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Title:
TILES AND METHODS OF MAKING THEREOF
Document Type and Number:
WIPO Patent Application WO/2019/222568
Kind Code:
A1
Abstract:
The present disclosure provides tiles and methods of making thereof. The tiles may comprise one or more layers that contain polymers and mineral fillers (e.g., metakaolin). The mineral fillers may prevent or delay the degradation of the polymers in the tiles.

Inventors:
PESHAVE CHINMAY (US)
SINGH VIRENDRA (US)
LYONS ANTHONY (US)
Application Number:
PCT/US2019/032770
Publication Date:
November 21, 2019
Filing Date:
May 17, 2019
Export Citation:
Click for automatic bibliography generation   Help
Assignee:
IMERYS USA INC (US)
International Classes:
B28C1/16; B32B18/00; C01B33/26; C04B24/24; C04B33/04; C09C1/42
Domestic Patent References:
WO2012066132A22012-05-24
Foreign References:
US20180111878A12018-04-26
CN105569257A2016-05-11
EP0757974A11997-02-12
US5328770A1994-07-12
Attorney, Agent or Firm:
TOTTEN, Jeffrey et al. (US)
Download PDF:
Claims:
CLAIMS

What is claimed is:

1. A tile comprising:

a first layer comprising a polymer and a mineral filler, wherein the mineral filler has a shape factor of at least about 20 and a soluble alumina content ranging from about 10% to about 30% by weight; and

a second layer covering an upper surface of the first layer, the second layer comprising at least one material chosen from a fiber, a polymer that is the same or different than the polymer of the first layer, or a combination thereof.

2. The tile of claim 1, wherein the upper surface of the second layer comprises a decorative surface.

3. The tile of claim 1 , wherein the tile is a vinyl floor tile, a wood polymer composite tile, or a carpet floor tile.

4. The tile of claim 1, wherein the polymer of the first layer comprises polyvinyl chloride, polypropylene, polyester, or a combination thereof.

5. The tile of claim 1, wherein the first layer comprises from about 30% to about 70% by weight of the polymer, and from about 30% to about 70% by weight of the mineral filler.

6. The tile of claim 1, wherein the mineral filler comprises metakaolin.

7. The tile of claim 6, wherein the metakaolin has a shape factor ranging from about 20 to about 100 or from about 50 to about 80.

8. The tile of claim 6, wherein the metakaolin has a soluble alumina content ranging from about 20% to about 24% by weight.

9. The tile of claim 6, wherein the first layer further comprises calcium carbonate. 10. The tile of claim 9, wherein the first layer comprises from about 0.5% to about 70% by weight metakaolin, from about 0.5% to about 70% by weight calcium carbonate, and from about 30% to about 70% by weight of the polymer.

11. The tile of claim 1, wherein the second layer comprises polyvinyl chloride, polyester, polypropylene, or a combination thereof; and wherein the tile further comprises a third layer covering the upper surface of the second layer, the third layer being transparent.

12. The tile of claim 1 , further comprising a fourth layer between the first layer and the second layer, wherein the fourth layer comprises the same polymer and mineral filler of the first layer.

13. The tile of claim 12, further comprising a fifth layer between the fourth layer and the first layer, wherein the fifth layer comprises a fiber.

14. The tile of claim 1, wherein a particle size distribution of the mineral filler has a d50 diameter ranging from about 0.2 mm to about 40 mm, from about 0.2 mm to about 10 mm, or from about 0.7 mm to about 40 mm, as measured by Sedigraph.

15. The tile of claim 1, wherein the first layer further comprises a plasticizer, a thermal stabilizer, a process aid, or a combination thereof.

16. The tile of claim 1, wherein the first layer comprises chloride and metakaolin, the metakaolin being capable of reacting with the chloride to delay or prevent degradation of the tile.

17. The tile of claim 1 , wherein the first layer comprises at least one metal and metakaolin, the metakaolin being capable of reacting with the at least one metal to delay or prevent degradation of the tile. 18. The tile of claim 1, wherein the first layer comprises at least one metal and metakaolin, the metakaolin being capable of reducing or preventing migration of the at least one metal in or from the tile.

19. The tile of claim 17 or 18, wherein the at least one metal comprises barium, zinc, cadmium, iron, tin, lithium, or a combination thereof.

20. The tile of claim 1, wherein the first layer comprises metakaolin and less than 0.1% by weight of metals relative to the total weight of the first layer, or wherein the first layer comprises metakaolin and is devoid of metals.

21. The tile of claim 1, wherein the first layer is a lower-most layer of the tile, and wherein the mineral filler is capable of sound dampening.

22. A method for making a tile, the method comprising:

forming a first layer comprising a polymer and a mineral filler, wherein the mineral filler has a shape factor of at least about 20 and a soluble alumina content ranging from about 10% to about 30% by weight; and

covering an upper side of the first layer with a second layer comprising at least one material chosen from a fiber, a polymer that is the same or different than the polymer of the first layer, or a combination thereof.

23. The method of claim 22, wherein forming the first layer comprises blending the polymer with metakaolin or a mixture of metakaolin and calcium carbonate, the metakaolin having a soluble alumina content ranging from about 20% to about 24% by weight relative to the total weight of the metakaolin.

24. The method of claim 22, wherein the second layer comprises the polymer that is the same or different than the polymer of the first layer, the method further comprising laminating a third layer to the second layer, wherein the third layer is transparent.

25. The method of claim 24, further comprising annealing the first layer, the second layer, and the third layer together.

26. A method of delaying or preventing degradation of a tile comprising a first layer and a second layer covering the first layer, the method comprising:

incorporating metakaolin into the first layer of the tile;

wherein the first layer further comprises a polymer and a component chosen from an ionic component, a metal component, or a combination thereof, that promotes degradation; and

wherein the metakaolin reacts with the component to delay or prevent degradation of the tile.

27. The method of claim 26, wherein the metakaolin has a shape factor of at least about

20.

28. The method of claim 26, wherein the component is chosen from chloride ion, barium, zinc, or a combination thereof.

29. The method of claim 26, wherein the tile maintains at least 70% dimensional stability after aging at 70°C for at least 7 days.

30. The method of claim 29, wherein the tile maintains at least 70% dimensional stability after aging at 90 °C for 14 days.

31. The method of claim 26, wherein the tile maintains a dimensional stability with less than 5% expansion or shrinkage over a temperature range of 20 °C to 90 °C.

32. The method of claim 26, wherein the tile has a DE value less than 3.

Description:
TILES AND METHODS OF MAKING THEREOF

CLAIM FOR PRIORITY

[0001] This PCT International Application claims the benefit of priority of U.S.

Provisional Patent Application No. 62/673,362, filed May 18, 2018, the subject matter of which is incorporated herein by reference in its entirety.

TECHNICAL FIELD

[0002] Embodiments of the present disclosure relate generally to tiles comprising mineral fillers and methods of making thereof.

BACKGROUND

[0003] Polymers such as polyvinyl chloride are often used for making tiles, yet chloride ions and heavy metals from various additives present in the polymers induce degradation of the polymers over time. Environmental factors such as exposure to ultraviolet light or heat can also induce damage. The degradation of polymers may cause damage to the tiles, e.g., weakening their structural integrity. Thus, there is a need to develop tiles less susceptible to degradation and/or better able to maintain durability over time.

SUMMARY OF THE DISCLOSURE

[0004] The present disclosure includes tiles with multiple layers. For example, the present disclosure includes a tile that comprises a first layer comprising a polymer and a mineral filler, wherein the mineral filler may have a shape factor of at least about 20 and a soluble alumina content ranging from about 10% to about 30% by weight; and a second layer covering an upper surface of the first layer, the second layer comprising at least one material chosen from a fiber, a polymer that is the same or different than the polymer of the first layer, or a combination thereof. The upper surface of the second layer may comprise a decorative surface. In some examples, the particle size distribution of the mineral filler may have a d 50 diameter ranging from about 0.2 mm to about 40 mm, from about 0.2 mm to about 10 mm, or from about 0.7 mm to about 40 mm, as measured by Sedigraph.

[0005] In some examples, the tile may be a vinyl floor tile, a wood polymer composite tile, or a carpet floor tile. The polymer of the first layer and/or second layer may comprise, for example, polyvinyl chloride, polypropylene, polyester, or a combination thereof. In some examples, the first layer may comprise from about 30% to about 70% by weight of the polymer, and from about 30% to about 70% by weight of the mineral filler.

[0006] According some aspects of the present disclosure, the mineral filler may comprise metakaolin. The metakaolin may have a shape factor ranging from about 20 to about 100, or from about 50 to about 80. In at least one example, the metakaolin may have a soluble alumina content ranging from about 20% to about 24% by weight.

[0007] In some examples, the first layer of the tile may further comprise calcium carbonate. In at least one example, the first layer may comprise from about 0.5% to about

70% by weight metakaolin, from about 0.5% to about 70% by weight calcium carbonate, and from about 30% to about 70% by weight of the polymer.

[0008] In some examples, the second layer of the tile may comprise polyvinyl chloride, polyester, polypropylene, or a combination thereof. Additionally or alternatively, the tile may further comprise a third layer covering the upper surface of the second layer, the third layer being transparent. In some examples, the tile may further comprise a fourth layer between the first layer and the second layer, wherein the fourth layer may comprise the same types of polymer and mineral filler components as in the first layer. In another example, the tile may further comprise a fifth layer between the fourth layer and the first layer, wherein the fifth layer may comprise a fiber.

[0009] According to some aspects of the present disclosure, one or more layers, e.g., the first layer, of the tile may further comprise a plasticizer, a thermal stabilizer, a process aid, or a combination thereof. In some examples, the first layer may comprise chloride and metakaolin, the metakaolin being capable of reacting with the chloride to delay or prevent degradation of the tile. In some examples, the first layer may comprise at least one metal and metakaolin, the metakaolin being capable of reacting with the at least one metal to delay or prevent degradation of the tile. In some examples, the first layer may comprise at least one metal and metakaolin, the metakaolin being capable of reducing or preventing migration of the at least one metal in or from the tile. For example, the at least one metal may comprise barium, zinc, cadmium, iron, tin, lithium, or a combination thereof. In at least one example, the first layer of the tile may comprise metakaolin and less than 0.1% by weight of metals relative to the total weight of the first layer, or wherein the first layer may comprise metakaolin and may be devoid of metals. In another example, the first layer may be a lowermost layer of the tile, and wherein the mineral filler may be capable of sound dampening.

[0010] Also disclosed herein are methods of making tiles. For example, the methods may comprise forming a first layer comprising a polymer and a mineral filler, wherein the mineral filler may have a shape factor of at least about 20 and a soluble alumina content ranging from about 10% to about 30% by weight; and covering an upper side of the first layer with a second layer comprising at least one material chosen from a fiber, a polymer that is the same or different than the polymer of the first layer, or a combination thereof. In some examples, forming the first layer may comprise blending the polymer with metakaolin or a mixture of metakaolin and calcium carbonate, the metakaolin having a soluble alumina content ranging from about 20% to about 24% by weight relative to the total weight of the metakaolin. In some examples, the second layer of the tile may comprise the polymer that is the same or different than the polymer of the first layer, the method further comprising laminating a third layer to the second layer, wherein the third layer is at least partially or fully transparent. In at least one example, the method may further comprise annealing the first layer, the second layer, and the third layer together.

[0011] Further disclosed herein are methods of delaying or preventing degradation of a tile, such as a tile comprising a first layer and a second layer covering the first layer, e.g., as discussed above and elsewhere herein. For example, the method may comprise incorporating metakaolin into the first layer of the tile; wherein the first layer may further comprise a polymer and a component chosen from an ionic component, a metal component, or a combination thereof, that promotes degradation; and wherein the metakaolin may react with the component to delay or prevent degradation of the tile. In at least one example, the metakaolin may have a shape factor of at least about 20. In some examples, the component may be chosen from chloride ion, barium, zinc, or a combination thereof.

[0012] According to some aspects of the present disclosure, the tile (e.g., any of the tiles discussed above or elsewhere herein) may maintain at least 70% dimensional stability after aging at 70°C for at least 7 days. For example, the tile may maintain at least 70% dimensional stability after aging at 90 °C for 14 days. In some examples, the tile may maintain a dimensional stability with less than 5% expansion or shrinkage over a temperature range of 20 °C to 90 °C. In some examples, the tile may have a DE value less than 3.

BRIEF DESCRIPTION OF DRAWINGS [0013] Embodiments and various aspects of the present disclosure are illustrated in the following detailed description and the accompanying figures. Various features shown in the figures are not drawn to scale.

[0014] FIG. 1 illustrates an exemplary tile with multiple layers in accordance with some aspects of the present disclosure.

[0015] FIG. 2 illustrates another exemplary tile with multiple layers in accordance with some additional aspects of the present disclosure.

[0016] FIG. 3 shows the shape factor and the soluble content of kaolin processed for making metakaolin according to an exemplary method described herein.

DETAILED DESCRIPTION

[0017] Particular aspects of the present disclosure are described in greater detail below. The terms and definitions provided herein control, if in conflict with terms and/or definitions incorporated by reference.

[0018] As used herein, the terms“comprises,”“comprising;” or any other variation thereof are intended to cover a non-exclusive inclusion, such that a process, method, composition, article, or apparatus that comprises a list of elements does not include only those elements, but may include other elements not expressly listed or inherent to such process, method, composition, article, or apparatus. The term“exemplary” is used in the sense of“example” rather than“ideal.”

[0019] As used herein, the singular forms“a,”“an," and“the” include plural reference unless the context dictates otherwise. The terms“approximately” and“about” refer to being nearly the same as a referenced number or value. As used herein, the terms “approximately” and“about” should be understood to encompass ± 5% of a specified amount or value.

[0020] The present disclosure includes tiles (e.g., floor tiles) with multiple layers.

One or more of the layers may comprise at least one polymer and/or at least one mineral filler. In some examples, the mineral filler(s) may delay or prevent the degradation of the polymers). For example, the tiles may comprise a first layer comprising a polymer and a mineral filler, and a second layer covering the upper surface of the first layer. The mineral filler may have a soluble alumina content that interacts with, and reduces the levels of, degradation-causing components (e.g., chloride ions or metals) in the tiles and/or the surrounding environment. The second layer may have a polymer that is the same or different than the polymer in the first layer. In some examples, the first layer may be a backing layer and the second layer may be a decorative layer.

[0021] Also disclosed herein are methods of making the tiles. The methods may comprise forming a first layer comprising a polymer and a mineral filler, and covering an upper surface of the first layer with a second layer comprising a fiber or a polymer that is the same or different than the polymer of the first layer. To form the first layer, the polymer, the mineral filler, and/or one or more additives may be blended together. In some examples, the methods may further comprise annealing some or all of the layers in the tiles.

[0022] The layers in the tiles herein may comprise one or more polymers. Exemplary polymers that may be used in the layers include, but are not limited to, polyvinyl chloride, polyvinyl acetate, polypropylene, polyethylene, vinyl ester, polyester, any copolymers thereof, any derivatives thereof, and any combinations thereof. In at least one example, the at least one layer of the tile comprises polyvinyl chloride and/or polyvinyl acetate. [0023] At least one or each layer of the tiles may comprise from about 0.1% to 100% by weight of the polymer(s), with respect to the total weight of the respective layer. For example, the polymers) may be present in a layer in an amount ranging from about 10% to about 90%, from about 20% to about 80%, from about 30% to about 70%, or from about 40% to about 60% by weight of the layer. In some examples, polymer(s) may be present in a layer in an amount ranging from about 30% to about 70% by weight of the layer.

[0024] The layers of the tiles herein may comprise one or more fillers such as, e.g., one or more minerals. In some examples, the mineral(s) may comprise or be derived from a natural or synthetic clay, such as a kaolin clay. Exemplary minerals that can be included in the tiles herein include, but are not limited to, kaolin, metakaolin, calcium carbonate (e.g., ground calcium carbonate or precipitated calcium carbonate), mica, talc, graphite, perlite, zeolite, magnetite, and combinations thereof. In some cases, the mineral(s) may comprise one or more additives, such as, for example, aluminum phosphates, aluminum silicates salts

(e.g., sodium aluminum silicates such as zeolites), and combinations thereof. In at least one example, the mineral(s) comprise metakaolin. According to some aspects of the present disclosure, at least one layer or each layer of the tiles may comprise only one mineral, e.g., metakaolin. Additionally or alternatively, at least one layer or each layer of the tiles may comprise a combination of two or more minerals. Different layers of the tiles may comprise different minerals or combinations of minerals (e.g., a first layer comprising metakaolin and a second layer comprising calcium carbonate, etc.). Alternatively, different layers of the tiles may comprise the same mineral(s).

[0025] The minerals herein may have a shape factor that provides desired

characteristics for the tiles. For example, the minerals may have a relatively high shape factor, e.g., to allow the tiles to have high dimensional stability and/or sound dampening capacity. As used herein, the term“shape factor” refers to a measure of an average value (on a weight average basis) of the ratio of mean particle diameter to particle thickness for a population of particles of varying size and shape. Shape factor may be measured using the electrical conductivity method and apparatus described in U.S. Patent No. 5,576,617 (also referred to as PANACEA (particle assessment [by] natural alignment [and] conductivity effect analysis)). In this method, the electrical conductivity of a fully dispersed aqueous suspension of the particles is measured as they flow through an elongated tube.

Measurements of the electrical conductivity are taken between (a) a pair of electrodes separated from one another along the longitudinal axis of the tube, and (b) a pair of electrodes separated from one another across the transverse width of the tube. The shape factor of the particulate material is determined from the difference between these two conductivity measurements. Higher shape factors generally describe more platy materials.

[0026] The minerals herein may have a shape factor of at least 10, at least 20, at least

40, at least 60, at least 80, at least 90, at least 100, at least 125, at least 150, or at least 200. In some cases, the minerals may have a shape factor ranging from about 10 to about 200, e.g., from about 20 to about 200, from about 20 to about 100, from about 50 to about 80, from about 50 to about 60, or from about 40 to about 60. In at least one example, the tile may comprise at least one layer comprising a mineral filler having a shape factor ranging from about 50 to about 80.

[0027] The minerals may have a particle size distribution suitable for use in the tiles.

For example, the minerals may have a d 10 diameter as measured by Sedigraph ranging from about 0.2 mm to about 4.0 mm, from about 0.2 mm to about 1.0 mm, from about 0.5 mm to about 1.5 mm, from about 1.0 mm to about 2.0 mm, from about 1.5 mm to about 2.5 mm, from about 2.0 mm to about 3.0 mm, from about 2.5 mm to about 3.5 mm, or from about 3.0 mm to about 4.0 mm. In some examples, the minerals may have a d 50 diameter as measured by

Sedigraph ranging from about 0.1 mm to about 50 mm, from about 0.5 mm to about 40 mm, from about 0.5 mm to about 10 mm, from about 0.5 mm to about 7.5 mm, from about 0.5 mm to about 5 mm, from about 1.0 mm to about 5.0 mm, from about 1.0 mm to about 3.5 mm, from about 1 mm to about 10 mm, from about 5 mm to about 15 mm, from about 10 mm to about 20 mm, from about 15 mm to about 25 mm, from about 20 mm to about 30 mm, from about 25 mm to about 35 mm, or from about 30 mm to about 40 mm. In at least one example, the minerals may have a d 50 from about 1.0 mm to about 5.0 mm. In some examples, the minerals may have a d 90 diameter as measured by Sedigraph ranging from about 15 mm to about 50 mm, from about 15 mm to about 25 mm, from about 20 mm to about 30 mm, from about 25 mm to about 35 mm, from about 30 mm to about 40 mm, from about 35 mm to about 45 mm, or from about 40 mm to about 50 mm. The particle size distribution of the minerals described herein may be measured by sedimentation of minerals in a fully dispersed condition in an aqueous medium using a Sedigraph 5100 machine as supplied by Micromeritics Instruments

Corporation, Norcross, Ga., USA. Such a machine may provide measurements and a plot of the cumulative percentage by weight of particles having a size, referred to as the“equivalent spherical diameter” (e.s.d.), less than given e.s.d. values. The mean particle size d 10 is the value determined in this way of the particle e.s.d. at which there are 10% by weight of the particles which have an e.s.d less than that d 10 value. The mean particle size d 50 is the value determined in this way of the particle e.s.d. at which there are 50% by weight of the particles which have an equivalent spherical diameter less than that d 50 value. The mean particle size d 50 is the value determined in this way of the particle e.s.d. at which there are 90% by weight of the particles which have an e.s.d. less than that dso value. In at least one example, from about 95% to about 100% by weight of the particles have an e.s.d. less than 10 mm and/or from about 40% to about 80% by weight of the particles have an e.s.d. less than 2 mm.

[0028] Without intending to be bound by theory, it is believed that incorporating one or more mineral fillers in the tiles may help delay or prevent degradation of the tiles. For example, the mineral filler(s) may react or otherwise interact with and reduce the level or decrease the effect of one or more degradation-causing components present in the tile or in the environment. Examples of such degradation-causing components include, but are not limited to, metals (e.g., heavy metals), ions, radiation, heat, and any combinations thereof. In at least one example, the degradation-causing components may comprise one or more metals such as, for example, barium, zinc, lead, cadmium, iron, tin, antimony, lithium, any mixtures thereof, or any alloys thereof. In at least one example, the degradation-causing components may comprise ions, such as, for example, chloride ions. In at least one example, the degradation-causing components may comprise combinations of any or all of the

degradation-causing metal components and any or all of the degradation-causing ions described herein. According to some aspects of the present disclosure, the mineral filler(s) that may help to delay or prevent degradation of the polymers comprise metakaolin. In some examples, the mineral filler(s) may be capable of reducing or preventing migration of one or metals in or from the tiles (e.g., within a layer of a tile, from one layer to another layer of the tile, or from the tile to the surrounding environment).

[0029] The fillers (e.g., mineral fillers) may have one or more constituents that react with and/or reduce the concentration of different components present in the tiles such as, e.g., components associated with polymer degradation. For example, according to some aspects of the present disclosure, the mineral filler(s) may comprise alumina, e.g., soluble alumina. For example, one or more layers of the tile may comprise a mineral having a soluble alumina content ranging from about 10% to about 30% by weight, or from about 12% to about 28%, or from about 14% to about 26%, or from about 18% to about 24%, or from about 20% to

24% by weight. In at least one example, the tile may comprise at least one layer that comprises metakaolin having a soluble alumina content ranging from about 18% to about

24% by weight. In at least one example, the layer(s) of the tile may comprise metakaolin having a soluble alumina content ranging from about 20% to about 24% by weight.

[0030] The amount of soluble alumina content may be measured using nitric acid. In an exemplary method, 100 milligrams of a sample is measured using an analytical balance and transferred to a 16 mm x 150 mm test tube with a screw-on cap. 10 mL of concentrated nitric acid is added to the test tube, which is capped loosely. The test tube is then heated in a water bath (with a temperature of 100 °C± 2C°) for 4 hours and allowed to cool down. The top part of the test tube is filled with deionized water and the solution in the test tube is then filtered through ashless filter paper into a 100 mL volumetric flask. A control sample is also prepared using concentrated nitric acid. The flask is then filled to the 100 mL mark and the solution is analyzed by inductively coupled plasma atomic emission spectroscopy (ICP- AES), using various dilutions of a 1000 ppm aluminum standard solution as standards. The soluble alumina content is then calculated using the following equation:

[0031] At least one layer or each layer of the tiles may comprise from about 0.1% to about 100% by weight of mineral(s), with respect to the total weight of the respective the layer. For example, the mineral(s) may be present in a layer in the tiles in an amount ranging from about 0.5% to about 90% by weight, such as from about 0.5% to about 70%, from about

10% to about 90%, from about 20% to about 80%, from about 30% to about 70%, or from about 40% to about 60% by weight of the layer. In at least one example, the mineral(s) may be present in a layer in an amount ranging from about 0.5% to about 70% by weight of the layer. In at least one example, the mineral(s) may be present in a layer in an amount ranging from about 30% to about 70% by weight of the layer.

[0032] As mentioned above, in some examples, one or more of the layers comprises metakaolin. Alternatively or additionally, one or more layers of the tile may comprise calcium carbonate. In some examples, at least one layer of the tile may comprise from about

0.1% to about 100% by weight metakaolin, e.g., from about 0.2% to about 90%, from about 0.5% to about 70%, from about 1% to about 90%, from about 10% to about 80%, from about

30% to about 70%, or from about 40% to about 60% by weight of the respective layer. In some examples, at least one layer of the tile may comprise from about 0.1% to about 100% by weight calcium carbonate, e.g., from about 0.2% to about 90%, from about 0.5% to about

70%, from about 1% to about 90%, from about 10% to about 80%, from about 30% to about

70%, or from about 40% to about 60% by weight of the respective layer. Further, in some examples, at least one layer of the tile may comprise metakaolin and calcium carbonate, the total of metakaolin and calcium carbonate ranging from about 0.1% to about 100% by weight, from about 0.2% to about 90%, from about 0.5% to about 70%, from about 1% to about 90%, from about 10% to about 80%, from about 30% to about 70%, or from about 40% to about 60% by weight of the respective layer. In such cases, the weight ratio of metakaolin to calcium carbonate may range from about 10:1 to about 1:10, e.g., a weight ratio

(metakaoiin:calcium carbonate) of about 10:1, about 5:1, about 3:1, about 2:1, about 5:2, about 3:2, about 7:5, about 4:3, about 1:1, about 3:4, about 5:7, about 2:3, about 2:5, about

1 :2, about 1 :3, about 1 :5, or about 1 :10. In some examples, at least one layer of the tile may comprise metakaolin, calcium carbonate, talc, mica, or a combination thereof. In at least one example, at least one layer of the tile may further comprise one or more additives, such as, for example, aluminum phosphates and/or aluminum silicate salts (e.g., sodium alumina silicate salts such as zeolites). In some examples, at least one layer of the tile may comprise one or more minerals of the feldspar group (including, e.g., metakaolin), optionally in combination with one or more zeolites.

[0033] According to some aspects of the present disclosure, the polymer(s) and mineral(s) may be present in a layer at a suitable ratio for the intended functions of the tiles.

In some examples, at least one layer in the tiles may comprise from about 30% to about 70% by weight of the polymer(s), and from about 30% to about 70% by weight of the mineral(s).

In at least one example, one or more layers in the tile may comprise from about 0.5% to about

70% by weight of the mineral(s), and from about 30% to about 70% by weight of the polymer(s), wherein the mineral(s) are chosen from metakaolin, calcium carbonate,· or a mixture thereof.

[0034] The layers of the tiles may further comprise one or more additives. Examples of additives that can be used in the tiles include, but are not limited to plasticizers, thermal stabilizers, process acids, slip agents, anti-blocking agents, antioxidants, ultraviolet light stabilizers, quenchers, colorants, mold release agents, lubricants, antistatic agents, fire retardants, and any combinations thereof.

[0035] According to some aspects of the present disclosure, at least one layer of the tiles may comprise one or more plasticizers. Exemplary plasticizers include, but are not limited to, phthalate ester, phosphate ester, ethoxyated soybean oil, epoxidized soybean oil, adipate plasticizers, epoxidized propylene glycol disoyate, dioctyl phthalate, dioctyl terphalate, dioctyl adipate, dibutyl sebacate, dinonyl phthalate, glyceryl stearates, or combinations thereof. In at least one example, plasticizer(s) in the tiles may comprise dioctyl terphalate, ethoxyated soybean oil, or any combinations thereof. [0036] The layers of the tiles may additionally or alternatively comprise one or more processing aids. Exemplary processing aids include, but are not limited to, acrylic ester polymers such as, for example, copolymers of methyl methacrylate with ethyl or butyl acrylate. In at least one example, the processing aids may comprise copolymers of methyl methacrylate, ethyl acrylate, and butyl acrylate.

[0037] The layers of the tiles may additionally or alternatively comprise one or more thermal stabilizers. Exemplary thermal stabilizers include, but are not limited to, carboxylic acid metal soaps (e.g., barium, calcium, cadmium, zinc and/or lead carboxylates), esters or mercaptides of alkyl tin, epoxy compounds, and a combination thereof. In at least one example, the thermal stabilizers may comprise barium/zinc thermal stabilizers, e.g., barium/zinc carboxylic acid metal soaps.

[0038] In some examples, one or more layers in the tile may comprise one or more metals, in addition to or as an alternative to, metal(s) present in a thermal stabilizer or other additive. According to some aspects of the present disclosure, at least one layer in the tile may comprise less than 1%, less than 0.5%, less than 0,2%, less than 0.1%, less than 0.05%, or less than 0.01% by weight metal(s) relative to the total weight of the layer. In at least one example, at least one layer in the tile may be devoid of metals.

[0039] The tiles herein may be of any type, e.g., the tiles designed for use in various applications. For example, the tiles herein may include vinyl tiles such as, for example, luxury vinyl tiles and vinyl sheets, carpet tiles, wood polymer composite tile, hardwood tiles, and laminate tiles. The tiles may also include those used outside a building, e.g., roofing tiles, roofing shingles, sidings, and claddings. In at least one example, the tiles herein may be floor tiles, such as vinyl floor tiles, e.g., luxury vinyl tiles. The term“vinyl tile” as used herein refers to any resilient floor tile product that may comprise, at least partially, vinyl, such as polyvinyl chloride or other thermoplastic resins. In at least one example, the tiles

herein may be carpet tiles, e.g., comprising one or more fibers.

[0040] The tiles may comprise one or more layers, e.g., the tiles being composite

tiles. In some examples, a tile disclosed herein may comprise 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or

more layers. As mentioned above, each layer may have the same composition, e.g.,

comprising the same po!ymer(s) and/or mineral(s) in the same ratio or amounts. In some

examples, at least one layer may have a different composition that one or more of the other

layers, e.g., different polymer(s), different amounts of polymers, different minerals, different

: ; v amounts of polymers and/or minerals, etc.

[0041] According to some aspects of the present disclosure, two or more of the layers may comprise the same polymer. In at least one example, the tiles may comprise a backing

layer and a decorative layer, both layers comprising polyvinyl chloride. In at least one

example, the tiles may comprise a first backing layer, a second backing layer, and a

decorative layer, all of which comprise polyvinyl chloride. In some examples, two or more

of the layers may comprise different polymers.

[0042] According to some aspects of the present disclosure, two or more of the layers may comprise the same filler (e.g., the same mineral or combination of minerals). In at least one example, the tile may comprise a backing layer and a decorative layer, both layers

comprising metakaolin. In at least one example, the tile may comprise a first backing layer, a second backing layer, and a decorative layer, all of which comprise metakaolin. In some

examples, one or more of the layers may comprise a filler while other layers do not comprise the same filler. In at least one example, the tiles may comprise a backing layer and a

decorative layer, in which the backing layer comprises metakaolin while the decorative layer comprises no metakaolin (i.e., the decorative layer being devoid of metakaolin). In some examples, two or more of the layers may comprise different fillers.

[0043] The tiles may comprise one or more backing layers. The backing layer(s) may be covered by one or more other layers. For example, a backing layer may be the bottom layer, e.g., the lower-most layer of a tile. The backing layer(s) may serve as a base of the tile that contacts the floor upon installation of the tile. Backing layers may provide support to other layers, provide underfoot comfort and springiness of tiles, and/or increase the tiles’ sound and/or thermal insulation. In some examples, the tiles herein may comprise 1, 2, 3 4, or 5 or more backing layers, which may be adjacent to each other or separated by one or more other layers such as a reinforcement layer. According to some aspects of the present disclosure, a backing layer may comprise at least one polymer, at least one mineral filler

(e.g., metakaolin and/or calcium carbonate) and/or at least one additive. In at least one example, a backing layer may comprise polyvinyl chloride, metakaolin (e.g., with a shape factor of at least 20 and soluble alumina content ranging from about 10% to about 30% by weight, or from about 12% to about 28%, or from about 14% to about 26%, or from about

18% to about 24%, or from about 20% to 24% by weight), calcium carbonate, plasticizers)

(e.g., dioctyl terphalate and/or ethoxyated soybean oil), thermal stabilizers) (e.g., barium/zinc thermal stabilizer(s)), processing aid(s) (e.g., acrylate(s)), or any combinations thereof. In some examples herein, the tile may include at least one backing layer comprise metakaolin as the only mineral filler, optionally in combination with additives. In some examples, the tile may include at least one backing layer comprising metakaolin and calcium carbonate, and optionally other fillers and/or additives.

[0044] The tiles may further comprise one or more decorative layers. The decorative layer(s) may comprise a decorative surface. The decorative surface may provide desired patterns for the floor. For example, the patterns may replicate ceramics, stone (e.g., marble or granite), wood, or other natural materials. In some examples, the pattern may also be artificially designed patterns. A decorative layer may also have a texture for a desired effect.

In some examples, the decorative layer may be embossed or granulated to imitate, for example, the grain of a hardwood floor. Further, for example, the decorative layer may comprise a textile material, such as carpet fibers. The decorative layers herein may be opaque. According to some aspects of the present disclosure, a decorative layer may cover the upper surface of another layer such as, e.g., a backing layer.

[0045] The decorative layers) of the tiles herein may comprise one or more polymers. For example, the decorative layers may comprise the same polymer(s) as some other layers (e.g., backing layers). Alternatively, the decorative layers may comprise different polymers than some other layers (e.g., backing layers). In some examples, the decorative layers may comprise one or more mineral fillers. The decorative layers may comprise the same mineral filler(s) as some other layers (e.g., backing layers). Alternatively, the decorative layers may comprise different mineral filler(s) than some other layers (e.g., backing layers). In some examples, the decorative layers) may comprise no mineral fillers

(e.g., the decorative layer(s) being devoid of minerals or other fillers). In at least one example, a decorative layer may comprise polyvinyl chloride, metakaolin (e.g., with a shape factor of at least 20 and soluble alumina content ranging from about 10% to about 30% ), plasticizers) (e.g., dioctyl terphalate and ethoxyated soybean oil), thermal stabilizers) (e.g., barium/zinc thermal stabilizers), process aid(s) (e.g., acrylates), or any combinations thereof.

[0046] The tiles may also comprise one or more wear layers. The wear layer(s) may provide protection for other layers underneath. For example, a wear layer may cover the upper surface of a decorative layer, e.g., in order to protect the patterns on top of the decorative layer. The wear layer(s) may further comprise embossing or texture, e.g., to compliment the look of the patterns on the decorative layer. The wear layer(s) may comprise one or more polymers described herein. Additionally or alternatively, the tiles herein may comprise one or more coating layers, e.g., forming an upper-most surface of the tile (opposite the lower-most surface of the tile formed by a backing layer). The coating layer(s) may comprise polyurethane, for example. In at least one example, a wear layer may be covered by a coating layer to provide further protection. The wear layer(s) and/or the coating layers) may be transparent.

[0047] According to some aspects of the present disclosure, the tiles may further comprise one or more reinforcement layers. The reinforcement layer(s) may provide sturdiness, insulation and/or comfort. In some examples, a reinforcement layer may cover the upper surface of a backing layer. In at least one example, a reinforcement layer may be underneath a backing layer. In at least one example, a reinforcement layer is between two backing layers. The reinforcement layer(s) may comprise fiber(s) and/or polymers, optionally in combination with one or more fillers as disclosed herein such as, e.g., one or more minerals.

[0048] An exemplary tile 100 in accordance with some aspects of the present disclosure is shown in cross-section in FIG. 1. Tile 100 comprises four layers: a coating layer 110, a wear layer 120, a decorative layer 130, and a backing layer 140. Another exemplary tile 200 in accordance with some aspects of the present disclosure is shown in cross-section in FIG. 2. Tile 200 comprises five layers: a wear layer 210, a decorative layer *

220, a first backing layer 230, a fiber reinforcement layer 240, and a second backing layer

250. In some examples, backing layers 140, 230, and/or 250 may comprise polyvinyl chloride, metakaolin, calcium carbonate, and one or more additives. FIGS. 1 and 2 are exemplary and for illustration purposes only. The various layers may have about the same thickness (e.g., as shown) or different thicknesses. The thicknesses for the layers can each range 500 microns to 1500 microns. For example, the coating layer 110 and/or wear layers

120, 210 may be relatively thin in comparison to the respective underlying decorative layers

130, 220.

[0049] Also disclosed herein are methods of making the tiles. The method may comprise forming one or more layers and assembling the layers together to make the tile. In some examples, the method may comprise forming a first layer and covering the upper side of the first layer with a second layer, and optionally covering the upper side of the second layer with a third layer, etc.

[0050] According to some aspects of the present disclosure, the method may comprise forming at least one layer or a plurality of layers comprising one or more polymers and one or more fillers. In some examples, forming the layer may comprise blending the polymer(s), the filler(s), and/or other components (e.g., additive(s)) and compounding the blended materials to form one or more sheets. In some examples, the compounding may be performed by calendering, double belt pressing, molding (e.g., injection molding, compression molding, etc.) and/or extrusion. In at least one example, the method may comprise forming a layer by blending a polymer or polymer blend with metakaolin. In at least one example, the method comprises forming a layer by blending a polymer or polymer blend with metakaolin and calcium carbonate. The metakaolin for such examples may have a shape factor of at least 20 and/or a soluble alumina content ranging from about 20% to about 24% by weight relative to the total weight of the metakaolin.

[0051] One or more layers in the tiles may have a suitable mineral loading that provides desired characteristics. For example, one or more layers in the tiles may have a mineral loading ranging from about 5 parts per hundred resin (PHR) to about 400 PHR, from about 8 PHR to about 300 PHR, from about 8 PHR to about 250 PHR, from about 5 PHR to about 100 PHR, from about 50 PHR to about 150 PHR, from about 100 PHR to about 200

PHR, from about 150 PHR to about 250 PHR, from about 200 PHR to about 300 PHR, from about 250 PHR to about 350 PHR, or from about 300 PHR to about 400 PHR. In some examples, one or more layers in the tiles may have a metakaolin and/or calcium carbonate loading ranging from about 20 PHR to about 70 PHR, from about 30 PHR to about 60 PHR, from about 40 PHR to about 50 PHR, from about 20 PHR to about 40 PHR, from about 30

PHR to about 50 PHR, from about 40 PHR to about 60 PHR, or from about 50 PHR to about

70 PHR.

[0052] The methods herein may further comprise attaching multiple layers together to assemble the tile. In some examples, attaching the multiple layers may comprise laminating the layers together into a composite sheet. According to some aspects of the present disclosure, attaching the multiple layers together may comprise annealing two or more layers.

[0053] The methods may also comprise additional steps, such as, e.g., cutting individual layers and/or sheets prior to or after assembling portions of the tile, stacking the layers, sanding and/or embossing surfaces of one or more of the layers, and/or calibrating the layers.

[0054] The fillers suitable for the tiles herein may be prepared, e.g., based on the desired particle size, shape, and/or composition. In cases where the filler(s) comprise metakaolin, the metakaolin may be prepared by processing a kaolin clay. In at least one example, such methods may produce metakaolin that has a shape factor ranging from about

20 to about 100, e.g., from about 30 to about 80, from about 40 to about 60, from about 45 to about 60, from about 50 to about 60, or from about 50 to about 55. The metakaolin may have a soluble alumina content ranging from about 10% to about 30% by weight, or from about

12% to about 28%, or from about 14% to about 26%, or from about 18% to about 24%, or

from about 20% to 24% by weight.

[0055] The methods of making metakaolin may comprise calcining kaolin clay at a

suitable temperature and for an appropriate amount of time. The temperature and time may

be sufficient to remove some of the water content from kaolin. In some examples, the

method of making metakaolin may comprise calcining kaolin at a temperature ranging from

about 500 °C to about 900 °C, e.g., from about 550 °C to about 850 °C, from about 600 °C to

about 800 °C, from about 650 °C to about 750 °C, or from about 680 °C to about 720 °C. In

some examples, the method of making metakaolin may comprise calcining kaolin for a time

· ranging from about 30 minutes to about 120 minutes, from about 40 minutes to about 110

minutes, from about 50 minutes to about 100 minutes, from about 60 minutes to about 90

minutes, from about 50 minutes to about 70 minutes, or from about 80 minutes to about 110

minutes. Such conditions may produce metakaolin having a shape factor of at least 20.

[0056] The kaolin clay used for making the metakaolin herein may comprise hyper

platy kaolin clay (e.g., kaolin having a shape factor of at least 50). According to some

aspects of the present disclosure, the shape factor of the kaolin clay may be reduced after

calcination (e.g., when the kaolin clay is made into metakaolin). However, the reduced shape

factor of the resulting metakaolin may be equal to or greater than 20.

[0057] Further provided herein are methods for delaying or preventing the

degradation of the tiles. The methods may comprise incorporating one or more fillers into

one or more layers of the tiles. With intending to be bound by theory, it is believed that the

mineral filler(s) may interact, e.g., react, with or otherwise reduce the level of degradation- causing components present in the tile. In at least one example, incorporating the filler(s) into the layer(s) of the tile may be performed when the layer(s) are made. In at least one example, incorporating the fillers) into the layer(s) may be performed during the processing and/or after the layer(s) are made, e.g., by applying a coating containing the filler(s) to the layer(s).

[0058] When made and/or treated with the methods herein, the tiles may have resistance to degradation induced by exterior radiation (such as ultraviolet (UV), infrared

(IR), visible-light radiation), and/or moisture (such as from condensation or water used for cleaning the tiles). In these cases, the tiles may not age significantly or lose its original properties and, for instance, become brittle, detach from the substrate, or degraded. The preservation of the properties may be measured in tests where the material is exposed to repeated cycling of heat and/or UV light In some cases, intermittent water and/or moisture may be imposed on the material between exposures to UV or heat. The mechanical properties and integrity of the tiles (e.g., brittleness or structure stability) are indications of the ability to withstand degradation-causing components.

[0059] When made and/or treated with the methods provided herein, the tiles may maintain a dimensional stability of at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or at least 99% after an aging process. In some examples, the aging may be performed at about 70 °C for at least 7 days. Alternatively or additionally, the aging process may be performed at about 90 °C for 14 days. In at least one example, the tiles may maintain a dimensional stability of at least 70% after such aging process(es). The term

“dimensional stability” as used herein refers to the ability of the tiles to maintain their structural integrity, particularly upon exposure to degradation-causing components. The dimensional stability may comprise the dimensional stability under stress such as, for example, tensile, tear, compression, heat, or any combinations thereof. The dimensional stability may be presented as elongation at break, impact strength, hardness of the material, heat deflection temperature, load deflection point, or any combinations thereof. In some examples, the tiles may maintain a dimensional stability with less than 20%, less than 15%, less than 10%, less than 5%, or less than 1% expansion or shrinkage over a temperature range of at least 30°C (e.g., a range of 20°C to 50°C, 50°C to 90°C, 40°C to 80°C, or 20°C to 90°C).

[0060] In some examples, the dimensional stability of the tiles may be evaluated using International Standard ISO 2551 (“Machine made textile floor coverings -

Determination of dimensional changes due to the effects of varied water and heat conditions”) (also referred to as the“Aachen test”), in which the samples are heated in a 60°C oven for 2 hours, submerged in water for 2 hours, then heated in a 60°C oven again for 2 hours. The changes in dimensions (e.g., length or width) of the tiles are then measured and compared to the original dimensions.

[0061] The compositions and methods herein may also help prevent or delay a change of color of the tiles. In some examples, color changes may be quantified according to the

Cielab system that quantifies color changes based on the DE value. In general, a smaller DE value indicates a lower level of color change. The Cielab system expresses DE according to the following formula:

[0062] In this formula, DL refers to the change in darkness or lightness (positive DL means that the tiles have become darker and negative DL means that the tiles have become lighter). The term Da. refers to the change of color in the red-green axis (positive means color change towards red range and negative towards green range), and Db refers to color changes in the blue-yellow axis (positive color change means towards yellow range and negative toward blue range). [0063] According to some aspects of the present disclosure, when made and/or treated with the methods provided herein, the tiles may maintain a DE value of no greater than 5, no greater than 4, no greater than 3, no greater than 2, or no greater than 1. In some examples, the tiles may maintain a DE value ranging from about 0.1 to about 5, from about 1 to about 3, from about 1 to about 2, or from about 2 to about 3.

[0064] Aspects of the present disclosure are further illustrated by reference to the following, non-limiting numbered paragraphs describing exemplaiy embodiments.

[0065] 1. A tile comprising a first layer comprising a polymer and a mineral filler, wherein the mineral filler has a shape factor of at least about 20 and a soluble alumina content ranging from about 10% to about 30% by weight; and a second layer covering an upper surface of the first layer, the second layer comprising at least one material chosen from a fiber, a polymer that is the same or different than the polymer of the first layer, or a combination thereof.

[0066] 2. The tile according to paragraph 1, wherein the upper surface of the second layer comprises a decorative surface.

[0067] 3. The tile according to paragraph 1 or 2, wherein the tile is a vinyl floor tile, a wood polymer composite tile, or a carpet floor tile.

[0068] 4. The tile according to any of paragraphs 1-3, wherein the polymer of the first layer comprises polyvinyl chloride, polypropylene, polyester, or a combination thereof.

[0069] 5. The tile according to any of paragraphs 1 -4, wherein the first layer comprises from about 30% to about 70% by weight of the polymer, and from about 30% to about 70% by weight of the mineral filler.

[0070] 6. The tile according to any of paragraphs 1-5, wherein the mineral filler comprises metakaolin. [0071] 7. The tile according to paragraph 6, wherein the metakaolin has a shape factor ranging from about 20 to about 100 or from about 50 to about 80.

[0072] 8. The tile according to paragraph 6 or 7, wherein the metakaolin has a soluble alumina content ranging from about 20% to about 24% by weight.

[0073] 9. The tile according to any of paragraphs 1-8, wherein the first layer further comprises calcium carbonate.

[0074] 10. The tile according to any of paragraphs 1-9, wherein the first layer comprises from about 0.5% to about 70% by weight metakaolin, from about 0.5% to about

70% by weight calcium carbonate, and from about 30% to about 70% by weight of the polymer.

[0075] 11. The tile according to any of paragraphs 1-10, wherein the second layer comprises polyvinyl chloride, polyester, polypropylene, or a combination thereof; and wherein the tile further comprises a third layer covering the upper surface of the second layer, the third layer being transparent.

[0076] 12. The tile according to any of paragraphs 1-11, further comprising a fourth layer between the first layer and the second layer, wherein the fourth layer comprises the same polymer and mineral filler of the first layer.

[0077] 13. The tile according to paragraph 12, further comprising a fifth layer between the fourth layer and the first layer, wherein the fifth layer comprises a fiber.

[0078] 14. The tile according to any of paragraphs 1-13, wherein a particle size distribution of the mineral filler has a d 50 diameter ranging from about 0.2 mm to about 40 mm, from about 0.2 mm to about 10 mm, or from about 0.7 mm to about 40 mm, as measured by Sedigraph. [0079] 15. The tile according to any of paragraphs 1-14, wherein the first layer further comprises a plasticizer, a thermal stabilizer, a process aid, or a combination thereof.

[0080] 16. The tile according to any of paragraphs 1-15, wherein the first layer comprises chloride and metakaolin, the metakaolin being capable of reacting with the chloride to delay or prevent degradation of the tile.

[0081] 17. The tile according to any of paragraphs 1-16, wherein the first layer comprises at least one metal and metakaolin, the metakaolin being capable of reacting with the at least one metal to delay or prevent degradation of the tile.

[0082] 18. The tile according to any of paragraphs 1-17, wherein the first layer comprises at least one metal and metakaolin, the metakaolin being capable of reducing or preventing migration of the at least one metal in or from the tile.

[0083] 19. The tile according to paragraph 17 or 18, wherein the at least one metal comprises barium, zinc, cadmium, iron, tin, lithium, or a combination thereof.

[0084] 20. The method according to any of paragraphs 1-19, wherein the first layer comprises metakaolin and less than 0.1% by weight of metals relative to the total weight of the first layer, or wherein the first layer comprises metakaolin and is devoid of metals.

[0085] 21. The tile according to any of paragraphs 1 -20, wherein the first layer is a lower-most layer of the tile, and wherein the mineral filler is capable of sound dampening.

[0086] 22. A method for making a tile, the method comprising: forming a first layer comprising a polymer and a mineral filler, wherein the mineral filler has a shape factor of at least about 20 and a soluble alumina content ranging from about 10% to about 30% by weight; and covering an upper side of the first layer with a second layer comprising at least one material chosen from a fiber, a polymer that is the same or different than the polymer of the first layer, or a combination thereof. [0087] 23. The method according to paragraph 22, wherein forming the first layer comprises blending the polymer with metakaolin or a mixture of metakaolin and calcium carbonate, the metakaolin having a soluble alumina content ranging from about 20% to about

24% by weight relative to the total weight of the metakaolin.

[0088] 24. The method according to paragraph 22 or 23, wherein the second layer comprises the polymer that is the same or different than the polymer of the first layer, the method further comprising laminating a third layer to the second layer, wherein the third layer is transparent.

[0089] 25. The method according to any of paragraphs 22-24, further comprising annealing the first layer, the second layer, and the third layer together.

[0090] 26. A tile made according to a method according to any of paragraphs 22-25.

[0091] 27. A method of delaying or preventing degradation of a tile comprising a first layer and a second layer covering the first layer, the method comprising: incorporating metakaolin into the first layer of the tile; wherein the first layer further comprises a polymer and a component chosen from an ionic component, a metal component, or a combination thereof, that promotes degradation; and wherein the metakaolin reacts with the component to delay or prevent degradation of the tile.

[0092] 28. The method according to paragraph 27, wherein the metakaolin has a shape factor of at least about 20.

[0093] 29. The method according to paragraph 27 or 28, wherein the component is chosen from chloride ion, barium, zinc, or a combination thereof.

[0094] 30. The method according to any of paragraphs 27-29, wherein the tile maintains at least 70% dimensional stability after aging at 70°C for at least 7 days. [0095] 31. The method according to paragraph 30, wherein the tile maintains at least

70% dimensional stability after aging at 90 °C for 14 days.

[0096] 32. The method according to any of paragraphs 27-31, wherein the tile maintains a dimensional stability with less than 5% expansion or shrinkage over a temperature range of 20 °C to 90 °C.

[0097] 33. The method according to any of paragraphs 27-32, wherein the tile has a

DE value less than 3.

[0098] 34. A method of making the tile according to any of paragraphs 1-21.

[0099] 35. A method of delaying or preventing degradation of the tile according to any of paragraphs 1-21.

[00100] The following examples are intended to illustrate the present disclosure without, however, being limiting in nature. It is understood that the present disclosure encompasses additional embodiments consistent with the foregoing description and following examples.

EXAMPLE

[00101] Hyper platy kaolin clay (shape fector = 100) was used to prepare metakaolin.

The kaolin was calcined at about 700°C for 90 minutes. Samples were taken after 30 minutes, 60 minutes, and 90 minutes of the calcination process. Shape factors and soluble alumina contents of the kaolin and the three samples were measured. The results are shown in FIG. 3, Characteristics of the kaolin and the metakaolin sample at 90 minutes are reported in Tables 1 and 2 below. Particle size distributions were measured by laser diffraction

(Malvern Zetasizer, Malvern Instruments) for metakaolin only, and by sedimentation (Sedigraph 5100, Micromeritics Instruments) for both kaolin and metakaolin. The shape factors of the metakaolin and the kaolin were measured by PANACEA.

Table 1

[00102] The chemical composition of the metakaolin by X-ray fluorescence is shown in Table 2 below, as well as the loss on ignition (LOI) measured at 1050°C as an indication of water content. Table 2

[00103] Other aspects and embodiments of the present disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the embodiments disclosed herein.

[00104] It is intended that the specification and examples therein be considered as exemplary only, with a true scope and spirit of the present disclosure being indicated by the following claims.