Process for making tiles

Abstract

Ceramic tiles may be prepared employing a process characterized by the addition to the ceramic raw materials of an aqueous slurry comprising a swellable clay of the smectite family, a binder and a water-soluble salt of a monovalent cation. The ceramic raw materials mixed and then subjected to wet grinding to produce a slip. The thus obtained slip is then subjected to spray drying.

Claims

1. A process for making ceramic tiles comprising: mixing ceramic raw materials; wet grinding the ceramic raw materials to produce a slip; spray drying the thus obtained slip to produce a powder; and pressing the powder to form green tiles, wherein from about 0.2 to about 3% by weight of an aqueous slurry is introduced to the slip prior to the spray drying, the aqueous slurry comprising: a) from about 5 to about 30% by weight of a swelling clay of the smectite family; b) from about 10 to about 30% by weight of a binder chosen among lignin sulfonates, naphthalene sulfonate-formaldehyde condensate salts, mono- and oligo-saccharides, water-soluble starches, water-soluble cellulose derivatives and mixture thereof; c) from about 0.1 to about 10% by weight of a water-soluble salt of a monovalent cation; and d) from 35 to 84.5% by weight of water, and said aqueous slurry being prepared by: dissolving the salt c) in water to form a first solution, and adding to the first solution the swelling clay of the smectite family a), the binder b), and optional additives.

2. The process of claim 1 wherein from about 0.4 to about 2% by weight of the aqueous slurry is introduced.

3. The process of claim 1, wherein the water-soluble slat of a monovalent cation is one or more selected from a group consisting of ammonium salts and alkali metal salts of chloride, bromide, and phosphate.

4. The process of claim 1, wherein the viscosity of the aqueous slurry has a Brookfield viscosity (25 C., 20 rpm) is below 3,000 mPa*s.

5. The process of claim 1, further comprising homogenizing the aqueous slurry prior to introduction to the slip.

6. The process of claim 1, further comprising homogenizing and sieving the aqueous slurry prior to introduction to the ceramic raw materials or the slip.

7. The process of claim 1, wherein the aqueous slurry comprises a) from about 10 to about 30% by weight of a swelling clay of the smectite family.

8. A process for making ceramic tiles comprising: mixing ceramic raw materials; wet grinding the ceramic raw materials to produce a slip; spray drying the thus obtained slip to produce a powder; and pressing the powder to form green tiles, wherein from about 0.2 to about 3% by weight of an aqueous slurry is introduced to the ceramic raw materials or the slip prior to the spray drying, the aqueous slurry comprising: a) from about 5 to about 30% by weight of a swelling clay of the smectite family; b) from about 10 to about 30% by weight of a binder chosen among lignin sulfonates, naphthalene sulfonate-formaldehyde condensate salts, mono- and oligo-saccharides, water-soluble starches, water-soluble cellulose derivatives and mixture thereof; c) from about 0.1 to about 10% by weight of a water-soluble salt of a monovalent cation; and d) from 35 to 84.5% by weight of water, and said aqueous slurry being prepared by: dissolving the salt c) in water to form a first solution, and adding to the first solution the swelling clay of the smectite family a), the binder b), and optional additives and homogenizing the aqueous slurry prior to introduction to the ceramic raw materials or the slip prior to spray drying.

9. The process of claim 8, wherein the aqueous slurry is introduced into the raw materials prior to or during the mixing of the ceramic raw materials.

10. The process of claim 9, wherein from about 0.4 to about 2% by weight of the aqueous slurry is introduced.

11. The process of claim 8, wherein the aqueous slurry is introduced into the slip prior to the spray drying of the slip.

12. The process of claim 11, wherein from about 0.4 to about 2% by weight of the aqueous slurry is introduced.

13. The process of claim 8, wherein from about 0.4 to about 2% by weight of the aqueous slurry is introduced.

Description

DESCRIPTION OF THE INVENTION

(1) It is a fundamental object of the present invention an aqueous slurry comprising: a) from 5 to 30% by weight of a swelling clay of the smectite family; b) from 10 to 30% by weight of a binder chosen among lignin sulfonates, naphthalene sulfonate-formaldehyde condensate salts, mono- and oligo-saccharides, water-soluble starches, water-soluble cellulose derivatives, and mixture thereof; c) from 0.1 to 10% by weight of a water-soluble salt of a monovalent cation.

(2) It is another object of the invention a process for making ceramic tiles comprising the following steps:

(3) I) mixing of the ceramic raw materials;

(4) II) wet grinding of the ceramic raw materials;

(5) III) spray drying of the thus obtained ceramic slip

(6) characterized by the addition during step I) or after step II) and before step III) of from 0.2 to 3% by weight, preferably from 0.4 to 2% by weight, of said aqueous slurry.

DETAILED DESCRIPTION OF THE INVENTION

(7) Preferably the aqueous slurry comprises:

(8) a) from 10 to 20% by weight of a swelling clay of the smectite family;

(9) b) from 15 to 25% by weight of said binder;

(10) c) from 0.5 to 5% by weight of said salt of a monovalent cation.

(11) Usually, the aqueous slurry of the invention comprises from 35 to 84.5% by weight of water.

(12) The swelling clays of the smectite family belong to a well known family of three-layer clay minerals containing a central layer of alumina or magnesia octahedra sandwiched between two layers of silica tetrahedra and have an idealized formula based on that of pyrophillite which has been modified by the replacement of some of the Al.sup.+3, Si.sup.+4, or Mg.sup.+2 by cations of lower valency to give an overall anionic lattice charge. The swelling clays of the smectite family include montmorillonite, which includes bentonite, beidellite, nontronite, saponite and hectorite. The swelling clays usually have a cation exchange capacity of from 80 to 150 meq/100 g dry mineral and can be dispersed in water relatively easily.

(13) For use according to the present invention, the swelling clay of the smectite family is preferably in the sodium or lithium form, which may occur naturally, but is more frequently obtained by cation exchange of naturally occurring alkaline earth clays, or in the hydrogen form which is obtainable by mineral acid treatment of alkali metal or alkaline earth metal clays. Such sodium, lithium or hydrogen-form clays generally have the property of increasing their basal spacing when hydrated to favor the phenomenon known as swelling.

(14) For the realization of the present invention, bentonite is the preferred swelling clay of the smectite family, sodium bentonite is particularly preferred.

(15) The binders b) suitable for the realization of the present invention are ligninsulfonate, naphthalene sulfonate-formaldehyde condensate salts, mono- and oligo-saccharides, water-soluble starches, water-soluble cellulose derivatives, such as carboxymethyl cellulose and hydroxyethyl cellulose, and mixture thereof. Examples of mono- and oligo-saccharides are sugars, such as glucose and sucrose; sugar alcohols, such as sorbitol; dextrins and maltodextrins. These binders are commonly used in the field and well known to the expert in the art.

(16) Particularly preferred binders for the realization of the invention are sodium or potassium ligninsulfonates.

(17) Ligninsulfonates are a by-product of the production of wood pulp. As the organic lignin molecule combines with strongly polar sulfonic acid groups during sulfite pulping, ligninsulfonates are readily soluble in water in the form of their sodium, calcium or ammonia salts. Ligninsulfonates are available as yellowish powders having variable compositions and also variable molecular dimensions. A typical weight average molecular weight of the ligninsulfonates is about 30,000 dalton (Da) and its typical number average molecular weight is about 3,000 dalton.

(18) Naphthalene sulfonate-formaldehyde condensate salts, also called NSF, have been known for some time and have been fully described also as dispersing agents in different sectors. In general these materials are made by condensing molten naphthalene with fuming sulfuric acid to form naphthalene sulfonic acid derivatives having varying position isomers. The sulfonic acid derivative is then condensed with water and formaldehyde at temperatures of about 90 C. and thereafter converted to a salt by the addition of alkali metal or ammonium hydroxides or carbonates. The weight-average molecular weight of the naphthalene sulfonate formaldehyde condensate salts, suitable for the realization of the present invention, is preferably around 10,000 Da.

(19) The carboxymethyl cellulose suitable for the realization of the present invention can be chosen among those commonly used in the ceramic field and known to those expert in the art. The carboxymethyl cellulose preferred for the realization of the present invention has degree of substitution comprised between 0.5 and 1.5, more preferably between 0.6 and 1.2. Preferably its Brookfield LVT viscosity, at 2% wt in water, 60 rpm and 20 C., is from 5 to 300 mPa.Math.s, more preferably from 5 to 50 mPa.Math.s.

(20) Preferred binders are ligninsulfonates, naphthalene sulfonate-formaldehyde condensate salts, sugars, sugar alcohols, carboxymethyl cellulose, and mixture thereof.

(21) The aqueous slurry comprises also a water soluble salt of a monovalent cation c), which reduces the swelling capacity of the smectite clay and lowers the viscosity of the slurry and subsequently of the ceramic slips. Salt containing divalent or higher valency cations (for instance calcium) can be used in some instances but these divalent ions tend to exchange with the monovalent ions that are present in the swellable clay initially and this can inhibit the subsequent swelling of the clay. It is generally preferred therefore that the cation of the salt is monovalent, for example ammonium or alkali metal. Examples of useful salts are ammonium salts (in particular NH.sub.4, tetra-C.sub.1-C.sub.4-alkyl ammonium and tetra-C.sub.1-C.sub.4-alkenyl ammonium salts, in which one or more of the alkyl or alkenyl groups is substituted by an OH group) or alkali metal salts of chloride, bromide, phosphate (monobasic, dibasic and tribasic phosphate) and mixtures thereof. Specific examples are sodium or potassium chloride, sodium or potassium bromide, monobasic sodium or potassium phosphate, dibasic sodium or potassium phosphate, tetraalkyl ammonium chloride, choline chloride and mixtures thereof.

(22) Preferably the monovalent cation is sodium, potassium or choline.

(23) The salt is preferably sodium chloride, potassium chloride and choline chloride, more preferably potassium chloride.

(24) In a preferred embodiment the aqueous slurry of the invention also comprises from 0.5 to 5% by weight, preferably from 1 to 3% by weight, of a dispersant, chosen among those commonly used in the field. Examples of dispersant are (meth)acrylic acid polymers, usually provided as sodium salt; phosphates and polyphosphates, such as sodium tripolyphosphate; sodium metasilicate; sodium di-silicate; liquid sodium silicate; and mixtures thereof. Particularly preferred dispersants are (meth)acrylic acid polymers with a weight average molecular weight below 20,000 Da, and preferably below 10,000 Da, for instance from 1,000 to 6,000 Da.

(25) Common ceramic additives can be also present in the aqueous slurry of the invention. Example of additives are antifoams, perfumes, preservatives, dyes and the like.

(26) The aqueous slurry is prepared by first dissolving in water the salt c), the binder b) and the optional additives and thereupon dispersing in the solution the swellable clay of the smectite family a). The clay-binder mixture is stirred with minimum shear, preferably as the clay is added. It has been found that the lower the shear of mixing, the higher the solids content that can be reached. Any mixing device capable of producing low-shear mixing can be employed.

(27) Usually, the final aqueous slurry has a Brookfield viscosity (25 C., 20 rpm) of below 3,000 mPa.Math.s, preferably from 500 to 1,500 mPa.Math.s.

(28) It is important to note that the slurries of the present invention have low viscosity and high solids content. They are also stable and characterized by prolonged shelf lives.

(29) The aqueous slurries described above can be used for making ceramic tiles according to the process of present invention. As already mentioned the slurries can be added in step I).

(30) According to this embodiment, the combination of the ceramic raw materials and the aqueous slurry is typically accomplished by mixing carefully the ceramic raw materials and the other additives such as deflocculants with the slurry to form a homogeneous mixture.

(31) The mixture of the ceramic raw materials is then subjected to wet grinding. This step may be performed using either the continuous or the discontinuous process.

(32) At the end of the grinding, the slips are sieved and sent to storage vats, from where they are pumped to an atomizer. The aqueous slurries of the invention can be also added to the slips any moment between grinding and spray-drying, even directly in the transfer line between the storage vats and the atomizer.

(33) In step III), the slips are dried as they are heated in the atomizer by a rising hot air column, forming small, free flowing granules that result in a powder suitable for forming.

(34) The process for the production of ceramic tiles further comprises the following steps: pressing the powdery intermediate to form green tiles, drying the green tiles, glazing the upper surface of the dried green tiles and finally firing the glazed tile bodies. These subsequent steps for the preparation of ceramic tiles can be accomplished by conventional techniques and procedures.

(35) The tile making process of the invention has several advantages compared to prior art processes of making ceramic tiles using directly a swellable clay of the smectite family. In particular, the performance is superior to that which is obtainable using the corresponding smectite in powder and without the inconvenience of having to handle powder.

(36) The process of the invention is suitable for the production of any kind of ceramic tile, such as wall tiles, floor tiles, stoneware, porcelain stoneware, rustic stoneware, earthenware tile, mosaic tiles, which can be both single and double fired.

(37) The following non-limiting examples illustrate exemplary aqueous slurries and process using the slurries in accordance with the present invention.

EXAMPLES

Examples 1-3

(38) Three aqueous slurries according to the invention were prepared with the commercially available components reported in Table 1.

(39) TABLE-US-00001 TABLE 1 Component (% w/w) Example 1 Example 2 Example 3 KCI 0.4 0.4 1.5 Sodium Ligninsulfonate 25 15 NSF 20 Bentonite 20 30 20 Reotan HS 5.0 Biocide 0.1 0.1 0.1 Perfume 0.3 0.2 Dye 0.1 0.1 0.1 Antifoam 0.1 Water to 100 to 100 to 100

(40) The slurries were prepared according to the following procedure: dissolve the salt in water; add the binder; dissolve under stirring, then add the dispersant and the other additives (if any); after 5 minutes, gradually pour under stirring the bentonite into the mixture; after 10 minutes of homogenization, sieve the slurry on a 100 micron sieve.

(41) Dissolution Test

(42) The effect of the slurries was evaluated on a ceramic raw material mixtures before grinding. The mixtures were prepared with the commercially available ceramic raw materials reported in Table 2 for Tile 4.

(43) The effect of the suspensions were evaluated by determining the Ford viscosity (ASTM Standard Method 01200-10) on a mixture prepared without any additive (blank), on a mixture prepared with 1% by weight of the slurry of Example 3 (Example 3A) and on a mixture prepared with 0.2% by weight of the same bentonite powder of Example 3 (Example B, with the same amount of bentonite of the slurry of Example 3A). The mixtures were homogenized by means of high speed mechanical stirrer equipped with a eight blades impeller, working at 320 rpm for 10 minutes.

(44) The following results were obtained:

(45) TABLE-US-00002 Blank* Example 3A Example B* Ford Viscosity (sec) 27 28 >60 *Comparative

(46) The results show the excellent stability of the viscosity of the mixture of ceramic raw materials comprising the slurry of Example 3.

(47) The use of the slurries according to the invention allows to avoid high viscosities and the problems that they would create, such as difficulties in grinding and in moving the slips through the various steps of the process. An analogous test was performed on ceramic slips obtained by grinding the ceramic raw materials described in Table 2 for Tile 1.

(48) The test was performed on a slip without additive (blank), a slip with 1% by weight of slurry of Example 3 (Example 3B) and a slip with 0.2% by weight of the same bentonite powder of the Example 3 (Example C, with the same amount of bentonite of the slurry of Example 3B). The mixtures were homogenized by means of high speed mechanical stirrer equipped with a eight blades impeller, working at 320 rpm for 10 minutes.

(49) After homogenization, 250 g of each slip were screened on a tared 63 microns ASTM sieve (100 mesh) and the amount of undissolved material (residue) was determined by weight difference after drying in oven at 105 C. for 2 hours.

(50) The following results were obtained:

(51) TABLE-US-00003 Blank* Example 3B Example C* Residue (% wt) 0.4 0.4 1 *Comparative

(52) The results show the mixture of ceramic raw materials containing the slurry of Example 3 has a lower content of residue.

(53) The presence of high concentrations of residues creates problems in the subsequent steps of the process and forces the user to filtrate the slip a second time before the spray-drying.

(54) Strength Test

(55) The performances of the slurries of the invention were determined on tiles bodies prepared with the commercially available ceramic raw materials reported in Table 2, wherein (parts) means (parts by weight) and (% wt) means the percentage by weight of the

(56) TABLE-US-00004 TABLE 2 Raw Materials Tile 1 Tile 2 Tile 3 Tile 4 Tile 5 Tile 6 Tile 7 German Clay (parts) 40 40 40 23 23 23 23 Quartz (parts) 60 60 60 German Kaolinitic 8.0 8.0 8.0 8.0 clay (parts) Italian Clay (parts) 7.4 7.4 7.4 7.4 Feldspar (parts) 28 28 28 28 Aplite (parts) 12.5 12.5 12.5 12.5 Sand (parts) 21.1 21.1 21.1 21.1 Example 1 (% wt) 0.3 0.6 Example 2 (% wt) 0.3 0.6 Example 3 (% wt) 0.3 0.6 0.9

(57) The slurries of Examples 1-3 were added to the ceramic slips obtained by grinding the ceramic raw materials and carefully homogenized using a mechanical stirrer.

(58) After homogenization, the slips were conditioned at 75-80 C. in oven for one night and grinded again to get particles with size below 0.75 mm.

(59) At the end of the grinding process, the water content of the ceramic slips was brought to about 6% by weight.

(60) Green tile bodies (5 cm10 cm, 0.5 cm thick) were prepared by means of a laboratory hydraulic press (Nannetti, Mod. Mignon SS/EA) applying a pressure of about 300 Kg/cm.sup.2 for wall tile bodies (Tile 1-3) and about 400 Kg/cm.sup.2 for standard gres tile bodies (Tile 4-7).

(61) Comparative green tiles were prepared with the same procedure and with the sole ceramic raw materials.

(62) The modulus of rupture (MOR) of the green tile bodies was determined according to the International Standard Test Method ISO 10545-4, using a laboratory fleximeter (Nannetti, Mod. FM96).

(63) The MOR of the dry tile bodies was determined on the remaining tile bodies after drying in oven for one night at 110 C.

(64) The modulus of rupture is an index of the strength of the tile bodies. The results expressed as % increase of the strength of the tile bodies prepared according to the invention compared to the strength of the comparative tile bodies are reported in Table 3.

(65) TABLE-US-00005 TABLE 3 Tile 1 Tile 2 Tile 3 Tile 4 Tile 5 Tile 6 Tile 7 % Green Strength +14.1 +35.3 +70.6 +11.1 +13.1 +5.0 +6.0 % Dry Strength +41.8 +49.1 +75.3 +19.4 +43.5 +11.4 +16.8