The resulted partial polymerized oil (TOO) had viscosity of 101 cp @ 90°C and viscosity of 2,272 cp @ 30°C.

[0413] The raw Tung oil has an initial viscosity of between 230-240cp in room temperature (25°C) and total viscosity -temperature response as shown in Figure 6A.

[0414] Any oil having viscosity of between 2,500 cP and 80,000cP at 30°C and overall behaviour like in Figure 6B, is suitable as liquid oxidized first drying oil.

[0415] Specifically, Figure 6B illustrates the full temperature-viscosity behavior of a first oxidized oil formulation, presented as three distinct curves:

[0416] The upper curve represents the maximum viscosity response expected across temperatures for this oil type.

[0417] The lower curve represents the minimum viscosity response across the same range.

[0418] The middle curve shows empirical measurements for the specific sample (FOO42.5), demonstrating its complete viscosity-temperature profile. For this sample, a viscosity of 42,500 cP was measured at 30°C.

[0419] Figure 6B thus provides a comprehensive view of the potential variability in viscosity over a range of temperatures (20°C to ~120°C). Two optional logarithmic equations are shown, corresponding to the boundary curves, offering a tool for calculating viscosity at intermediate temperatures if desired.

[0420] Further, any oil having viscosity of between 300cP and 10,000cP at30°C and overall behaviour like in Figure 6C, is suitable as the liquid oxidized second drying oil and the liquid oxidized third drying oil.

[0421] Specifically, Figure 6C presents an analysis similar to Figure 6B, yet for a second oxidized oil: The upper and lower bounds of the viscosity-temperature response are shown as two curves.

[0422] The middle curve corresponds to a specific oil example, with a measured viscosity of 2,300 cP at 30°C.

[0423] This Figure 6C also spans a broad temperature range (20°C to 160°C), supporting estimation of viscosity across practical conditions. Like Figure 6B, two equations are provided for reference, enabling approximation of viscosity values where needed.

[0424] Example 2: Preparing Article of manufacture

[0425] All the mixtures that were prepared and presented in the non-limiting examples, were prepared as described below:

[0426] Dry mixture preparation - weighting and dry mixing in a rotation mixer all the inorganic particles with the organic fibers until reaching homogenisation.

[0427] Water wetting - unless otherwise stated, wet mixing of the dry mixture was done using a double shaft mixer. All the required amount of ionized-water was first introduced into the dry mixture while mixing until homogenization is reached, after which the liquid first oxidized oil was added, followed by mixing again until homogenization.

[0428] Reference mixtures were prepared only with the ionized-water, having no oil addition to it.

[0429] The mixture was divided to portions for the pressing cycle, each portion was placed in a tile mold cavity. Compression forces were applied to the wet blend in the mold cavities, in all cases the applied pressure was 120 bar, this pressure was maintained for 3 minutes until extra water was squeezed down below 10%w water content.

[0430] The squeezed blends were further placed into an oven of about 100°C for one hour until the humidity was reduced down to below l%w to obtain the solid cores of the tiles. The dried solid cores were coated with the liquid second oxidized Tung oil (SOO), by two dipping stages in the oxidized oil heated to a temperature of about 90°C with thermal treatment in an oven of 2 hours after each dipping.

[0431] Example 3: Comparative Examples

[0432] Example 3A - Necessity for partial polymerization / oxidation

[0433] In this example tiles samples were prepared with FOO obtained with different thermal treatment duration. The procedures are as described above.

[0434] Tile Sample 1 (reference) - l%w raw Tung oil, added into the wet mixture as described above. The dry solid core was coated with raw Tung oil after air saturation process.

[0435] Tile Sample 2 - obtained by using FOO3.6 as defined above as the liquid first oxidized oil, which was added at a content of l%w into the wet mixture followed by drying the solid core, and then coating with SOO as described above.

[0436] Tile Sample 3 - obtained by using FOO42.5 as defined above as the liquid first oxidized oil, which was added at a content of 1.5%w into the wet mixture followed by drying the solid core, and then coating with SOO as described above.

[0437] Table 4 provides the % water absorption as well as the flexural strength of the different samples, before applying the coating (raw Tung oil or the SOO, referred to as "Uncoated"), after applying the coating (raw Tung oil or the SOO, referred to as "Coated"), before wetting (referred to as "Dry") and after wetting (referred to as "Wet"). The Flexural strength is provided in MPa.

[0438] Table 4: Absorption and flexural strengths

[0439] As can be seen, the addition of oxidized oil, even after short oxidation period, improves the properties of better sealant (1.04%w vs. 4.0% water absorption) and higher wet flexural strength (4.0MPa vs. 2.06MPa). Moreover, higher oxidation degree results with better results (0.51%w vs. 1.04% water absorption, 5.57MPa vs. 4.0MPa wet flexural strength). However, there is no straight forward relations between low absorption and high wet strength, those are independent properties that being enhanced with this technique.

[0440] Example 3B: The effect of FOO

[0441] To evaluate the importance of including FOO in the inorganic mixture, two samples were prepared:

[0442] Tile Sample 4 - No FOO was added to the dry mixture and the solid core obtained (in the absence of any FOO) was only coated with oxidized Tung oil (SOO), as in US patent application no. 63 / 535,164)

[0443] Tile Sample 5 - FOO42.5 was introduced into the dry mixture, as described, at a total content of 3%w oil, and the solid core thus obtained was coated with the oxidized Tung oil (SOO).

[0444] It was assumed that in the absence of FOO, namely, Tile Sample 4, will result in a tile which after cutting will absorb full capacity of water (18.5%), in such case the article will lose completely its strength (OMPa) and its dimensional stability (swallow beyond the permitted values of EN 14617-12). As for dry flexural strength, it was assumed that the coating hardens the tile's surface and thus will increase the flexural strength of the tile.

[0445] Table 5 provides the % water absorption as well as the flexural strengths of the different samples, before wetting (referred to as "Dry") and after wetting (referred to as "Wet"). The Flexural strength is provided in MPa.

[0446] Table 5: Absorption and flexural strengths with or without SOO Table 5 shows that there is a need for the combined oxidized oil within the solid core as well as on the surface, the latter being applied as a second layer over the solid core. Further, Table 5 shows that the presence of the SOO on the surface of the solid core significantly reduces the water absorption and increase the wet flexural strength.

[0447] Example 3C: Influence of the amount of FOO introduced into the mixture

[0448] For determining the effect of % of FOO introduced into the dry mixture, the following tile samples were prepared:

[0449] Tile Sample 6 - 1.5%w FOO42.5 in the mixture

[0450] Tile Sample 7 - 3.0%w FOO42.5 in the mixture

[0451] Table 6 provides the % water absorption as well as the flexural strengths of the different samples, before wetting (referred to as "Dry") and after wetting (referred to as "Wet"). The Flexural strength is provided in MPa.

[0452] Table 6: Absorption and flexural strengths

[0453] The results in Table 6 show that addition of FOO above 1% already influence the wet flexural strength to above 5.5 MPa. Addition of more FOO can maintain properties improvement up to certain concentration, as long as it is not over filled with oil, and in this case even an addition of 3% FOO creates the desired sealing and enhancement effect.

[0454] Example 3D - Thermal treatment without bubbling of air

[0455] For determining the effect of thermal treatment on the surface coating, tiles with no first oxidized drying oil (FOO) were used.

[0456] The tiles in this example were coated with the SOO and TOO, according to the procedures described in the previous non-limiting examples. Sample 8 - solid core over which raw tung oil was applied, without air bubbling, however, with the use of a large surface exposure of the raw oil to surrounding air, and vigorous mixing of same, to allow the desired enrichment with oxygen and thermally treating by heating over a hot plate heated to a temperature set of 200°C, for 6.5 hours, as described above.

[0457] Sample 9 - solid core over which oxygen enriched tung oil (raw tung oil pretreated with bubbling) was applied and thereafter thermally treatment as with Sample 8.

[0458] Both Sample 8 and Sample 9 were then top-coated with oxygen enriched tung oil (the TOO) and subjected to thermal treatment by heating in an oven at a temperature set to 200°C, for 6.5 hours, as described above.

[0459] Table 7 provides the % water absorption as well as the flexural strengths of the Samples 8 and 9, before wetting the samples with water (referred to as "Dry") and after wetting the samples with water for 24 hours (referred to as "Wet"). The Flexural strength is provided in MPa.

[0460] Table 7: Absorption and flexural strengths

[0461] The results in Table 7 show that thermal treating the oil with even only large surface exposure to external air and mixing vigorously (with no active air bubbling), is sufficient to achieve the required oxidized oil, preserving all properties similar to tiles prepared with air-bubbled raw oil as the starter before thermal treatment.

[0462] Example 3E -Ultrasonic Assisted Coating

[0463] In this example tiles samples were prepared with FOO42.5 at a total content of 1 ,4wt% in the core region and having a surface layer of the SOO either subjected or not to ultrasonic vibration. The example tiles were finally coated with the TOO. The procedures are as described above. Sample 12 - the core region was surface coated with SOO by dipping the core region in the SOO.

[0464] Sample 13 - the core region was surface coated with SOO by dipping into the SOO and applying ultrasonic vibration (device model: UD600SH-28L manufactured by KWUN WAH INTERNATIONAL LIMITED, marketed under the Eumax brand, device volume of 28 liters, an ultrasonic power output of 600 W, and operates at a frequency of 40 kHz)

[0465] Table 8 provides the % water absorption as well as the flexural strengths of the different samples, before wetting with water (referred to as "Dry") and after wetting with water for 24 hours (referred to as "Wet"). The Flexural strength is provided in MPa.

[0466] Table 9: Effect of US Vibration on Absorption and flexural strengths

[0467] The results in Table 9 show that using ultrasonic assisted dipping leads to better water sealing and improved dry strength of the tile. The strength of the wet tiles was identical, both above 6MPa. It may be that the ultrasonic waves improve the SOO penetration, thereby creating a more sealed and denser surface layer, while the bulk protection remains identical with / without the ultrasonic assistance.

Claims

CLAIMS:

1. A process for producing an article of manufacture, the process comprising: providing a liquid blend of (i) a liquid oxidized first drying oil (ii) water, (iii) inorganic particulate matter comprising rock particles, unfired clay particles and (iv) fibrous material; molding within a mold the liquid blend under conditions to cause the blend to solidify into a shaped core region of a solid body; applying, at least once, over the solidified shaped core region of the solid body, a liquid oxidized second drying oil, which can be the same or different from said liquid oxidized first drying oil, to form a surface layer of the solid body, the surface layer being peripheral to said solidified core region of the solid body; and optionally, applying a topcoat composition over said surface layer to form a topcoat layer, said topcoat composition comprises a resin and a liquid oxidized third drying oil.

2. The process of claim 1, wherein said liquid oxidized first drying oil has a viscosity of between about 2,500 cP and about 80,000 cP as determined at a temperature of 30°C.

3. The process of claim 1 or 2, wherein said liquid oxidized second drying oil has a viscosity of between about 300 cP and about 10,000 cP as determined at a temperature of 30°C.

4. The process of any one of claims 1 to 3, wherein said liquid oxidized third drying oil, if present, has a viscosity of between about 300 cP and about 10,000 cP as determined at a temperature of 30°C.

5. The process of any one of claims 1 to 4, wherein said conditions comprises reduction in water content to below 10wt%.

6. The process of any one of claims 1 to 5, wherein said liquid oxidized first drying oil, said liquid oxidized second drying oil and said liquid oxidized third drying oil, if present, may be subjected, independently, by introducing into the raw drying oil gas containing oxygen to form respectively, an oxygen enriched first, second or third dryingoil and subjecting the oxygen enriched first, second or third drying oil to thermal treatment.

7. The process of any one of claims 1 to 6, wherein said liquid oxidized first drying oil, said liquid oxidized second drying oil and said liquid oxidized third drying oil, if present, are obtained, independently, by subjecting raw drying oil to thermal treatment and / or to irradiation.

8. The process of any one of claims 1 to 7, comprising sequentially applying more than once the liquid oxidized second drying oil over said solid core or over previously applied liquid oxidized second drying oil, the two or more applications may comprise the same or different liquid oxidized second drying oil.

9. The process any one of claims 1 to 8, wherein said liquid blend comprises said liquid oxidized first drying oil content of at least 0.5wt% or between 0.5wt% and about 5wt% out of the total weight of said blend, without said water.

10. The process of any one of claims 1 to 9, wherein said liquid oxidized first drying oil, liquid oxidized second drying oil and liquid oxidized third drying oil, are each, independently, obtained from a plant derived drying oil or fish derived drying oil.

11. The process of any one of claims 1 to 10, wherein said inorganic particulate matter of said solid core comprises water insoluble inorganic particles.

12. The process of any one of claims 1 to 11, wherein said inorganic particulate matter are natural inorganic materials having a Mohs hardness of at least 3.

13. The process of any one of claims 1 to 12, wherein said unfired clay particles comprise at least one clay mineral having a plasticity index above 20% and liquid limit above 40% as determined according to ASTM4318.

14. The process of any one of claims 1 to 13, wherein said inorganic particulate matter in the blend have particle size distribution ranging from 0. Imicron to 20mm.

15. The process of any one of claims 1 to 14, wherein said fibrous material has a longitudinal dimension of between 2mm and 30mm.

16. The process of any one of claims 1 to 15, wherein said fibrous material is in an amount of at least 1% or between about 1% and 20% out of a total volume of the blend.

17. The process of any one of claims 1 to 16, comprising applying said topcoat composition over said surface layer.

18. The process of any one of claims 1 to 17, wherein said topcoat composition comprises topcoat inorganic particles.

19. The process of claim 18, wherein said inorganic particles of the topcoat composition have a Mohs hardness above 3, according to the Mohs hardness scale.

20. The process of claim 18 or 19, wherein said inorganic particles of the topcoat composition have a particle size ranging from about lOnm to about l,000nm.

21. The process of any one of claims 1 to 20, wherein conditions causing the blend to solidify in said mold comprises a combination of thermal treatment and compression of the liquid blend.

22. The process of claim 21, wherein said thermal treatment of the liquid blend in said mold comprises heating to a temperature of at least 30°C or between about 30°C and about 140°C.

23. The process of any claim 21 or 22, wherein said compression comprises a pressure of at least 10 Bar.

24. The process of any one of claims 21 to 23, comprising applying negative air pressure during at least portions of the compression duration.

25. The process of any one of claims 1 to 24, comprising extracting the shaped core region from said mold and drying the shaped core region to a moisture content of between 0.1% and 1%.

26. The process of any one of claims 1 to 25, comprising applying said liquid oxidized second drying oil in a total concentration, in a volume unit, that is greater than the concentration of the liquid oxidized first drying oil in a same volume unit, in the core region.

27. The process of any one of claims 1 to 26, comprising applying thermal treatment onto the solid body after formation of said surface layer and / or prior to applying the topcoat composition, the thermal treatment comprises heating the solid body to a temperature of between 30°C and about 300°C.

28. The process of any one of claims 1 to 27, wherein said liquid blend comprises heavy metal content or a content of a metal selected from the group consisting of lead, manganese, vanadium, titanium, zinc and cobalt, of less than 200ppm.

29. An article of manufacture comprising a solid body including a core region, a surface layer, the surface layer being at a periphery segment of said core region, and optionally a topcoat over said surface layer; the core region comprises an essentially homogenous blend of (i) inorganic particulate matter comprising rock particles and unfired clay particles, (ii) fibrous material and (iii) a polymerized first drying oil; the surface layer comprises a polymerized second drying oil which may be the same or different from said polymerized first drying oil; the topcoat layer, if present, comprises a polymerized third drying oil and a resin; wherein said inorganic particulate matter have a particle size within a range of about 0.1 micron and about 20mm; and wherein at least one of the following is fulfilled: said polymerized first drying oil and said polymerized second drying oil are from different raw drying oils; and said polymerized second drying oil is present, in a volume unit, at a concentration, that is greater than concentration of said polymerized first drying oil in a same volume unit of said core region.

30. The article of manufacture of claim 29, wherein said polymerized first drying oil and said polymerized second drying oil are of different raw drying oils, and at least a portion of said surface layer comprises the polymerized first drying oil and the polymerized second drying oil.

31. The article of manufacture of claim 29 or 30, wherein said polymerized first drying oil is in direct contact with said inorganic particulate matter.

32. The article of manufacture of any one of claims 29 to 31, wherein said surface layer has a layer width and a penetration depth into said core region, the penetration depth being the same or smaller than the layer width.

33. The article of manufacture of any one of claims 29 to 32, wherein shaped core region and said surface layer have a common polymerized drying oil, and at least a portion of said shaped core region has a concentration, in a volume unit, of the common polymerized drying oil that is different from the concentration of the common polymerized drying oil at the periphery of the solid body.

34. The article of manufacture of any one of claims 29 to 33, wherein said surface layer is present along the entire periphery of said solid core region.

35. The article of manufacture of any one of claims 29 to 34, comprising said polymerized first drying oil, at a concentration, in a volume unit of said core region, of at least 0.5wt% or between 0.5wt% and about 5wt% out of a total dry weight of said solid core.

36. The article of manufacture of any one of claims 29 to 35, having has a flexural strength of at least 3MPa, when measured on surface-dry article, without said topcoat layer, after said article has been immersed in water at room temperature for 24 hours.

37. The article of manufacture of any one of claims 29 to 36, wherein said inorganic particulate matter have a particle size within a range of about 0.1 micron and about 20mm.

38. The article of manufacture of any one of claims 29 to 37, having a moisture content of less than lwt%.

39. The article of manufacture of any one of claims 29 to 38, wherein said first drying oil and second drying oil are each, independently, selected from a plant derived drying oil, or animal derived drying oil.

40. The article of manufacture of any one of claims 29 to 39, wherein said inorganic particulate matter comprises water insoluble inorganic particles.

41. The article of manufacture of any one of claims 29 to 40, wherein said inorganic particulate matter are natural inorganic materials having a Mohs hardness of at least 3.

42. The article of manufacture of any one of claims 29 to 41, wherein said unfired clay particles comprise at least one clay mineral having a plasticity index above 20% and liquid limit above 40% as determined according to ASTM4318.

43. The article of manufacture of any one of claims 29 to 42, wherein said fibrous material is a natural fibrous material.

44. The article of manufacture of any one of claims 29 to 43, wherein said fibrous material has a longitudinal dimension of between about 2mm and about 30mm.

45. The article of manufacture of any one of claims 29 to 44, wherein said fibrous material is present in a volume unit of said core region, at a concentration of at least 1% or between about 1% and 20%.

46. The article of manufacture of any one of claims 29 to 45, wherein said topcoat comprises topcoat inorganic particles.

47. The article of manufacture of claim 46, wherein said topcoat inorganic particles have a Mohs hardness above 3, according to the Mohs hardness scale.

48. The article of manufacture of claim 29 or 47, wherein said topcoat inorganic particles have a particle size ranging from about 10 to about l,000nm.

49. The article of manufacture of any one of claims 29 to 48, wherein said core region is a compressed region.

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