Table 1.
Clay materials with halloysite for their potential use in traditional ceramics.
| Origin of Halloysite | Starting Raw Materials | Basic Mineral Composition of Clay Raw Material | Characteristics of Halloysite (Type, Morphology, Particle Size, Amount in Raw Material) |
Synthesis/Processing | Potential Use/ Ceramic Product |
Ref. |
|---|---|---|---|---|---|---|
| Central Italy | Halloysite-rich clay | Halloysite, siliceous amorphous, feldspars, limonite, biotite, chabazite | Halloysite 10 Å, 48–70 wt%, |
Sintering/crushing and grounding of samples. Pressing at 300 N/mm2. Slow firing (2 °C/min), at 1200 °C and remaining for 10 h, slow cooling inside the industrial kiln in 10 h. Rapid firing at 1085 or 1120 °C in 41 min and 1195 °C in 60 min, rapid cooling inside the kiln. | Mullite-based ceramic | Gualtieri and Bertolani (1992) |
| Troshkovsk (Russia) | Kaolinite–halloysite clay | Halloysite, alumina kaolinite, montmorillonite | 10–40 wt% | Not provided | Refractory products | Shelest, (1992) |
| Not provided | Kaolinite-rich clay or halloysite-rich clay, magnesium hydroxide | Halloysite, accessories | Needle like halloysite, 0.5–1 μm in size | Sintering/mixtures of (i) kaolinite, synthesized magnesium hydroxide and (ii) halloysite, synthesized magnesium hydroxide sintered at 1350 °C at a rate of 100 °C/min in a reducing atmosphere | Cordierite Ceramics | Sumi et al. (1998) |
| Cameroon | Kaolinite–halloysite clay | Kaolinite, halloysite, illite, quartz, goethite, feldspar | Not provided | Not provided | Burnt bricks, ceramics, earthenware | Elueze et al. (2004) |
| Algeria | Halloysite-rich clay | Halloysite, accessories | Halloysite 10 and 7 Å | Spark plasma sintering/sintering at 1300 °C with a rate of 100 °C/min under pressure of 40 MPa in a reducing atmosphere | Nano-mullite-based ceramic | Imai et al. (2006) |
| New Zealand | Kaolinite-rich clay or halloysite-rich clay with or without alumina | Not provided | Not provided | Sintering/prepared starting mixtures pressed at 113 MPa by uniaxial pressing and at 120 MPa by cold isostating pressing. Heating at a maximum temperature of 1500 °C with a heating and cooling rate of 10 °C/min. | Mullite-based ceramic | Tezuka et al. (2006) |
| Indonesia | Halloysite-rich clay | Halloysite, feldspar, montmorillonite, mica, quartz | Not provided | Sintering/Halloysite-rich clay fired at 1100 and 1200 °C | Several traditional ceramic products and tiles | Septawendar et al. (2007) |
| Cameroon | Kaolinite–halloysite clay | Kaolinite, halloysite, quartz, feldspars, illite, carbonates, phosphates, iron hydroxides, anatase | Tubular halooysite 10 and 7 Å | Not provided | Conventional ceramics, earthen bricks | Pialy et al. (2008) |
| Patagonia | Halloysite-rich clay | Kaolinite–halloysite clay /kaolinite, halloysite, smectite, illite/smectite, quartz, feldspars | Tubular halloysite, | Not provided | Sanitary ware, porcelain, stoneware | Dondi et al. (2008) |
| Bulgaria | Halloysite-rich clay | Halloysite, sanidine | Not provided | Not provided | Tiles, bricks | Djambazov et al. (2009) |
| New Zealand | Kaolinite-rich clay or halloysite-rich clay, alumina, fluoride additives, oxide additives. | Halloysite, cristobalite, quartz | Not provided | Sintering/preparation mixtures of 50 wt% halloysite (or kaolinite), 50 wt% alumina, 1.5 or 3.0 wt% TiO2 additive or 2.5–5 wt% Fe2O3 additive. Pressing at 110–113 MPa by uniaxial pressing and at 120–200 MPa by cold isostating pressing. Heating at 1300–1600 °C with a heating rate of 1.5 °C/min. | Alumina/Clay ceramics | Tezuka et al. (2009) |
| New Zealand | Halloysite-rich clay, lithium hydroxide or lithium silicate | Halloysite, cristobalite, quartz | Not provided | Conventional method of geopolymer, solid state, thermal reactions, sintering/dehydroxylation of halloysite at 570 °C. Synthesis of lithium aluminosilicate precursors compounds: (i) after dehydroxylated halloysite with lithium hydroxide or lithium silicate at alkaline conditions or (ii) by solid state reaction of dehydroxylated halloysite with lithium hydroxide at 570 °C for 4 h or (iii) firing of dehydroxylated halloysite with lithium hydroxide, fine silica fune powder at 600 °C. Sintering of precursors up to 1275 °C. | Lithium aluminosilicate ceramics | Conor and MacKenzie (2010) |
| E. Algeria | Halloysite-rich clay, kaolinite-rich clay, chamotte | Halloysite, kaolinite, quartz, calcite, goetite, plagioclase | Not provided | Sintering/prepared mixtures of 30 wt% halloysite clay, 35 wt% kaolinite clay, 30 wt% chamotte. Pressing under 35 MPa and firing at 1350 °C for 33 h. | Refractory | Amrane et al. (2011) |
| N. Thailand | Kaolinite-rich clays, Kaolinite–halloysite clay, halloysite-rich clay, ball clay | Kaolinite, halloysite, illite, microcline, quartz, anatase, gibbsite | Hollow microtubules and plates of halloysite 7 Å, with dimensions 0.08–0.2 μm diameter and 0.50–4.5 μm length, 70 wt% | Sintering/prepared dry powders pressed under 5000 kg and firing from 880 to 1300 °C. | Ware ceramics, porous ceramics, inorganic polymer | Bordeepong et al. (2011), Bordeepong et al. (2012) |
| N. Tunisia | Kaolinite–halloysite clay, Clays with quartz-feldspar and low philosilicates | Halloysite, kaolinite | Halloysite7 Å < 2 μm, 59–61 wt% | Sintering/piles: prepared mixtures pressed at 250 bar and sintered at 800–950° (10 °C/min for 30 min). Bricks: prepared mixtures sintered at 950–1100° (15 °C/min for 30 min). |
Bricks, tiles | Moussi et al. (2011) |
| Algeria (Guelma and Constantine region) |
Halloysite-rich clay, calcite with or without methocel, amijel | Halloysite, accessories | Halloysite nano rodes, <1.21 μm in particle size, type, 70–90 wt% |
Sintering/(i) mixing of halloysite-rich clay, 10–28 wt% calcite, compacting at 75 MPa, small sized discs configuration, sintering at 1300 °C for 1 h. (ii) Mixing of halloysite-rich clay, 15 wt% calcite, 4 wt% methocel, 3 wt% amijel, extrusion or roll pressing, tubular or flat configuration, sintering at 1100–1250 °C for 1 h. | Porous mullite-based ceramics | Harabi et al. (2014) |
| Commercial | (i) Kaolinite-rich clay, alumina, starches (potato or corn), (ii) commercial aluminosilicate powder of, starches (potato or corn) |
Kaolinite, halloysite, talc, quartz, accessories | Tubular halloysite 10 and 7 Å | Consolidation, sintering/preparation of water-based ceramic–starch suspension by mixing of the aluminosilicate raw materias with starches and water (in a ratio of 60 solid/40 water). Consequent homogenizing for 4 h, deggasion in vacuum for 20 min and consolidation at 80 °C for 4 h. Heating at 1 °C/min up to 650 °C, 3 °C/min up to 1330 °C and cooling at 5 °C/min. | Ceramic with thermal insulating properties/porous cordierite-based ceramics | Gass et al. (2015) |
| W. Tunisia | Halloysite-rich clay | Halloysite, quartz, calcite, dolomite, smectite, iron and zinc oxides | Halloysite 10 Å, tubular or fibrous and seldom platelets, <2 μm particle size, 25–30 wt% | Sintering/prepared mixture of 95 wt% halloysite clay, 5 wt% dolomite. Sintering up to 1050 °C with a heating rate of 5 °C/min | Tiles and refractory | Jemai et al. (2015) |
| East Algeria | Halloysite-rich clay | Halloysite, nacrite, gibbsite, chlorite, quartz kaolinite, hematite, todorokite, dickite, magnetite | Halloysite 10 Å, tubular halloysite and tubular rods 63–66 wt% | Not provided | Several ceramic applications | Senoussi et al. (2016) |
| Algeria | Halloysite rich clay, calcite | Halloysite, illite, calcite, quartz | Hollow nano-rods halloysite 7 Å, <1 μm in particle size | Sintering/calcination of CaCO3 at 900° C for 12 h. Prepared mixtures of 80 wt% halloysite-rich clay and 20 wt% CaO (produced after calcite calcination). Milling for 17 h, using a vibratory milling system and calcination at 800 °C for 1 h. Prepared discs after pressing under 75 MPa. Sintering at 800–1100 °C for 1 h. | Anorthite-based ceramics | Zaiou et al. (2016) |
| W.-S. Sinai, Egypt | Kaolinite–halloysite clay | Kaolinite, halloysite, dickite, quartz, smectite, illite, gypsum, dolomite, hematite | Not provided | Not provided | Ceramic products, Portland cement, refractory products, glaze manufacturing | El-Kammar et al. (2017). |
| E. Algeria | Halloysite-rich clay, boehmite, zirconia | Not provided | Halloysite 10 Å with platty or irregular shape, 10–50 μm particle size | Sintering /preparation of mixtures with halloysite-rich clay, boehmite and zirconia. Pressing under 75 MPa and firing at 1250–1650 °C for 2 h. | Mullite–zirconia ceramics | Raghdi et al. (2017) |
| Algeria | Kaolinite–halloysite clay, ΒaCO3 | Kaolinite, halloysite, traces of organic matter | 14 wt% | Sintering/preparation of mixtures with clay and 0–60 wt% ΒaCO3. Pressing under 55 MPa. Sintering at 1100 and 1200 °C for 3 h, with a heating rate of 10 °C/min. | Barium aluminosilicate ceramics | Bouzidi et al. (2018) |
| Nador (NE Morocco) | Halloysite-rich clay | Halloysite, gibbsite, alunite, K-feldspar, smectite, illite | Tubular halloysite 7 Å, seldom agglomerated, 0.15 μm diameter, 600 μm length, ~70 wt% and | Sintering/Prepared specimens pressed under 100 MP and heated up to 1100 °C. | Refractory products | Haddar et al. (2018) |
| New Zealand | Halloysite-rich clay, kaoline-rich clay, feldspar flux, quartz sand | Halloysite kaolinite, minor quartz. | Tabular 7 Å, 0.3 μm in particle size, 88 wt% | Sintering /preparation of mixtures with 53 wt% halloysite-rich clay or kaoline-rich clay, 33 wt% feldspar and 14 wt% quartz sand. Sintering in an electric kiln at 1270, 1300, 1320 and 1340 °C with a fast (5°/min for 90 min) and a slow (2°/min for 180 min) heating rate. | Porcelain | Sanz et al. (2018) |
| NE Morocco | Halloysite-rich clay, diatomite, marl, silica sand, recycled alumina | Halloysite, amorphous, K-feldspar, amorpous phase, traces of tridymite, alunite, fluorite, halite, illite, smectite, diopside, gibbsite | Halloysite 7 Å, 68 wt% | Sintering/Preparation of mixtures with raw materials pressed under 30 MPa and firing up to 1300 and 1500 °C in an electric furnace with a heating and cooling rate of 3 and 5 °C/min | Refractory | Haddar et al. (2019) |
| Korea, China, Vietnam | Kaolinite–halloysite clays | Kaolinite, muscovite feldspar, halloysite, rutile, gibbsite, quartz | Needle-like halloysite, <1 μm in diameter diameter, ~5 wt% | Sintering/specimens heated at 1200 and 1250 °C | Porcelain | Kim and Hwang (2019) |
| China | Halloysite-rich clay, calcined talc, α-Al2O3 powder, MgO | Halloysite, accessories | Tubular halloysite 10 Å | Sintering/prepared mixtures of raw materials were pressed under 10 MPa and were fired at 1200–1400 °C for 2 h in a silicon–molybdenum furnace. | High temperature thermal storage applications/cordierite ceramics | Lao et al. (2019) |
| Algeria | Halloysite-rich clay, kaoline-rich clay, ZrO2 | Halloysite, minor quartz and orthoclase | Nano-rod halloysite ~20 wt% | Sintering/preparation of mixtures with 5 and 8% ZrO2 additive. Sintering up to 1250 °C. | Porcelain | Serragdj et al. (2019) |
| E. Algeria | Halloysite-rich clay and/or kaolinite–rich clay, fireclay, talc | Halloysite, minor albite, orthoclase, calcitehematite | 90 wt% | Sintering/prepared mixtures of raw materials were pressed under 250 bars and were fired up to 1330 °C for 43 h in an intermittent oven | Mullite–cordierite Refractory | Cheraitia et al. (2021) |